EP0192252A1 - Method for improving the holdout of printing inks, lacquers and coating compositions on sheetlike structures made of fibers and for improving the deinking of the fibers composition for implementing the method, and sheetlike structures produced therewith - Google Patents
Method for improving the holdout of printing inks, lacquers and coating compositions on sheetlike structures made of fibers and for improving the deinking of the fibers composition for implementing the method, and sheetlike structures produced therewith Download PDFInfo
- Publication number
- EP0192252A1 EP0192252A1 EP8686102140A EP86102140A EP0192252A1 EP 0192252 A1 EP0192252 A1 EP 0192252A1 EP 8686102140 A EP8686102140 A EP 8686102140A EP 86102140 A EP86102140 A EP 86102140A EP 0192252 A1 EP0192252 A1 EP 0192252A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- organophilic complex
- complex
- fibers
- paper
- coating
- 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.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 56
- 238000007639 printing Methods 0.000 title claims abstract description 55
- 239000000976 ink Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004922 lacquer Substances 0.000 title claims abstract description 23
- 239000008199 coating composition Substances 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims description 8
- 239000002761 deinking Substances 0.000 title 1
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004744 fabric Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000004888 barrier function Effects 0.000 claims abstract description 5
- 150000004010 onium ions Chemical class 0.000 claims abstract description 5
- 239000004990 Smectic liquid crystal Substances 0.000 claims abstract description 4
- 239000000123 paper Substances 0.000 claims description 84
- 238000000576 coating method Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 35
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000000049 pigment Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 11
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 238000001246 colloidal dispersion Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002966 varnish Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002657 fibrous material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 150000003867 organic ammonium compounds Chemical class 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910000276 sauconite Inorganic materials 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 87
- 238000007646 gravure printing Methods 0.000 description 21
- 239000000440 bentonite Substances 0.000 description 20
- 229910000278 bentonite Inorganic materials 0.000 description 20
- 229940092782 bentonite Drugs 0.000 description 20
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 9
- 235000012211 aluminium silicate Nutrition 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000002023 wood Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000018185 Betula X alpestris Nutrition 0.000 description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- -1 quaternary ammonium ions Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
Definitions
- the invention relates to a method for improving the holdout of printing inks, lacquers and coating compositions, on fabrics made of fibers, in particular on paper, and for improving the de-inking of the fibers.
- the printing ink strikes the paper and diffuses, i.e. it spreads out in the paper, which leads to a non-uniform and fuzzy and mostly matt print image.
- the main reason for the improved color level is seen in the fact that the hydratable, film-forming, colloidal clays contain a considerable proportion of bound water. This water cannot escape at the drying temperatures normally used in a paper machine and, since it is immiscible with the solvent of the gravure printing ink, causes a kind of rejection of the printing ink.
- the present invention aims at an improvement of the H oldouts organic solvent systems, such as printing inks, paints and coating compositions, in other ways.
- the problem of holdouts is particularly pronounced in gravure printing processes, since gravure inks have to have a much lower viscosity compared to other inks (for high pressure or offset printing).
- the invention is therefore primarily applicable in the field of gravure printing, which is why the explanations below relate primarily to this field.
- the fabrics made of fibers to be printed according to the invention are primarily those made of paper, although nonwovens or textiles (for example silk, cotton and linen fabrics) can also be printed using the present invention.
- the line of the coated varieties In order to have a good level of gravure ink on the paper surface, the line of the coated varieties must have a minimum thickness of about 6.5 to 7 g / m 2 and page; with double-sided coated low
- Printing paper with a total weight of 50 g / m 2 results in a base paper of approximately 36 g / m2. From today's perspective, this is a lower limit, since it is only the fibers of the coating base paper that contribute to the physical strength values of the printing paper.
- the uncoated rotogravure papers are not equivalent to the coated rotogravure papers neither in the whiteness nor in the gloss of the print products that can be produced.
- the consumption of gravure printing ink is about two and a half to three times that of the coated paper, because the porosity and thus the absorbency of the gravure printing paper is much greater.
- the shining through of the print on the back (the so-called print opacity) is a particular problem with these papers when the basis weight is further reduced.
- the invention has for its object to treat the surface of fabrics made of fibers, in particular paper, so that the coating composition or printing ink or the lacquer, in particular a low-viscosity gravure printing ink, dispersed or dissolved in an organic solvent, as little as possible into the Paper strikes.
- the invention therefore primarily relates to a method for improving the holdout of printing inks, lacquers and coating compositions, containing organic solvents, on fabrics made of fibers, in particular on paper, and for improving the de-inking of the fibers by introducing water-insoluble substances into the fiber mass or in the surface of the fiber structure.
- the organophilic complex with the organic solvent gives a more or less strong swelling reaction.
- This swelling reaction is surprisingly so strong and so fast that the capillary forces of the fibrous sheet or even a line, especially a sheet of natural paper, do not take effect. That possibly also an adsorption of the colors or their binders on the particles of the organophilic complex takes place, is of minor importance, since the holdout behavior of the treated surface for the pure solvent is practically as great as for the solution or dispersion of the printing ink of the Paint or the coating composition.
- the organophilic complex for example, a fully hydrated, cation-exchangeable, colloidal film-forming smectic layered silicate with an ion exchange capacity of 50 to 130, preferably 70 to 100 meq / 100 g is used.
- an exchange of the cations in the vicinity of 100% is preferred.
- the degree of exchange is preferably about 20 to 60%.
- Montmorillonite, hectorite, saponite, sauconite, beidellite and / or nontronite are preferably used as smectitic layered silicate to produce the organophilic complex.
- Bentonite which is available as a mineral substance with different exchangeable cations (Na, Ca, Mg) and whose main constituent is montmorillonite, is generally used as a smectitic layered silicate for practical purposes.
- the organophilic complexes are preferably reaction products of the inorganic sheet silicate with an organic ammonium compound, preferably a quaternary ammonium compound; instead of the quaternary ammonium compound, other organic compounds with a quaternary onium ion, e.g. quaternary phosphonium compounds can be used. Further usable organophilic complexes are also the partially reacted complexes of the layered inorganic silicates with quaternary onium compounds.
- organophilic complexes with partially converted inorganic phyllosilicates can often still be colloidal solutions.
- the converted part reacts with the organic solvents of the printing ink, the lacquer or the coating compound.
- the suitable organophilic complex will become an integral part of the gravure printing ink or the coating composition or the lacquer after drying. This is important for the so-called de-inking, since the organophilic complex separates from the fiber together with the color, the lacquer or the coating material.
- the wettability of the printing inks, especially gravure printing inks, is particularly favorably influenced by the oleophilic character of the organic residues of the organophilic complex which face outwards.
- organic solvents used for dissolving or dispersing printing inks, lacquers, coating compositions or adhesives are suitable as organic solvents.
- An organic solvent from the group of toluene is preferably used in gravure printing inks, Xylene or petrol, possibly in a mixture with higher-boiling components. Such components are common in printing technology and serve to influence the evaporation behavior when the printing ink dries.
- the usual coating solvents such as esters, acetone, alcohols, etc. are used for coating compositions.
- the invention can also be used to improve the holdout of pressure-sensitive adhesive coating compositions.
- These coating compositions contain sticky resins such as polyacrylates and polyisobutylene, some of which are mixed with plasticizers.
- Preferred solvents for such coating compositions are those based on hydrocarbons, such as gasoline.
- the reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion.
- the dispersions of the reactive organophilic complexes according to the invention in organic solvents are strongly thixotropic, which is important for application, e.g. is cheap in a gravure printing unit with an anilox roller.
- the organophilic complex can either be introduced into the fiber mass or into the surface of the fiber structure.
- the process according to the invention can be used, in particular for the production of satined papers, in such a way that the reactive organophilic complex is introduced into the suspended fiber mass in aqueous dispersion before the sheet is produced, with or without the fillers.
- a variant of the process according to the invention is characterized in that the organophilic complex is generated in situ in the fiber mass by reacting the inorganic layered silicate with the organic compound before the fabric is produced.
- the filler suspension can also be provided instead of the fiber mass (pulp), or fibers and filler are already present as a total.
- the advantage of generating in situ, e.g. B. In the paper mill, is particularly the fact that the paper machine also acts as a dryer for the organophilic complex, so energy is saved.
- the usual fillers can be partially replaced by the organophilic complex.
- the usual retention aids and other additives, such as paints, can also be used.
- a process variant which is particularly suitable for the production of coated, highly satinized papers is characterized in that the reactive organophilic complex, optionally with a binder, a surfactant and / or an inert coating pigment, in aqueous suspension in or on the surface of the fabric brings.
- the reactive organophilic complex optionally with a binder, a surfactant and / or an inert coating pigment, in aqueous suspension in or on the surface of the fabric brings.
- the usual white pigments which improve the opacity can be used as inert coating pigments.
- a line or a surface preparation is not expected to contribute to the opacity of a sheet of paper, but if only the print opacity is in the foreground and thus the ink consumption and gloss of the print, then a variant of this process can be used to situate the organophilic complex in situ generate the surface of the fabric by making the inorganic layered silicate in the form of an aqueous colloidal dispersion which optionally contains binders, surfactants and / or coating pigments, introduces them into the surface and then reacts with the organic compound. This is possible, for example, in all those coating machines that have two coating devices on each side, which is common today. Machines with two size presses are also particularly suitable.
- the inorganic layered silicate is introduced into the fiber mass in the form of an aqueous colloidal dispersion, which optionally contains binders, surfactants and / or pigments, and then only in the surface reacted with the organic compound to obtain the organophilic complex.
- aqueous colloidal dispersion which optionally contains binders, surfactants and / or pigments, and then only in the surface reacted with the organic compound to obtain the organophilic complex.
- aqueous colloidal dispersion which optionally contains binders, surfactants and / or pigments
- the organophilic complex in situ in the surface can also be produced by reacting the inorganic sheet silicate with the organic compound in the presence of binders, surfactants and / or coating pigments and bringing the reaction product as a coating composition into or onto the surface of the fiber material.
- a further method variant is characterized in DAB, if appropriate, with a binder and / or an inert coating pigment, for example an opacity enhancing pigment rganischen in a D solvent as a pre-preparation by means of a solvent coating machine or a printing press in D of the reactive organophilic complex brings the surface of the fabric, after which the printing ink (s), the lacquer or the coating composition are applied after an intermediate drying.
- a binder and / or an inert coating pigment for example an opacity enhancing pigment rganischen in a D solvent as a pre-preparation by means of a solvent coating machine or a printing press in D of the reactive organophilic complex brings the surface of the fabric, after which the printing ink (s), the lacquer or the coating composition are applied after an intermediate drying.
- the reactive organophilic complex according to the invention can in principle be applied from the organic solution or dispersion to a so-called solvent coater at high speeds and in the widths of modern paper machines (about 7 to 8 meters).
- the method according to the invention can advantageously also be carried out in the printing house.
- a printing unit e.g. a simple screen gravure printing unit, can therefore be used in the process variant described above to produce an invisible form of the organophilic complex, which is dried as usual before the actual gravure begins.
- the costs for gravure printing are limited if, as usual, 92 to 96% of the solvent is recovered. Since, according to the invention, the organic dispersant for the organophilic complex is the same as for the solvent for the subsequent printing inks, the joint recovery makes no problems.
- the pre-stretching unit i.e. the first printing unit used here, can retain its function as such, because the form with the reactive organophilic complex can be printed over the entire surface and without registering.
- the same or similar organic solvents can be used as dispersants for the reactive organophilic complex and the printing ink (s) or the lacquer or the coating composition.
- the invention further relates to a mass for carrying out the method variants described above, which is applied to the surface of the fiber structure.
- This mass is characterized in that it is in the form of a dispersion of a reactive organophilic complex in an aqueous or organic medium.
- the reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion, in particular in an organic solvent such as toluene or xylene. In an aqueous medium, the reactive organophilic complex is preferably in a 2 to 20% dispersion.
- the invention further relates to fabrics made of fibers, in particular paper, which are characterized in that they contain in the surface and / or in the fiber mass a reactive organophilic complex which can be obtained by the process according to the invention.
- the organophilic complex is in the surface of the flat structures according to the invention, it is preferably present in a finely divided amount in an amount of 0.1 to 3, preferably 0.2 to 0.8 g / m 2 and side. If it is in the fiber mass, it is preferably present in an amount of about 1.5 to 12% by weight.
- the invention can also be used, for example, for the production of zinc oxide papers. With these papers, a toluene varnish, which is filled with photoconductive zinc oxide and non-conductive binders, is spread onto the surface of a conductive base paper. The conductivity of the base paper is obtained by adding a conductive polymer (coneuctie polymer) to the size press preparation from starch ethers or starches or from polyvinyl alcohol.
- the toluene coating behaves analogously to a printing ink. Because of the barrier effect of the reactive organophilic complex in the fiber mass or in the surface of the fiber structure, the toluene lacquer filled with zinc oxide is prevented from penetrating into the fiber mass. Until now, it was only possible to achieve a holdout for toluene that is hole-free, only with great effort, partly double size press coating, partly pre-coating with the conductive polymer and the colloidal binder. By adding the reactive organophilic layered silicate in the size press preparation and / or in the primer, it is possible to achieve a spot-free toluene density for the subsequent coating.
- the conductive base paper has a flaw, i.e. If toluene is absorbed, a defect in the image reproduction occurs in the surface of the zinc oxide paper.
- the present invention can also be used to prevent the penetration of lacquers such as nitro lacquer, zapon lacquer, plastic lacquer, spirit lacquer etc. into fiber structures.
- lacquers such as nitro lacquer, zapon lacquer, plastic lacquer, spirit lacquer etc.
- label papers are coated with a so-called protective label varnish after printing so that the labels on the bottles are scrub-resistant and not unsightly due to the absorption of moisture.
- a label paper In order for a label paper to be paintable, it usually has to be coated on one side. So-called natural label papers cannot be varnished because the varnish does not remain on the surface but penetrates into the fiber material.
- the reactive barrier layer made of the organophilic complex according to the invention prevents the label lacquer from penetrating into the fiber material.
- the precoating of a paper surface or another sheet-like fiber structure with the spontaneously reacting organophilic complex materials can make it printable, in particular paintable and coatable from organic solution, for which this was previously not possible.
- this includes the simple wood-containing and wood-free natural papers, including those that are not or hardly filled and that have not been satined.
- the invention is particularly important for cardboard, where, whether coated or not, every satin finish and smoothing in a smoothing unit leads to an undesirable loss of volume and thus a loss of rigidity.
- the invention is also suitable for the production of adhesive labels.
- PSA coatings are made from an organic solution of the adhesives.
- the impact behavior of the adhesive coating masses in the paper plays an important role. This is because they should hit the paper as little as possible. So far, in such cases, expensive glue press preparations such as Casein, or polyvinyl alcohol, tries to improve holdout.
- coating with the reactive organophilic complex not only leads to a reduction in the application of pressure-sensitive adhesive, but also enables the use of previously little or unsuitable fabrics, such as nonwovens or textiles. According to the invention, these materials can also be made printable.
- quaternary ammonium compounds are contained in the organophilic complexes, they influence the electrical properties of the fabrics according to the invention, e.g. the surface or volume resistance. These values play a role in printability.
- the modification according to the invention reduces the surface and volume resistances and thereby eliminates interference caused by electrostatic charges.
- a semi-bleached needle sulfate pulp is pulped in a pulper at a consistency of 5% and at a pH of 7 to 7.8 and then brought to a degree of grinding of 26 ° SR (Schopper-Riegler) in a refiner.
- This pulp is mixed in a ratio 25: 75 in a pulping center with a splinter-free wood pulp with a freeness of 78 ° SR.
- a separately produced kaolin slurry of 40% at a pH of 7 to 7.8 is mixed into the fiber mixture in a ratio of 70 parts of fibers to 30 parts of kaolin (all air dry).
- a slurry of 3.5% solids of a pre-swollen sodium bentonite with an ion exchange capacity of 90 mVal / 100 g is mixed into this total substance until, based on fibers and filler, 4% by weight of the bentonite has been introduced. The whole thing will take about 10 min. well mixed.
- a 4% strength aqueous solution of dimethyl-benzyl-alkyl- (C12-C22) ammonium chloride is then mixed in in an amount equimolar to the complete ion exchange.
- a commercially available organophilic bentonite coated with quaternary ammonium ions (Tixogel VZ ( R ) from F a. Süd-Chemie AG) is mixed in a high-speed mixer with high shear forces as a dispersion with a solids content of 20% by weight in the presence of a nonylphenol ethoxylate type 15 min. sheared.
- This dispersion is admixed to the fibers produced as in Example 1 and then the kaolin slurry is added in an amount such that, based on the total, 6% by weight of the reactive organophilic clay are in the total.
- a coated rotogravure paper is produced which, after satinizing, has a Bekk smoothness of 1500 to 1600 seconds and a toluene holdout of 65 seconds.
- a comparable coated rotogravure paper has a toluene holdout of 40 seconds.
- Example 1 a wood-containing, kaolin-filled, satined, gravure printing paper without bentonite or quaternary ammonium compound is produced in bulk.
- a 5% slurry of a commercially available bentonite, the exchangeable cations of which are 40% Na and 60% Ca is applied in the first and third coating unit.
- the order is about 1.5 g / m 2 and side.
- a 4% solution of the quaternary ammonium compound from Example 1 is applied in the coating units 2 and 4 in the relation given there.
- This solution reacts by ion exchange in the surface with the bentonite to form the reactive organophilic complex. Since both the hydrated bentonite is film-forming and the reactive organophilic complex forms a film, even if it adheres poorly, the use of colloidal and / or disperse binders is not necessary.
- a wood-containing, highly filled paper which, according to EU-PS 0 017 793, was produced with a film-forming colloidal bentonite, the sodium-magnesium atomic ratio of which was 60:40, and, based on the paper, contains 2.5% by weight of the film-forming bentonite , is treated at the end of the dryer section of a paper machine using a conventional size press with the dilute 3% aqueous solution of the quaternary ammonium compound from Example 1. Since the fibers and fillers of this paper in any case carry a film of bentonite, albeit a thin one, this enters into ion exchange with the quaternary ammonium compound and results in the reactive organophilic complex according to the invention being present especially in the surface after renewed drying. The resulting sodium and magnesium chloride does not interfere.
- So-called solvent coaters are found in many factories that deal with the finishing of paper. These are coating machines that use various organic solvents as solvents or dispersants instead of water and usually recover them from the exhaust air.
- a wood-containing gravure printing paper with a basis weight of 40 g / m 2 has a filler content of 18% by weight. Its opacity and print opacity are unsatisfactory.
- a commercial bentonite (Tixogel VP ( R ) from Süd-Chemie AG) coated with quaternary ammonium ions is in the form of a dispersion with a solids content of 3.5% by weight in a solvent mixture of 99 parts by weight of toluene and 1 Part by weight of ethanol 10 min. dispersed in a high shear high-speed mixer. This dispersion is applied to both sides of the paper by means of a reverse roll coater, so that 0.5 g / m 2 of application (air-dry calculated) result on each side.
- the paper pretreated in this way has a toluene holdout of 60 seconds.
- Printing with a black gravure ink shows almost no show through on the back and an increased print gloss.
- a colorless pre-printing ink is pre-printed with a 3% by weight colloidal dispersion in toluene, produced analogously to Example 6, using a screen roller with a 70 screen and an engraving depth of 65 ⁇ m over the entire surface and regardless of registration.
- this form applies an application of 0.3 g / m 2 to the paper to be printed. While sec at a lightly filled wood-containing N aturpapier the absorption time for dyed toluene solution is about 6., It yields at the "preprinted" paper at a coating of 0.3 g / m 2 has a value of 70 sec.
- a further increase of the order of reactive organophilic complex from the toluene solution, for example 0.6 g / m 2 does not give a higher value nor a sharper level of the colored toluene drop, since with a coating of only 0.3 g / m 2 the printing paper was already fully sealed against toluene is.
- a wood-free label paper is made from 60 parts by weight of highly bleached needle sulfate pulp with a freeness of 30 ° SR and 40 parts by weight of bleached birch sulfate pulp with a freeness of 45 ° SR.
- 10 parts by weight of kaolin, 5 parts by weight of TiO 2 and 5 parts by weight of aluminum hydroxide are added.
- the paper is taken out with 2.5 parts by weight of resin glue with the addition of a melamine-formaldehyde resin to improve the wet strength at a pH of 4.6 as smooth paper on one side and heated to 136 ° C. at the end of the drying section in order to crosslink the melamine. Ensure formaldehyde resin.
- This label paper should be coated with a scouring varnish after printing.
- the label printing is carried out in gravure printing, a dispersion of the reactive organophilic complex according to Example 6 in toluene being pre-printed in the first gravure printing unit.
- the protective label varnish is applied as a nitro varnish. It does not penetrate the natural printing paper treated according to the invention, although it has not been deleted.
- a non-coated chromo replacement cardboard with a basis weight of 300 g / m 2 was printed with a dispersion according to Example 6 by gravure printing, the dried application being only 0.2 g / m 2 .
- a nitro lacquer, which would otherwise be knocked off, remains shiny on the pre-treated cardboard.
- a nonwoven fabric made of 80% polyester fiber and 20% bleached needle sulfate pulp as a dispersing fiber is impregnated with a plastic dispersion of polyacrylic acid ester after it has been produced in an aqueous suspension on a steep sieve machine.
- This nonwoven is to be prepared for textile screen printing. Similar to gravure inks, screen printing inks are low-viscosity and contain toluene as a solvent.
- a 3.5% by weight suspension of the organophilic complex according to Example 6 which is blended with a further 5% by weight of a fine calcium carbonate and contains a 2% by weight polyvinyl acetate additive, spread out. It is advisable to choose the knife coating process so that the large pores of the nonwoven material close.
- a toluene-containing screen printing ink has a toluene holdout of 10 to 15 seconds for an untreated nonwoven, the holdout is improved by the line to about 40 seconds.
- the print gloss that can be achieved is increased and the consumption of screen printing ink is reduced.
- a swollen Na-Mg-bentonite slurry with 5% by weight solids is mixed into a suspension of bleached needle sulfate pulp of 4.5% by weight consistency and a freeness of 23 ° SR until a 10th, based on the pulp wt .-% share is reached.
- a 3% by weight solution of the quaternary ammonium compound according to Example 1 is prepared in a separate dissolving vessel.
- the wood-free paper thus produced using standard methods has a Bekk smoothness of 1100 sec. At 80 g / m 2 , a density of 1.35 g / cm 2 and a toluene holdout by the drop method (toluene colored with Ceres red) of 15 sec compared to 3 seconds for untreated paper.
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Abstract
Das erfindungsgemäße Verfahren zur Verbesserung des Holdouts von Druckfarben, Lacken und Beschichtungsmassen, enthaltend organische Lösungsmittel auf Flächengebilden aus Fasern, insbesondere auf Papier sowie zur Verbesserung des De-Inkings der Fasern, besteht darin, daß man einen organophilen Komplex aus (a) einem wasserunlöslichen hydratisierten kationenaustauschfähigen filmbildenden smektitischen Schichtsilikat mit einer Ionenaustauschfähigkeit von wenigstens 50 mVal/100 g und (b) einem daran gebundenen, aus einer Oniumverbindung abgeleiteten organischen Rest in die Fasermasse oder in die Oberfläche des Fasergebildes einbringt, wobei der organophile Komplex durch Reaktion mit dem organischen Lösungsmittel eine Sperrschicht bildet.The process according to the invention for improving the holdout of printing inks, lacquers and coating compositions containing organic solvents on fabrics made of fibers, in particular on paper and for improving the de-inking of the fibers, consists in that an organophilic complex of (a) a water-insoluble hydrated cation-exchangeable film-forming smectic layered silicate with an ion exchange capacity of at least 50 meq / 100 g and (b) an attached organic residue derived from an onium compound into the fiber mass or into the surface of the fiber structure, the organophilic complex by reaction with the organic solvent Barrier forms.
Description
Die Erfindung betrifft ein Verfahren zur Verbesserung des Holdouts von Druckfarben, Lacken und Beschichtungsmassen, auf Flächengebilden aus Fasern, insbesondere auf Papier sowie zur Verbesserung des De-Inkings der Fasern.The invention relates to a method for improving the holdout of printing inks, lacquers and coating compositions, on fabrics made of fibers, in particular on paper, and for improving the de-inking of the fibers.
Es ist beispielsweise aus der EU-PS 0 017 793 bekannt, die Bedruckbarkeit von Papier dadurch zu verbessern, daß hydratisierbare filmbildende, kolloidale Tone, z.B. Bentonite, Attapulgit oder Sepiolith in die Papiermasse eingearbeitet werden. An diese kolloidalen Tone können auch Makromoleküle von Polyglykol mit einem Molekulargewicht von 5000 bis 100 000 angehängt werden. Die durch diese Maßnahmen bedingte Verbesserung der Satinierbarkeit und Bedruckbarkeit besteht in einem verbesserten "Farbstand", d.h. die Druckfarbe schlägt kurzzeitig (zwischen ihrem Auftrag auf das Papier und ihrer Trocknung) nicht so schnell weg, sondern es liegen die gleichen Farbkonturen, wie sie auf das Papier aufgebracht werden, auch auf dem fertig bedruckten und getrockneten Papier vor. Bei einem schlechten "Farbstand" schlägt die Druckfarbe dagegen in das Papier ein und diffundiert, d.h. sie breitet sich im Papier aus, was zu einem uneinheitlichen und unscharfen und meist matten Druckbild führt. Der wesentliche Grund für den verbesserten Farbstand wird darin gesehen, daß die hydratisierbaren, filmbildenden, kolloidalen Tone einen erheblichen Anteil an gebundenem Wasser enthalten. Dieses Wasser kann bei den Trockentemperaturen, wie sie in einer Papiermaschine üblicherweise angewendet werden, nicht entweichen und bewirkt, da es mit dem Lösungsmittel der Tiefdruckfarbe nicht mischbar ist, gewissermaßen eine Abstoßung der Druckfarbe.It is known, for example from EU-PS 0 017 793, to improve the printability of paper by the fact that hydratable film-forming, colloidal clays, e.g. Bentonite, attapulgite or sepiolite can be incorporated into the paper pulp. Macromolecules of polyglycol with a molecular weight of 5,000 to 100,000 can also be attached to these colloidal clays. The improvement in the satinability and printability caused by these measures consists in an improved "color balance", i.e. the printing ink does not blow away as quickly for a short time (between its application to the paper and its drying), but the same color contours as are applied to the paper are also present on the finished printed and dried paper. If the "color level" is poor, on the other hand, the printing ink strikes the paper and diffuses, i.e. it spreads out in the paper, which leads to a non-uniform and fuzzy and mostly matt print image. The main reason for the improved color level is seen in the fact that the hydratable, film-forming, colloidal clays contain a considerable proportion of bound water. This water cannot escape at the drying temperatures normally used in a paper machine and, since it is immiscible with the solvent of the gravure printing ink, causes a kind of rejection of the printing ink.
Bei der Verwendung eines Gemisches von kolloidalen Tonen und Polyglykolen wird davon ausgegangen, daß die Polyglykole sich wie das Wasser zwischen die kolloidalen Tone einlagern, also keine Reaktionsprodukte bilden, und wegen ihrer wachsartigen Beschaffenheit nach der Trocknung die Satinierbarkeit verbessern. Eine Reaktion mit dem organischen Lösungsmittel, in dem die Druckfarbe gelöst oder dispergiert ist, tritt nicht ein.When using a mixture of colloidal clays and polyglycols, it is assumed that the polyglycols, like the water, are deposited between the colloidal clays, that is, they do not form any reaction products, and because of their waxy nature, they improve the satinability after drying. There is no reaction with the organic solvent in which the ink is dissolved or dispersed.
Die vorliegende Erfindung bezweckt eine Verbesserung des Holdouts organischer Lösungsmittelsysteme, wie Druckfarben, Lacke und Beschichtungsmassen, auf andere Weise. Das Problem des Holdouts ist bei Tiefdruckverfahren besonders ausgeprägt, da Tiefdruckfarben, verglichen mit anderen Druckfarben (für den Hochdruck bzw. für den Offsetdruck) eine wesentlich geringere Viskosität haben müssen. Die Erfindung ist also in erster Linie auf dem Gebiet des Tiefdruckes anwendbar, weshalb sich die nachstehenden Ausführungen vorwiegend auf dieses Gebiet beziehen. Ferner handelt es sich bei den erfindungsgemäß zu bedruckenden Flächengebilden aus Fasern in erster Linie um solche aus Papier, obwohl auch Vliesstoffe oder Textilien (z.B. Seiden-, Baumwolle- und Leinenstoffe) unter Benutzung der vorliegenden Erfindung bedruckt werden können.The present invention aims at an improvement of the H oldouts organic solvent systems, such as printing inks, paints and coating compositions, in other ways. The problem of holdouts is particularly pronounced in gravure printing processes, since gravure inks have to have a much lower viscosity compared to other inks (for high pressure or offset printing). The invention is therefore primarily applicable in the field of gravure printing, which is why the explanations below relate primarily to this field. Furthermore, the fabrics made of fibers to be printed according to the invention are primarily those made of paper, although nonwovens or textiles (for example silk, cotton and linen fabrics) can also be printed using the present invention.
Der Tiefdruck gehört zu den am meisten verbreiteten Druckarten bei Massendrucksachen aller Art. Zum Einsatz kommen im wesentlichen zwei Papierarten, nämlich
- 1. das hochgefüllte, satinierte, meist holzhaltige Tiefdruckpapier in Flächengewichten zwischen 40 bis etwa 80 g/m2 und
- 2. das gestrichene, holzhaltige oder holzfreie hochsatinierte Tiefdruckpapier in Flächengewichten zwischen 45 und etwa 135 g/m 2.
- 1. The highly filled, satin, mostly wood-containing T iefdruckpapier in basis weights between 40 to about 80 g / m 2 and
- 2. The coated, wood-containing or wood-free, highly satinized gravure printing paper in basis weights between 45 and about 135 g / m 2 .
Aus wirtschaftlichen sowie aus postalischen Gründen besteht seit Jahren die Tendenz, die Flächengewichte derartiger Papiere zu verringern. Diesem Wunsch sind insbesondere beim gestrichenen Tiefdruckpapier, aber auch beim Naturtiefdruckpapier Grenzen gesetzt.For economic and postal reasons, there has been a tendency for years to reduce the basis weights of such papers. There are limits to this wish, especially with coated gravure paper, but also with natural gravure paper.
Um einen guten Stand der Tiefdruckfarbe auf der Papieroberfläche zu haben, muß bei den gestrichenen Sorten der Strich eine Mindeststärke von etwa 6,5 bis 7g/m2 und Seite haben; bei doppelseitig gestrichenem Tief-In order to have a good level of gravure ink on the paper surface, the line of the coated varieties must have a minimum thickness of about 6.5 to 7 g / m 2 and page; with double-sided coated low
druckpapier resultiert hieraus bei 50 g/m2 Gesamtgewicht ein Streichrohpapier von etwa 36 g/m2. Dies istaus heutiqer Sicht eine Untergrenze, da es nur die Fasern des Streichrohpapiers sind, die zu den physikalischen Festigkeitswerten des Druckpapiers beitragen. Andererseits sind die ungestrichenen Naturtiefdruckpapiere weder in der Weiße noch im Glanz der erzeugbaren Drucksachen den gestrichenen Tiefdruckpapieren gleichwertig. Besonders der Verbrauch an Tiefdruckfarbe liegt größenordnungsmäßig bei etwa dem zweieinhalb- bis dreifachen des der gestrichenen Papiere, weil die Porosität und damit die Saugfähigkeit der Naturtiefdruckpapiere wesentlich größer ist. Demzufolge ist auch das Durchscheinen des Druckes auf der Rückseite (die sogenannte Druckopazität) bei diesen Papieren bei weiterer Absenkung des Flächengewichts ein besonderes Problem.Printing paper with a total weight of 50 g / m 2 results in a base paper of approximately 36 g / m2. From today's perspective, this is a lower limit, since it is only the fibers of the coating base paper that contribute to the physical strength values of the printing paper. On the other hand, the uncoated rotogravure papers are not equivalent to the coated rotogravure papers neither in the whiteness nor in the gloss of the print products that can be produced. In particular, the consumption of gravure printing ink is about two and a half to three times that of the coated paper, because the porosity and thus the absorbency of the gravure printing paper is much greater. As a result, the shining through of the print on the back (the so-called print opacity) is a particular problem with these papers when the basis weight is further reduced.
Durch die in der vorstehend genannten EU-PS 0 017 793 beschriebene Anwendung von hydratisierbaren filmbildenden kolloidalen Tonen gelang es zwar in einem gewissen Grad, die Oberfläche der ungestrichenen Naturtiefdruckpapiere etwas zu schließen, und die Bedruckbarkeit zu verbessern. Die so behandelten Tiefdruckpapiere sind jedoch noch nicht mit den gestrichenen Tiefdruckpapieren auch nur annähernd in der Farbaufnahme vergleichbar. Eine Verwendung der in der EU-PS 0 017 793 beschriebenen hydratisierten filmbildenden Tone in Streichrezepturen oder als Oberflächenbeschichtung ist aber aus rheologischen Gründen unmöglich.The use of hydratable film-forming colloidal clays described in the above-mentioned EU-PS 0 017 793 succeeded to a certain extent in closing the surface of the uncoated gravure printing paper somewhat and in improving the printability. The rotogravure papers treated in this way, however, are not yet approximately comparable in color with the coated rotogravure papers. However, the use of the hydrated film-forming clays described in EU-PS 0 017 793 in coating formulations or as a surface coating is impossible for rheological reasons.
Der Erfindung liegt die Aufgabe zugrunde, die Oberfläche von Flächengebilden aus Fasern, insbesondere von Papier, so zu behandeln, daß die in einem organischen Lösungsmittel dispergierte oder gelöste Beschichtungsmasse oder Druckfarbe bzw. der Lack, insbesondere eine niedrigviskose Tiefdruckfarbe, so wenig wie möglich in das Papier hineinschlägt.The invention has for its object to treat the surface of fabrics made of fibers, in particular paper, so that the coating composition or printing ink or the lacquer, in particular a low-viscosity gravure printing ink, dispersed or dissolved in an organic solvent, as little as possible into the Paper strikes.
Je weniger diese eindringen, umso geringer ist der ver-brauch und umso schöner ist der Glanz der behandelten Fläche (Druckglanz). The less they penetrate, the lower the consumption and the more beautiful the gloss of the treated surface (pressure gloss).
Gegenstand der Erfindung ist somit in erster Linie ein Verfahren zur Verbesserung des Holdouts von Druckfarben, Lacken und Beschichtungsmassen, enthaltend organische Lösungsmittel, auf Flächengebilden aus Fasern, insbesondere auf Papier, sowie zur Verbesserung des De-Inkinns der Fasern, durch Einbringen von wasserunlöslichen Substanzen in die Fasermasse oder in die Oberfläche des Fasergebildes.The invention therefore primarily relates to a method for improving the holdout of printing inks, lacquers and coating compositions, containing organic solvents, on fabrics made of fibers, in particular on paper, and for improving the de-inking of the fibers by introducing water-insoluble substances into the fiber mass or in the surface of the fiber structure.
Das Verfahren ist dadurch gekennzeichnet, daß man einen organophilen Komplex aus
- (a) einem wasserunlöslichen hydratisierten kationenaustauschfähigen filmbildenden smektitischen Schichtsilikat mit einer lonenaustauschfähigkeit von wenigstens 50 mVal/100 g und
- (b) einem daran gebundenen, aus einer Oniumverbindung abgeleiteten organischen Rest in die Fasermasse oder in die Oberfläche des Fasergebildes einbringt, wobei der organophile Komplex durch Reaktion mit dem organischen Lösungsmittel eine Sperrschicht bildet.
- Der organische Rest, der in der Regel ein Molekulargewicht von weniger als 1000 hat, ist in einer Ionenbindung an das anorganische Schichtsilikat gebunden. Die Eigenschaft des anorganischen Schichtsilikats, in wäßriger Phase ein Gel zu bilden, ist offenbar wichtig, damit auch der organophile Komplex mit dem organischen Lösungsmittel reagiert und unter Gelbildung aufquillt. Da der organische Rest über eine Ionenbindung an das anorganische Schichtsilikat gebunden werden soll, hat das anorganische Schichtsilikat zweckmäßig ein hohes Ionenaustauschvermögen.
- (a) a water-insoluble, hydrated, cation-exchangeable film-forming smectic layered silicate with an ion exchange capacity of at least 50 meq / 100 g and
- (b) introduces an attached organic residue derived from an onium compound into the fiber mass or into the surface of the fiber structure, the organophilic complex forming a barrier layer by reaction with the organic solvent.
- The organic residue, which usually has a molecular weight of less than 1000, is bound to the inorganic layered silicate in an ion bond. The property of the inorganic layered silicate to form a gel in the aqueous phase is obviously important so that the organophilic complex also reacts with the organic solvent and swells to form a gel. Since the organic residue is to be bound to the inorganic layered silicate via an ion bond, the inorganic layered silicate expediently has a high ion exchange capacity.
Man nimmt an, daß der organophile Komplex mit dem organischen Lösungsmittel eine mehr oder weniger starke Quellreaktion ergibt. Diese Quellreaktion ist überraschenderweise so stark und auch so schnell, daß die kapillaren Kräfte des faserigen Flächengebildes oder auch eines Striches, insbesondere eines Naturpapierblattes, nicht wirksam werden. Daß möglicherweise auch eine Adsorption der Farben oder ihrer Binder an den Teilchen des organophilen Komplexes stattfindet, dürfte von untergeordneter Bedeutung sein, da das Holdout-Verhalten der behandelten Oberfläche für das reine Lösungsmittel praktisch genau so groß ist wie für die Lösung oder Dispersion der Druckfarbe des Lackes oder der Beschichtungsmasse.It is believed that the organophilic complex with the organic solvent gives a more or less strong swelling reaction. This swelling reaction is surprisingly so strong and so fast that the capillary forces of the fibrous sheet or even a line, especially a sheet of natural paper, do not take effect. That possibly also an adsorption of the colors or their binders on the particles of the organophilic complex takes place, is of minor importance, since the holdout behavior of the treated surface for the pure solvent is practically as great as for the solution or dispersion of the printing ink of the Paint or the coating composition.
Zur Herstellung des organophilen Komplexes verwendet man beispielsweise ein vollhydratisiertes, kationenaustauschfähiges kolloidales filmbildendes smektitisches Schichtsilikat mit einer Ionenaustauschfähigkeit von 50 bis 130, vorzugsweise von 70 bis 100 mVal/100g. Zur Erzeugung des organophilen Komplexes werden vorzugsweise mindestens 50 % der austauschfähigen Kationen durch organische Reste ausgetauscht. Soll der organophile Komplex in organischer Phase weiterverarbeitet werden, wird ein Austausch der Kationen in der Nähe von 100 % bevorzugt. Soll der organophile Komplex in einer wäßrigen Phase dispergiert werden, so beträgt der Austauschgrad vorzugsweise etwa 20 bis 60 %.To produce the organophilic complex, for example, a fully hydrated, cation-exchangeable, colloidal film-forming smectic layered silicate with an ion exchange capacity of 50 to 130, preferably 70 to 100 meq / 100 g is used. To generate the organophilic complex, at least 50% of the exchangeable cations are preferably replaced by organic residues. If the organophilic complex is to be processed further in the organic phase, an exchange of the cations in the vicinity of 100% is preferred. If the organophilic complex is to be dispersed in an aqueous phase, the degree of exchange is preferably about 20 to 60%.
Als smektitisches Schichtsilkat verwendet man zur Herstellung des organophilen Komplexes vorzugsweise Montmorillonit, Hectorit, Saponit, Sauconit, Beidellit und/oder Nontronit.Montmorillonite, hectorite, saponite, sauconite, beidellite and / or nontronite are preferably used as smectitic layered silicate to produce the organophilic complex.
Für praktische Zwecke verwendet man als smektitisches Schichtsilikat im allgemeinen Bentonit, der als mineralische Substanz mit unterschiedlichen austauschfähigen Kationen (Na, Ca, Mg) zur Verfügung steht und dessen Hauptbestandteil Montmorillonit ist.Bentonite, which is available as a mineral substance with different exchangeable cations (Na, Ca, Mg) and whose main constituent is montmorillonite, is generally used as a smectitic layered silicate for practical purposes.
Es ist aus der Literaturstelle "Das Papier", 35. Jahrgang, Heft 9, Seiten 407 und 416 (1981) bekannt, Kaolin mit kationischen Polymeren zu behandeln, um den Füllstoffgehalt bei gleicher Festigkeit im Papier zu erhöhen. Der Kaolin hat jedoch für die Zwecke der vorliegenden Erfindung ein zu geringes Ionenaustauschvermögen. Außerdem ist Kaolin in wäßriger Phase nicht filmbildend und nicht zu einem Gel hydratisierbar.It is known from the reference "Das Papier", 35th year, volume 9, pages 407 and 416 (1981) to treat kaolin with cationic polymers in order to increase the filler content in the paper with the same strength. However, the kaolin has too little ion exchange capacity for the purposes of the present invention. In addition, kaolin is not film-forming in the aqueous phase and cannot be hydrated to form a gel.
Bei den organophilen Komplexen handelt es sich vorzugsweise um Reaktionsprodukte des anorganischen Schichtsilikats mit einer organischen Ammoniumverbindung, vorzugsweise einer quaternären Ammoniumverbindung; statt der quaternären Ammoniumverbindung können für die Umsetzung mit dem anorganischen Schichtsilikat auch andere organische Verbindungen mit einem quaternären Oniumion, z.B. quaternäre Phosphoniumverbindungen, verwendet werden. Weitere brauchbare organophile Komplexe sind auch die teilumgesetzten Komplexe der anorganischen Schichtsilikate mit quaternären Oniumverbindungen.The organophilic complexes are preferably reaction products of the inorganic sheet silicate with an organic ammonium compound, preferably a quaternary ammonium compound; instead of the quaternary ammonium compound, other organic compounds with a quaternary onium ion, e.g. quaternary phosphonium compounds can be used. Further usable organophilic complexes are also the partially reacted complexes of the layered inorganic silicates with quaternary onium compounds.
Während bei voller Ausnützung der reaktionsfähigen Valenzen der organophile Komplex zur Flockung neigt, können organophile Komplexe mit teilumgesetzten anorganischen Schichtsili- katen, besonders in wäßrigen Dispersionen oft noch kolloidale Lösungen sein. Natürlich reagiert nur der umgesetzte Anteil mit den organischen Lösungsmitteln der Druckfarbe, des Lacks oder der Beschichtungsmasse.While the organophilic complex tends to flocculate when the reactive valences are fully utilized , organophilic complexes with partially converted inorganic phyllosilicates, especially in aqueous dispersions, can often still be colloidal solutions. Of course, only the converted part reacts with the organic solvents of the printing ink, the lacquer or the coating compound.
Da aber die Feinverteilung in einem Papierblatt oder in seiner Oberfläche für das erfindungsgemäße Verfahren von Bedeutung ist, um auch im Mikrobereich die kapillaren Saugkräfte aufzuheben, liegt eine bevorzugte Anwendung bei allen wäßrigen Systemen in der Teilumsetzung, was in der Konsequenz zu einem höheren Eintrag oder Auftrag führt.However, since the fine distribution in a sheet of paper or in its surface is important for the process according to the invention in order to eliminate the capillary suction forces in the micro range as well, a preferred application for all aqueous systems is partial conversion, which results in a higher entry or application leads.
Man kann wahrscheinlich davon ausgehen, daß der geeignete organophile Komplex nach dem Trocknen integraler Bestandteil der Tiefdruckfarbe bzw. der Beschichtungsmasse oder des Lacks wird. Dies ist für das sogenannte De-Inken von Bedeutung, da sich hierbei der organophile Komplex zusammen mit der Farbe, dem Lack oder der Beschichtungsmasse von der Faser trennt.It can probably be assumed that the suitable organophilic complex will become an integral part of the gravure printing ink or the coating composition or the lacquer after drying. This is important for the so-called de-inking, since the organophilic complex separates from the fiber together with the color, the lacquer or the coating material.
Die Benetzbarkeit der Druckfarben, insbesondere Tiefdruckfarben, wird durch den oleophilen Charakter der nach außen weisenden organischen Reste des organophilen Komplexes besonders günstig beeinflußt.The wettability of the printing inks, especially gravure printing inks, is particularly favorably influenced by the oleophilic character of the organic residues of the organophilic complex which face outwards.
Als organische Lösungsmittel eignen sich erfindungsgemäß alle zum Auflösen oder Dispergieren von Druckfarben, Lacken, Beschichtungsmassen oder Klebmassen verwendeten Lösungsmittel. Vorzugsweise verwendet man bei Tiefdruckfarben ein organisches Lösungsmittel aus der Gruppe Toluol, Xylol oder Benzin, gegebenenfalls im Gemisch mit höhersiedenden Komponenten. Derartige Komponenten sind in der Drucktechnik üblich und dienen zur Beeinflussung des Abdampfverhaltens beim Trocknen der Druckfarbe. Bei lackartigen Beschichtungsmassen verwendet man die üblichen Lacklösungsmittel wie Ester, Aceton, Alkohole usw.According to the invention, all solvents used for dissolving or dispersing printing inks, lacquers, coating compositions or adhesives are suitable as organic solvents. An organic solvent from the group of toluene is preferably used in gravure printing inks, Xylene or petrol, possibly in a mixture with higher-boiling components. Such components are common in printing technology and serve to influence the evaporation behavior when the printing ink dries. The usual coating solvents such as esters, acetone, alcohols, etc. are used for coating compositions.
Die Erfindung ist auch zur Verbesserung des Holdouts von Haftkleber -Beschichtungsmassen anwendbar. Diese Beschichtungsmassen enthalten klebrige Harze, wie Polyacrylate und Polyisobutylen, die zum Teil mit Weichmachern vermischt sind. Bevorzugte Lösungsmittel für derartige Beschichtungsmassen sind solche auf Kohlenwasserstoffbasis, wie Benzin.The invention can also be used to improve the holdout of pressure-sensitive adhesive coating compositions. These coating compositions contain sticky resins such as polyacrylates and polyisobutylene, some of which are mixed with plasticizers. Preferred solvents for such coating compositions are those based on hydrocarbons, such as gasoline.
Da die organophilen Komplexe in organischen Lösungsmitteln quellen und/oder in kolloidalen Dispersionen vorliegen, kann man im allgemeinen nur begrenzte Feststoffgehalte bis zu 10 Gew.-% erreichen. Vorzugsweise liegt der reaktive organophile Komplex in Form einer 1,5 bis 10%igen Dispersion vor. Die Dispersionen der erfindungsgemäßen reaktiven organophilen Komplexe in organischen Lösungsmitteln sind stark thixotrop, was für das Auftragen, z.B. in einem Tiefdruckwerk mit einer Rasterwalze günstig ist.Since the organophilic complexes swell in organic solvents and / or are present in colloidal dispersions, generally only limited solids contents of up to 10% by weight can be achieved. The reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion. The dispersions of the reactive organophilic complexes according to the invention in organic solvents are strongly thixotropic, which is important for application, e.g. is cheap in a gravure printing unit with an anilox roller.
Der organophile Komplex kann entweder in die Fasermasse oder in die Oberfläche des Fasergebildes eingebracht werden.The organophilic complex can either be introduced into the fiber mass or into the surface of the fiber structure.
Das erfindungsgemäße Verfahren kann, insbesondere zur Herstellung von satinierten Papieren, in einer solchen Weise angewendet werden, daß der reaktive organophile Komplex vor der Erzeugung des Flächengebildes in wäßriger Dispersion in die suspendierte Fasermasse eingebracht wird, und zwar mit den oder ohne die Füllstoffe.The process according to the invention can be used, in particular for the production of satined papers, in such a way that the reactive organophilic complex is introduced into the suspended fiber mass in aqueous dispersion before the sheet is produced, with or without the fillers.
Eine Variante des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß man den organophilen Komplex vor der Erzeugung des Flächengebildes in situ in der Fasermasse durch Umsetzung des anorganischen Schichtsilikats mit der organischen Verbindung erzeugt. Auch bei dieser Umsetzung, z.B. mit einer quaternären Ammoniumverbindung, kann statt der Fasermasse (Pulpe) auch die Füllstoffsuspension vorgelegt sein, oder es liegen Fasern und Füllstoff bereits als Gesamtstoff vor.A variant of the process according to the invention is characterized in that the organophilic complex is generated in situ in the fiber mass by reacting the inorganic layered silicate with the organic compound before the fabric is produced. Also with this implementation, e.g. with a quaternary ammonium compound, the filler suspension can also be provided instead of the fiber mass (pulp), or fibers and filler are already present as a total.
Der Vorteil der Erzeugung in situ, z.B.in der Papierfabrik, liegt besonders darin, daß die Papiermaschine als Trockner auch für den organophilen Komplex wirkt, also Energie gespart wird.The advantage of generating in situ, e.g. B. In the paper mill, is particularly the fact that the paper machine also acts as a dryer for the organophilic complex, so energy is saved.
Wenn die beiden vorstehend angegebenen Verfahrensvarianten in der Papierfabrik durchgeführt werden, können die üblichen Füllstoffe teilweise durch den organophilen Komplex ersetzt werden. Es können auch die üblichen Retentionsmittel und weitere Zusätze, wie Farben, verwendet werden.If the two above-mentioned process variants are carried out in the paper mill, the usual fillers can be partially replaced by the organophilic complex. The usual retention aids and other additives, such as paints, can also be used.
Eine Verfahrensvariante, die insbesondere zur Herstellung von gestrichenen, hochsatinierten Papieren geeignet ist, ist dadurch gekennzeichnet, daß man den reaktiven organophilen Komplex, gegebenenfalls mit einem Bindemittel, einem Tensid und/oder einem inerten Streichpigment, in wäßriger Suspension in oder auf die Oberfläche des Flächengebildes bringt. Als inerte Streichpigmente können beispielsweise die üblichen Weißpigmente, welche die Opazität verbessern, verwendet werden.A process variant which is particularly suitable for the production of coated, highly satinized papers is characterized in that the reactive organophilic complex, optionally with a binder, a surfactant and / or an inert coating pigment, in aqueous suspension in or on the surface of the fabric brings. For example, the usual white pigments which improve the opacity can be used as inert coating pigments.
Wenn von einem Strich oder einer Oberflächenpräparation kein Beitrag zur Opazität eines Papierblattes erwartet wird, sondern wenn nur die Druckopazität im Vordergrund des Interesses steht und damit der Druckfarbenverbrauch und der Glanz des Druckes, so kann man nach einer Variante dieses Verfahrens den organophilen Komplex in situ in der Oberfläche des Flächengebildes erzeugen, indem man das anorganische Schichtsilikat in Form einer wäßrigen kolloidalen Dispersion die gegebenfalls Bindemittel, Tenside und/oder Streichpigmente enthält, in die Oberfläche einbringt und anschließend mit der organischen Verbindung umsetzt. Dies ist z.B. in allen denjenigen Streichmaschinen möglich, die je Seite zwei Streicheinrichtungen haben, was heute üblich ist. Besonders geeignet sind auch Maschinen mit zwei Leimpressen. Dabei wird z.B. in der ersten Leimpresse ein filmbildender hydratisierter hochquellfähiger Bentonit aufgegeben. Ein eigener Binder ist nicht erforderlich. In der zweiten Leimpresse wird dann die verdünnte Lösung einer quaternären Ammoniumverbindung aufgetragen.If a line or a surface preparation is not expected to contribute to the opacity of a sheet of paper, but if only the print opacity is in the foreground and thus the ink consumption and gloss of the print, then a variant of this process can be used to situate the organophilic complex in situ generate the surface of the fabric by making the inorganic layered silicate in the form of an aqueous colloidal dispersion which optionally contains binders, surfactants and / or coating pigments, introduces them into the surface and then reacts with the organic compound. This is possible, for example, in all those coating machines that have two coating devices on each side, which is common today. Machines with two size presses are also particularly suitable. In this case, for example, in the first L eimpresse a film-forming hydrated highly swellable bentonite abandoned. A separate binder is not required. The dilute solution of a quaternary ammonium compound is then applied in the second size press.
Eine weitere Möglichkeit, die nur eine Leimpresse oder eine ähnliche Auftragseinrichtung erfordert, besteht darin, daß man das anorganische Schichtsilikat in Form einer wäßrigen kolloidalen Dispersion,die gegebenenfalls Bindemittel, Tenside und/oder Pigmente enthält, in die Fasermasse einbringt und anschließend nur in der Oberfläche mit der organischen Verbindung umsetzt, um den organophilen Komplex zu erhalten. In diesem Fall setzt man vorzugsweise 3 bis 5 Gew.-% des hydratisierten anorganischen filmbildenden Schichtsilikat bezogen auf den Gesamtstoff in der Papiermasse, zu.Another possibility, which only requires a size press or a similar application device, is that the inorganic layered silicate is introduced into the fiber mass in the form of an aqueous colloidal dispersion, which optionally contains binders, surfactants and / or pigments, and then only in the surface reacted with the organic compound to obtain the organophilic complex. In this case, preferably 3 to 5% by weight of the hydrated inorganic film-forming sheet silicate, based on the total substance in the paper pulp, is added.
Anstatt den organophilen Komplex in situ in der Oberfläche zu erzeugen, kann man ihn auch durch Umsetzung des anorganischen Schichtsilikats mit der organischen Verbindung in Gegenwart von Bindemitteln, Tensiden und/oder Streichpigmenten erzeugen und das Umsetzungsprodukt als Streichmasse in oder auf die Oberfläche des Fasermaterials bringen.Instead of generating the organophilic complex in situ in the surface, it can also be produced by reacting the inorganic sheet silicate with the organic compound in the presence of binders, surfactants and / or coating pigments and bringing the reaction product as a coating composition into or onto the surface of the fiber material.
Alle diese Verfahrensvarianten zur Herstellung von gestrichenen Papieren werden in der Papierfabrik durchgeführt.All of these process variants for the production of coated papers are carried out in the paper mill.
Eine weitere Verfahrensvariante ist dadurch gekennzeichnet, daB man den reaktiven organophilen Komplex gegebenenfalls mit einem Bindemittel und/oder einem inerten Streichpigment, z.B. einem die Opazität erhöhenden Pigment, in einem Drganischen Lösungsmittel als Vorpräparation mittels einer Lösungsmittel-Streichmaschine oder eine Druckmaschine in Dder auf die Oberfläche des Flächengebildes bringt, worauf man nach einer Zwischentrocknung die Druckfarbe(n), den Lack bzw. die Beschichtungsmasse aufbringt.A further method variant is characterized in DAB, if appropriate, with a binder and / or an inert coating pigment, for example an opacity enhancing pigment rganischen in a D solvent as a pre-preparation by means of a solvent coating machine or a printing press in D of the reactive organophilic complex brings the surface of the fabric, after which the printing ink (s), the lacquer or the coating composition are applied after an intermediate drying.
Das Aufbringen des erfindungsgemäßen reaktiven organophilen Komplexes aus der organischen Lösung oder Dispersion kann grundsätzlich auf einen sogenannten Solvent-Coater bei hohen Geschwindigkeiten und in den Breiten moderner Papiermaschinen (etwa 7 bis 8 Meter) erfolgen.The reactive organophilic complex according to the invention can in principle be applied from the organic solution or dispersion to a so-called solvent coater at high speeds and in the widths of modern paper machines (about 7 to 8 meters).
Der Vorteil solcher Lösungsmittelstreichmaschinen liegt unter anderem darin, daß bezüglich des Strichauftrages sowie der Zumischung eventuell opazifierender Pigmente jeder Freiheitsgrad besteht.The advantage of such solvent coating machines lies, inter alia, in the fact that there is every degree of freedom with regard to the application of the coat and the admixture of any opacifying pigments.
Da bei den Druckern im Rollentiefdruck in vielen Fällen im ersten Druckwerk keine Farbe läuft, sondern das Papier nur "vorgestreckt"wird, da weiterhin in manchen Großdruckereien pro Seite 4, 5 oder 6 Druckwerke vorgesehen sind, die nicht in allen Fällen zum Einsatz kommen, z.B. bei Werbedrucksachen, kann das erfindungsgemäße Verfahren mit Vorteil auch in der Druckerei durchgeführt werden.Since in rotogravure printing in many cases no ink runs in the first printing unit, but the paper is only "pre-stretched", since in some large printing plants there are still 4, 5 or 6 printing units per page that are not used in all cases, e.g. in the case of advertising printed matter, the method according to the invention can advantageously also be carried out in the printing house.
Ein Druckwerk, z.B. ein einfaches Rastertiefdruckwerk, kann also bei der vorstehend beschriebenen Verfahrensvariante dazu verwendet werden, um einen unsichtbaren Vordruck des organophilen Komplexes herzustellen, der wie üblich zwischengetrocknet wird, bevor der eigentliche Tiefdruck beginnt.A printing unit, e.g. a simple screen gravure printing unit, can therefore be used in the process variant described above to produce an invisible form of the organophilic complex, which is dried as usual before the actual gravure begins.
Die Kosten für die Tiefdruckerei liegen in bescheidenen Grenzen, wenn, wie üblich, das Lösungsmittel zu 92 bis 96 % zurückgewonnen wird. Da erfindungsgemäß das organische Dispergiermittel für den organophilen Komplex dasselbe ist wie für das Lösungsmittel für die nachfolgenden Druckfarben, macht die gemeinsame Rückgewinnung keine Probleme. Das Vorstreckwerk, also das hier zum Einsatz kommende erste Druckwerk, kann seine Funktion als solches beibehalten, denn der Vordruck mit dem reaktiven organophilen Komplex kann vollflächig und ohne Passerhaltung gedruckt werden.The costs for gravure printing are limited if, as usual, 92 to 96% of the solvent is recovered. Since, according to the invention, the organic dispersant for the organophilic complex is the same as for the solvent for the subsequent printing inks, the joint recovery makes no problems. The pre-stretching unit, i.e. the first printing unit used here, can retain its function as such, because the form with the reactive organophilic complex can be printed over the entire surface and without registering.
Bei dieser Verfahrensvariante ist es auch möglich, den organophilen Komplex nur partiell in die Oberfläche des Flächengebildes einzubringen. An diesen Stellen erscheint die Druckfarbe glänzend, während sie an den anderen Stellen, die in der Oberfläche keinen organophilen Komplex enthalten, wegschlägt und deshalb matt erscheint.With this method variant, it is also possible to introduce the organophilic complex only partially into the surface of the fabric. The printing ink appears glossy in these areas, while it strikes away in the other areas that do not contain any organophilic complex in the surface and therefore appears matt.
Im allgemeinen kann man als Dispergiermittel für den reaktiven organophilen Komplex und die Druckfarbe(n) bzw. den Lack oder die Beschichtungsmasse gleiche oder gleichartige organische Lösungsmittel verwenden.In general, the same or similar organic solvents can be used as dispersants for the reactive organophilic complex and the printing ink (s) or the lacquer or the coating composition.
Gegenstand der Erfindung ist ferner eine Masse zur Durchführung des vorstehend beschreibenen Verfahrensvarianten, die auf die Oberfläche des Fasergebildes aufgebracht wird. Diese Masse ist dadurch gekennzeichnet, daß sie in Form einer Dispersion eines reaktiven organophilen Komplexes in einem wäßrigen oder organischen Medium vorliegt.The invention further relates to a mass for carrying out the method variants described above, which is applied to the surface of the fiber structure. This mass is characterized in that it is in the form of a dispersion of a reactive organophilic complex in an aqueous or organic medium.
Vorzugsweise liegt der reaktive organophile Komplex in Form einer 1,5 bis 10%igen Dispersion vor, insbesondere in einem organischen Lösungsmittel, wie Toluol oder Xylol. In einem wäßrigen Medium liegt der reaktive organophile Komplex vorzugsweise in einer 2 bis 20%igen Dispersion vor.The reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion, in particular in an organic solvent such as toluene or xylene. In an aqueous medium, the reactive organophilic complex is preferably in a 2 to 20% dispersion.
Gegenstand der Erfindung sind ferner Flächengebilde aus Fasern, insbesondere Papier, die dadurch gekennzeichnet sind, daß sie in der Oberfläche und/oder in der Fasermasse einen reagierenden organophilen Komplex enthalten, der nach dem erfindungsgemäßen Verfahren erhältlich ist.The invention further relates to fabrics made of fibers, in particular paper, which are characterized in that they contain in the surface and / or in the fiber mass a reactive organophilic complex which can be obtained by the process according to the invention.
Wenn sich der organophile Komplex in der Oberfläche der erfindungsgemäßen Flächengebilde befindet, so liegt er vorzugsweise feinverteilt in einer Menge von 0,1 bis 3, vorzugsweise von 0,2 bis 0,8 g/m2 und Seite vor. Wenn er sich in der Fasermasse befindet, so liegt er vorzugsweise in einer Menge von etwa 1,5 bis 12 Gew.-% vor. Die Erfindung kann außerdem z.B. zur Herstellung von Zinkoxidpapieren angewendet werden. Bei diesen Papieren wird ein Toluollack, der mit photohalbleitendem Zinkoxid und nichtleitenden Bindern gefüllt ist, auf die Oberfläche eines leitfähigen Rohpapiers aufgestrichen. Die Leitfähigkeit des Rohpapiers wird dadurch gewonnen, daß ein leitfähiges Polymer (conäuctiiepolymer) der Leimpressenpräparation aus Stärkeäthern oder -estern oder aus Polyvinylalkohol zugesetzt wird. Der Toluollack verhält sich analog wie eine Druckfarbe. Wegen der Sperrwirkung des reaktiven organophilen Komplexes in der Fasermasse bzw. in der Oberfläche des Fasergebildes wird der mit Zinkoxid gefüllte Toluollack daran gehindert, in die Fasermasse einzudringen. Bisher war es nur durch großen Aufwand, teilweise doppelte Leimpressenbeschichtung, teilweise Vorstreichen mit dem leitfähigen Polymer und dem kolloidalen Binder, möglich, einen Holdout für Toluol, der lochfrei ist, zu erzielen. Durch Zusatz des reaktiven organophilen Schichtsilikats in die Leimpressenpräparation und/oder in den Vorstrich ist es möglich, für die nachfolgende Beschichtung eine punktfreie Toluoldichte zu erreichen.If the organophilic complex is in the surface of the flat structures according to the invention, it is preferably present in a finely divided amount in an amount of 0.1 to 3, preferably 0.2 to 0.8 g / m 2 and side. If it is in the fiber mass, it is preferably present in an amount of about 1.5 to 12% by weight. The invention can also be used, for example, for the production of zinc oxide papers. With these papers, a toluene varnish, which is filled with photoconductive zinc oxide and non-conductive binders, is spread onto the surface of a conductive base paper. The conductivity of the base paper is obtained by adding a conductive polymer (coneuctie polymer) to the size press preparation from starch ethers or starches or from polyvinyl alcohol. The toluene coating behaves analogously to a printing ink. Because of the barrier effect of the reactive organophilic complex in the fiber mass or in the surface of the fiber structure, the toluene lacquer filled with zinc oxide is prevented from penetrating into the fiber mass. Until now, it was only possible to achieve a holdout for toluene that is hole-free, only with great effort, partly double size press coating, partly pre-coating with the conductive polymer and the colloidal binder. By adding the reactive organophilic layered silicate in the size press preparation and / or in the primer, it is possible to achieve a spot-free toluene density for the subsequent coating.
An allen den Stellen, an denen das leitfähige Rohpapier eine Fehlstelle hat, d.h. Toluol aufsaugt, tritt in der Oberfläche des Zinkoxidpapiers eine Fehlstelle in der Bildwiedergabe ein. Durch die erfindungsgemäße Mitverwendung der reaktiven organophilen Schichtsilikate können diese Fehlstellen ausgeschaltet werden.Wherever the conductive base paper has a flaw, i.e. If toluene is absorbed, a defect in the image reproduction occurs in the surface of the zinc oxide paper. By using the reactive organophilic phyllosilicates according to the invention, these defects can be eliminated.
Die vorliegende Erfindung kann auch angewendet werden, um das Eindringen von Lacken, wie Nitrolack, Zaponlack, Kunststofflack, Spirituslack usw. in Fasergebilde zu verhindern. Beispielsweise werden Etikettenpapiere nach dem Druck mit einem sogenannten Etikettenschutzlack überlackiert, damit die Etiketten auf den Flaschen scheuerfest und nicht durch Aufnahme von Feuchtigkeit unansehnlich werden.The present invention can also be used to prevent the penetration of lacquers such as nitro lacquer, zapon lacquer, plastic lacquer, spirit lacquer etc. into fiber structures. For example, label papers are coated with a so-called protective label varnish after printing so that the labels on the bottles are scrub-resistant and not unsightly due to the absorption of moisture.
Damit ein Etikettenpapier lackierfähig wird, muß es meist einseitig gestrichen sein. Sogenannte Naturetikettenpapiere lassen sich nicht lackieren, da der Lack nicht auf der Oberfläche bleibt, sondern in das Fasermaterial eindringt. Durchdie erfindungsgemäße reaktive Sperrschicht aus dem organophilen Komplex wird ein Eindringen des Etikettenlacks in das Fasermaterial vermieden.In order for a label paper to be paintable, it usually has to be coated on one side. So-called natural label papers cannot be varnished because the varnish does not remain on the surface but penetrates into the fiber material. The reactive barrier layer made of the organophilic complex according to the invention prevents the label lacquer from penetrating into the fiber material.
Zusätzlich sei bemerkt, daß durch die Vorbeschichtung einer Papieroberfläche oder eines anderen flächenförmigen Fasergebildes mit den spontan reagierenden organophilen komplexen Materialienbedruckbar, insbesondere lackierbar und aus organischer Lösung beschichtbar gemacht werden können, bei denen dies bisher praktisch nicht möglich war. Hierzu gehören neben den Vliesstoffen die einfachen holzhaltigen und holzfreien Naturpapiere, und zwar auch diejenigen, die nicht oder kaum gefüllt sind und die nicht satiniert wurden.In addition, it should be noted that the precoating of a paper surface or another sheet-like fiber structure with the spontaneously reacting organophilic complex materials can make it printable, in particular paintable and coatable from organic solution, for which this was previously not possible. In addition to the nonwovens, this includes the simple wood-containing and wood-free natural papers, including those that are not or hardly filled and that have not been satined.
Unter diesem Aspekt ist die Erfindung insbesondere für Karton wichtig, wo, ob gestrichen oder nicht, jede Satinage und jede Glättung in einem Glättwerk zu einem unerwünschten Volumenverlust und damit Steifigkeitsverlust führt.From this point of view, the invention is particularly important for cardboard, where, whether coated or not, every satin finish and smoothing in a smoothing unit leads to an undesirable loss of volume and thus a loss of rigidity.
Die Erfindung ist ferner für die Herstellung von Haftetiketten geeignet.The invention is also suitable for the production of adhesive labels.
Haftklebebeschichtungen erfolgen in den meisten Fällen aus einer organischen Lösung der Klebstoffe. Dabei spielt das Einschlagverhalten der Klebebeschichtungsmassen in das Papier eine große Rolle. Sie sollen nämlich so wenig wie möglich in das Papier hineinschlagen. Bisher hat man in solchen Fällen mit teuren Leimpressenpräparationen, wie z.B. Casein oder Polyvinylalkohol, versucht, den Holdout zu verbessern. Auch hier führt eine Beschichtung mit dem reaktiven organophilen Komplex nicht nur zu einer Verminderung des Haftkleberauftrages, sondern ermöglicht auch den Einsatz bisher wenig oder ungeeigneter Flächengebilde, wie Vliesstoffe oder Textilien. Diese Materialien können erfindungsgemäß auch bedruckbar gemacht werden.In most cases, PSA coatings are made from an organic solution of the adhesives. The impact behavior of the adhesive coating masses in the paper plays an important role. This is because they should hit the paper as little as possible. So far, in such cases, expensive glue press preparations such as Casein, or polyvinyl alcohol, tries to improve holdout. Here too, coating with the reactive organophilic complex not only leads to a reduction in the application of pressure-sensitive adhesive, but also enables the use of previously little or unsuitable fabrics, such as nonwovens or textiles. According to the invention, these materials can also be made printable.
Wenn in den organophilen Komplexen quaternäre AmmonlumveLbindungen enthalten sind, so beeinflussen diese die elektrischen Eigenschaften der erfindungsgemäßen Flächengebilde, z.B. den Oberflächen- oder Durchgangswiderstand. Diese Werte spielen eine Rolle für die Bedruckbarkeit. Durch die erfindungsgemäße Modifizierung werden die Oberflächen- und Durchgangswiderstände reduziert und dadurch Störungen, die durch elektrostatische Aufladungen bedingt sind, ausgeschaltet.If quaternary ammonium compounds are contained in the organophilic complexes, they influence the electrical properties of the fabrics according to the invention, e.g. the surface or volume resistance. These values play a role in printability. The modification according to the invention reduces the surface and volume resistances and thereby eliminates interference caused by electrostatic charges.
Die Erfindung ist durch die nachstehenden Beispiele in nicht einschränkender Weise erläutert.The invention is illustrated in a non-limiting manner by the examples below.
Ein halbgebleichter Nadelsulfatzellstoff wird in einem Pulper bei einer Stoffdichte von 5 % und bei einem pH-Wert von 7 bis 7,8 zerfasert und anschließend in einem Mahlgerät (Refiner) auf einen Mahlgrad von 26° SR (Schopper-Riegler) gebracht.A semi-bleached needle sulfate pulp is pulped in a pulper at a consistency of 5% and at a pH of 7 to 7.8 and then brought to a degree of grinding of 26 ° SR (Schopper-Riegler) in a refiner.
In einer Stoffmischzentrale wird dieser Zellstoff im Verhältnis 25 : 75 mit einem splitterfreien Holzschliff von einem Mahlgrad von 78°SR gemischt. Eine getrennt hergestellte Kaolin-Slurry von 40 % bei einem pH-Wert von 7 bis 7,8 wird dem Fasergemisch im Verhältnis 70 Teile Fasern zu 30 Teile Kaolin (alles lufttrocken gerechnet) zugemischt. Diesem Gesamtstoff wird eine Slurry von 3,5 % Feststoff eines vorgequollenen Natriumbentonits mit einem Ionentauschvermögen von 90 mVal/100g zugemischt, bis, bezogen auf Fasern und Füllstoff, 4 Gew.-% des Bentonits eingetragen sind. Das Ganze wird etwa 10 min. gut gemischt. Darauf wird eine 4%ige wäßrige Lösung von Dimethyl-Benzyl-Alkyl-(C12-C22)-Ammoniumchlorid in einer für den vollständigen Ionenaustausch äquimolaren Menge zugemischt.This pulp is mixed in a ratio 25: 75 in a pulping center with a splinter-free wood pulp with a freeness of 78 ° SR. A separately produced kaolin slurry of 40% at a pH of 7 to 7.8 is mixed into the fiber mixture in a ratio of 70 parts of fibers to 30 parts of kaolin (all air dry). A slurry of 3.5% solids of a pre-swollen sodium bentonite with an ion exchange capacity of 90 mVal / 100 g is mixed into this total substance until, based on fibers and filler, 4% by weight of the bentonite has been introduced. The whole thing will take about 10 min. well mixed. A 4% strength aqueous solution of dimethyl-benzyl-alkyl- (C12-C22) ammonium chloride is then mixed in in an amount equimolar to the complete ion exchange.
Nach einer Mischzeit von 15 min. wird aus diesem Stoff nach Verdünnung auf 0,6 % auf einer Papiermaschine Papier mit einem Flächengewicht von 40 g/m2 erzeugt und bei der Trocknung auf eine Restfeuchte von 8,5 Gew.-% herausgefahren. Danach wird das Papier auf einem Superkalander satiniert. Es hat eine Bekk-Glätte von 900 sec. bei einer Dichte von 1,10 g/cm3. Es enthält etwa 5 Gew.-%, bezogen auf den Gesamtstoffeintrag, reaktiven organophilen Bentonit. Es hat einen Toluol-Holdout (gemessen nach der Auftropfmethode, mit 0,05 ml Toluol, das mit Ceresrot angefärbt ist) von 65 sec., verglichen mit 36 sec. bei einem ansonsten gleichen Papier ohne den organophilen Bentonit. Der organophile Bentonit haftet gut an den Fasern und Füllstoffen. Die geringe Menge von NaCl stört im Abwasser nicht.After a mixing time of 15 min. After dilution to 0.6%, paper with a basis weight of 40 g / m 2 is produced from this substance on a paper machine and dried to a residual moisture content of 8.5% by weight. Then the paper is satined on a super calender. It has a Bekk smoothness of 900 seconds with a density of 1.10 g / cm 3 . It contains about 5% by weight, based on the total input, of reactive organophilic bentonite. It has a toluene holdout (measured by the spotting method, with 0.05 ml toluene stained with Ceres red) of 65 seconds compared to 36 seconds for an otherwise identical paper without the organophilic bentonite. The organophilic bentonite adheres well to the fibers and fillers. The small amount of NaCl does not interfere in the wastewater.
Ein handelsüblicher, mit quaternären Ammoniumionen belegter organophiler Bentonit (Tixogel VZ(R) der Fa. Süd-Chemie AG) wird in einem Schnellmischer mit hohen Scherkräften als Dispersion mit einem Feststoffgehalt von 20 Gew.-% in Gegenwart eines nichtionogenen Tensids von Nonylphenolethoxylattyp 15 min. geschert. Diese Dispersion wird den wie nach Beispiel 1 hergestellten Fasern zugemischt und dann die Kaolinslurry dazugegeben, und zwar in einer Menge, daß, bezogen auf den Gesamtstoff, 6 Gew.-% des reaktiven organophilen Tons im Gesamtstoff sind. Das auf konventionelle Weise nach Verdünnung, Einstellen des pH-Wertes auf 5,8 hergestellte Blatt von 60 g/m2 hat einen Gehalt von 5,5 bis 6 Gew.-% des organophilen Tons. Nach der Satinage mit geheizten Stahlwalzen bei 90°C hat es eine Glätte von 1300 Bekk.-sec. und einen Toluol-Holdout von 50 sec.A commercially available organophilic bentonite coated with quaternary ammonium ions (Tixogel VZ ( R ) from F a. Süd-Chemie AG) is mixed in a high-speed mixer with high shear forces as a dispersion with a solids content of 20% by weight in the presence of a nonylphenol ethoxylate type 15 min. sheared. This dispersion is admixed to the fibers produced as in Example 1 and then the kaolin slurry is added in an amount such that, based on the total, 6% by weight of the reactive organophilic clay are in the total. The sheet of 60 g / m 2 produced in a conventional manner after dilution, adjustment of the pH to 5.8, has a content of 5.5 to 6% by weight of the organophilic clay. After calendering with heated steel rollers at 90 ° C, it has a smoothness of 1300 Bekk.-sec. and a toluene holdout of 50 sec.
Ein holzhaltiges Streichrohpapier mit 55 Gew.-% Anteil an halbgebleichtem Nadelsulfatzellstoff und 45 Gew.-% Anteil an Holzschliff und einem Flächengewicht von 38 g/m2 wird mit einer Streichmasse folgender Zusammensetzung gestrichen:
- 96 Teile Streichkaolin
- 4 Teile feindispergierter reaktiver organophiler Bentonit in Form einer 20 gew.-%igen wäßrigen Dispersion nach Beispiel 2
- 96 parts of coated kaolin
- 4 parts of finely dispersed reactive organophilic bentonite in the form of a 20% by weight aqueous dispersion according to Example 2
Diese Bestandteile werden in einem Caddy-Mischer intensiv gemischt. Anschließend werden 4,5 Teile einer Kunststoffdispersion aus einem Copolymer von Styrol und Acrylsäure als Tiefdruckbinder sowie zusätzlich 1,5 Teile eines vollverseiften mittelviskosen Polyvinylalkohols zugegeben. Der pH-Wert wird auf 8,5 eingestellt. Der Feststoffgehalt der Streichmasse wird auf 50 Gew.-% eingestellt.These components are mixed intensively in a caddy mixer. Then 4.5 parts of a plastic dispersion of a copolymer of styrene and acrylic acid as a gravure binder and an additional 1.5 parts of a fully saponified medium-viscosity polyvinyl alcohol are added. The pH is adjusted to 8.5. The solids content of the coating slip is adjusted to 50% by weight.
Nach dem Strich von je 7 g/m2 und Seite wird ein gestrichenes Tiefdruckpapier erzeugt, das nach Satinage eine Bekk-Glätte von 1500 bis 1600 sec. und einen Toluol-Holdout von 65 sec. hat. Ein vergleichbares gestrichenes Tiefdruckpapier hat einen Toluol-Holdout von 40 sec.After the line of 7 g / m 2 and page, a coated rotogravure paper is produced which, after satinizing, has a Bekk smoothness of 1500 to 1600 seconds and a toluene holdout of 65 seconds. A comparable coated rotogravure paper has a toluene holdout of 40 seconds.
Gemäß Beispiel 1 wird ein holzhaltiges, kaolingefülltes satiniertes Naturtiefdruckpapier ohne Bentonit oder quaternäre Ammoniumverbindung in der Masse hergestellt. In einer Streichmaschine mit zwei Streichköpfen je Seite und jeweiliger Zwischentrocknung wird im ersten und im dritten Streichwerk eine 5 %ige Slurry eines handelsüblichen Bentonits, dessen austauschfähige Kationen zu 40 % aus Na- und zu 60 % aus Ca-Kationen bestehen, aufgetragen. Der Auftrag beträgt etwa 1,5 g/m2 und Seite.According to Example 1, a wood-containing, kaolin-filled, satined, gravure printing paper without bentonite or quaternary ammonium compound is produced in bulk. In a coating machine with two coating heads on each side and the respective intermediate drying, a 5% slurry of a commercially available bentonite, the exchangeable cations of which are 40% Na and 60% Ca, is applied in the first and third coating unit. The order is about 1.5 g / m 2 and side.
In den Streichwerken 2 und 4 wird nach Zwischentrocknung eine 4%ige Lösung der quaternären Ammoniumverbindung von Beispiel 1 in der dort angegebenen Relation aufgetragen. Diese Lösung reagiert durch Ionenaustausch in der Oberfläche mit dem vorgelegten Bentonit unter Bildung des reaktiven organophilen Komplexes. Da sowohl der hydratisierte Bentonit filmbildend ist und auch der reaktive organophile Komplex einen wenn auch schwach haftenden Film bildet, ist die Mitverwendung kolloidaler und/oder disperser Binder nicht erforderlich.After intermediate drying, a 4% solution of the quaternary ammonium compound from Example 1 is applied in the coating units 2 and 4 in the relation given there. This solution reacts by ion exchange in the surface with the bentonite to form the reactive organophilic complex. Since both the hydrated bentonite is film-forming and the reactive organophilic complex forms a film, even if it adheres poorly, the use of colloidal and / or disperse binders is not necessary.
Ein holzhaltiges hochgefülltes Papier, das gemäß der EU-PS 0 017 793 mit einem filmbildenden kolloidalen Bentonit, dessen Natrium-Magnesium-Atomverhältnis 60:40 betrug, gefertigt wurde und, bezogen auf das Papier 2,5 Gew.-% des filmbildenden Bentonits enthält, wird am Ende der Trockenpartie einer Papiermaschine mittels einer konventionellen Leimpresse mit der verdünnten 3%igen wäßrigen Lösung der quaternären Ammoniumverbindung von Beispiel 1 behandelt. Da auf jeden Fall Fasern und Füllstoffe dieses Papiers einen wenn auch dünnen Überzug von filmbildendem Bentonit tragen, tritt dieser mit der quaternären Ammoniumverbindung in Ionenaustausch und führt dazu, daß besonders in der Oberfläche nach erneutem Trocknen der erfindungsgemäße reaktive organophile Komplex vorliegt.
Das dabei entstehende Natrium- und Magnesiumchlorid stört nicht.A wood-containing, highly filled paper which, according to EU-PS 0 017 793, was produced with a film-forming colloidal bentonite, the sodium-magnesium atomic ratio of which was 60:40, and, based on the paper, contains 2.5% by weight of the film-forming bentonite , is treated at the end of the dryer section of a paper machine using a conventional size press with the dilute 3% aqueous solution of the quaternary ammonium compound from Example 1. Since the fibers and fillers of this paper in any case carry a film of bentonite, albeit a thin one, this enters into ion exchange with the quaternary ammonium compound and results in the reactive organophilic complex according to the invention being present especially in the surface after renewed drying.
The resulting sodium and magnesium chloride does not interfere.
In vielen Fabriken, die sich mit dem Veredeln von Papier beschäftigen, stehen sogenannte Solvent-Coater. Es sind dies Streichmaschinen, die als Lösungs- oder Dispergiermittel statt Wasser verschiedene organische Lösungsmittel verwenden und diese meist aus der Abluft wiedergewinnen.So-called solvent coaters are found in many factories that deal with the finishing of paper. These are coating machines that use various organic solvents as solvents or dispersants instead of water and usually recover them from the exhaust air.
Ein holzhaltiges Naturtiefdruckpapier mit einem Flächengewicht von 40 g/m2 hat einen Füllstoffgehalt von 18 Gew.-%. Seine Opazität und seine Druckopazität sind unbefriedigend.A wood-containing gravure printing paper with a basis weight of 40 g / m 2 has a filler content of 18% by weight. Its opacity and print opacity are unsatisfactory.
Ein handelsüblicher, mit quaternären Ammoniumionen belegter Bentonit (Tixogel VP (R) der Fa. Süd-Chemie AG) wird in Form einer Dispersion mit einem Feststoffgehalt von 3,5 Gew.-% in einem Lösungsmittelgemisch aus 99 Gew.-Teilen Toluol und 1 Gewichtsteil Ethanol 10 min. in einem stark scherenden Schnellmischer dispergiert. Diese Dispersion wird mittels eines Reverse-Roll-Coaters beidseitig auf das Papier aufgetragen, so daß je Seite 0,5 g/m2 Auftrag (lufttrocken gerechnet) resultieren.A commercial bentonite (Tixogel VP ( R ) from Süd-Chemie AG) coated with quaternary ammonium ions is in the form of a dispersion with a solids content of 3.5% by weight in a solvent mixture of 99 parts by weight of toluene and 1 Part by weight of ethanol 10 min. dispersed in a high shear high-speed mixer. This dispersion is applied to both sides of the paper by means of a reverse roll coater, so that 0.5 g / m 2 of application (air-dry calculated) result on each side.
Während das nicht gestrichene Papier einen Toluol-Holdout von 5 sec. hat, hat das so vorbehandelte Papier einen Toluol-Holdout von 60 sec. Der Druck mit einer schwarzen Tiefdruckfarbe zeigt fast kein Durchscheinen auf der Rückseite und einen erhöhten Druckglanz.While the uncoated paper has a toluene holdout of 5 seconds, the paper pretreated in this way has a toluene holdout of 60 seconds. Printing with a black gravure ink shows almost no show through on the back and an increased print gloss.
In einer Tiefdruckmaschine bestehen pro Seite vier Druckwerke. Es soll aber nur ein Dreifarbentiefdruck gedruckt werden. Üblicherweise läßt man das erste Druckwerk ohne Farbe mitlaufen, um die Papierbahn vorzustrechen.There are four printing units per page in a gravure printing machine. However, only a three-color rotogravure should be printed. Usually the first printing unit is run without color in order to pre-rip the paper web.
In diesem ersten Druckwerk wird mittels einer Rasterwalze mit einem 70er Raster und einer Gravurtiefe von 65 µm eine farblose Vordruckfarbe vollflächig und ohne Rücksicht auf Passerhaltigkeit mit einer 3 Gew.-%igen kolloidalen Dispersion in Toluol, hergestellt analog Beispiel 6, vorgedruckt. Dieser Vordruck bringt nach der üblichen Trocknung einen Auftrag von 0,3 g/m2 auf das zu bedruckende Papier auf. Während bei einem wenig gefüllten holzhaltigen Naturpapier die Wegschlagzeit für angefärbte Toluollösung etwa 6 sec. beträgt, ergibt sie auf dem "vorgedruckten" Papier bei einer Beschichtung von 0,3 g/m2 einen Wert von 70 sec. Eine weitere Erhöhung des Auftrages des reaktiven organophilen Komplexes aus der Toluollösung, z.B. 0,6 g/m2 ergibt keinen höheren Wert und auch keinen schärferen Stand des angefärbten Toluoltropfens, da bei einem Auftrag von nur 0,3 g/m2 bereits eine volle Versiegelung des Druckpapieres gegen Toluol eingetreten ist.In this first printing unit, a colorless pre-printing ink is pre-printed with a 3% by weight colloidal dispersion in toluene, produced analogously to Example 6, using a screen roller with a 70 screen and an engraving depth of 65 µm over the entire surface and regardless of registration. After the usual drying, this form applies an application of 0.3 g / m 2 to the paper to be printed. While sec at a lightly filled wood-containing N aturpapier the absorption time for dyed toluene solution is about 6., It yields at the "preprinted" paper at a coating of 0.3 g / m 2 has a value of 70 sec. A further increase of the order of reactive organophilic complex from the toluene solution, for example 0.6 g / m 2 does not give a higher value nor a sharper level of the colored toluene drop, since with a coating of only 0.3 g / m 2 the printing paper was already fully sealed against toluene is.
Da die Verbesserung des Holdouts für lösungsmittelhaltige Druckfarben mit einer Erhöhung des Glanzes der Druckfarbe auf ihrem maximalen Wert verbunden ist, ergibt sich die Möglichkeit, im ersten Druckwerk partiell bedruckte Flächen mit der 3 gew.-%igen kolloidalen Dispersion in Toluol gemäß Beispiel 7 zu erhalten. Alle nachfolgenden Drucke, die auf nicht vorbehandelte Flächenteile treffen, schlagen weg und ergeben einen matten Druck. Since the improvement of the holdout for solvent-based printing inks is associated with an increase in the gloss of the printing ink to its maximum value, there is the possibility in the first printing unit of partially printed areas with the 3% by weight colloidal dispersion in toluene according to Example 7 receive. All subsequent prints, which meet non-pretreated parts of the surface, fold away and result in a matt print.
Alle Tiefdruckfarben, die auf die vorbehandelten Flächenteile treffen, bleiben auf der Druckoberfläche stehen und entwickeln ihren maximal möglichen Druckglanz. Man kann so z.B. in einer Werbedrucksache den anzupreisenden Artikel hochglänzend auf einem matten Fond herausstellen.All gravure inks that meet the pretreated surface parts remain on the printing surface and develop their maximum possible printing gloss. You can e.g. In an advertising printed matter, highlight the article to be priced in high gloss on a matt background.
Betont sei nochmals zu den Beispielen 7 und 8, daß beim Vordrucken einer kolloidalen Dispersion des reaktiven organophilen Komplexes ein Bindemittel deswegen nicht notwendig ist, weil die Filmbildungsfähigkeit dieser Produkte groß genug ist, um eine ausreichende Haftung zu gewährleisten.It should be emphasized again for Examples 7 and 8 that when a colloidal dispersion of the reactive organophilic complex is pre-printed, a binder is not necessary because the film-forming ability of these products is large enough to ensure adequate adhesion.
In all den Fällen, in denen eine oder mehrere weitere Druckfarben ebenfalls mit Toluol auf den Vordruck gedruckt werden,muß man annehmen, daß dieser Vordruck integraler Bestandteil des gesamten Druckes wird.In all cases in which one or more other printing inks are also printed on the form with toluene, it must be assumed that this form becomes an integral part of the entire print.
Ein holzfreies Etikettenpapier wird aus 60 Gewichtsteilen hochgebleichtem Nadelsulfatzellstoff mit einem Mahlgrad von 30°SR und 40 Gewichtsteilen gebleichtem Birkensulfatzellstoff mit einem Mahlgrad von 45°SR hergestellt. Zur Verbesserung der Opazität werden 10 Gewichtsteile Kaolin, 5 Gewichtsteile Ti02 und 5 Gewichtsteile Aluminiumhydroxid zugegeben. Das Papier wird mit 2,5 Gewichtsteilen Harzleim unter Zusatz eines Melamin-Formaldehydharzes zur Verbesserung der Naßfestigkeit bei einem pH-Wert von 4,6 als einseitig glattes Papier herausgefahren und am Ende der Trockenpartie auf 136°C erhitzt, um die Vernetzung des Melamin-Formaldehydharzes sicherzustellen. Dieses Etikettenpapier soll nach dem Druck mit einem Scheuerschutzlack überzogen werden.A wood-free label paper is made from 60 parts by weight of highly bleached needle sulfate pulp with a freeness of 30 ° SR and 40 parts by weight of bleached birch sulfate pulp with a freeness of 45 ° SR. To improve the opacity, 10 parts by weight of kaolin, 5 parts by weight of TiO 2 and 5 parts by weight of aluminum hydroxide are added. The paper is taken out with 2.5 parts by weight of resin glue with the addition of a melamine-formaldehyde resin to improve the wet strength at a pH of 4.6 as smooth paper on one side and heated to 136 ° C. at the end of the drying section in order to crosslink the melamine. Ensure formaldehyde resin. This label paper should be coated with a scouring varnish after printing.
Der Etikettendruck wird im Tiefdruck durchgeführt, wobei im ersten Tiefdurckwerk eine Dispersion des reaktiven organophilen Komplexes gemäß Beispiel 6 in Toluol vorgedruckt wird. Nach dem graphischen Druck wird der Etikettenschutzlack als Nitrolack aufgebracht. Er dringt in das erfindungsgemäß behandelte Naturdruckpapier nicht ein, obwohl dieses nicht gestrichen ist.The label printing is carried out in gravure printing, a dispersion of the reactive organophilic complex according to Example 6 in toluene being pre-printed in the first gravure printing unit. After graphic printing, the protective label varnish is applied as a nitro varnish. It does not penetrate the natural printing paper treated according to the invention, although it has not been deleted.
Es empfiehlt sich, in allen Fällen der Beispiele 7, 8 und 9 dasselbe organische Lösungsmittel zu verwenden, gegebenenfalls auch mit Beimischungen von Hochsiedern, damit das aus einer Lösungsmittelrückgewinnungsanlage erhaltene Kondensat gleichmäßig wiederverwendet werden kann.It is advisable to use the same organic solvent in all cases of Examples 7, 8 and 9, if appropriate also with admixtures of high boilers, so that the condensate obtained from a solvent recovery system can be reused uniformly.
Ein nicht gestrichener Chromoersatz-Karton mit einem Flächengewicht von 300 g/m2 wurde mit einer Dispersion gemäß Beispiel 6 im Tiefdruck bedruckt, wobei der getrocknete Auftrag nur 0,2 g/m2 betrug. Auf dem so vorbehandelten Karton bleibt ein Nitrolack, der sonst weggeschlagen würde, glänzend stehen.A non-coated chromo replacement cardboard with a basis weight of 300 g / m 2 was printed with a dispersion according to Example 6 by gravure printing, the dried application being only 0.2 g / m 2 . A nitro lacquer, which would otherwise be knocked off, remains shiny on the pre-treated cardboard.
Ein Vliesstoff aus 80 % Polyesterfaser und 20 % gebleichtem Nadelsulfatzellstoff als Dispergierfaser wird mit einer Kunststoffdispersion von Polyacrylsäureester imprägniert, nachdem er auf einer Steilsiebmaschine in wäßriger Suspension hergestellt worden war.A nonwoven fabric made of 80% polyester fiber and 20% bleached needle sulfate pulp as a dispersing fiber is impregnated with a plastic dispersion of polyacrylic acid ester after it has been produced in an aqueous suspension on a steep sieve machine.
Dieser Vliesstoff soll für einen textilen Siebdruck vorbereitet werden. Die Siebdruckfarben sind ähnlich wie die Tiefdruckfarben niedrigviskos und enthalten als Lösungsmittel Toluol.This nonwoven is to be prepared for textile screen printing. Similar to gravure inks, screen printing inks are low-viscosity and contain toluene as a solvent.
In einer konventionellen Streichmasse für organische Lösungsmittel wird eine 3,5gew.-%ige Suspension des organophilen Komplexes nach Beispiel 6, die mit weiteren 5 Gew.-% eines feinen Calciumcarbonats verschnitten ist und einen Polyvinylacetat-Zusatz von 2 Gew.-% enthält, aufgestrichen. Dabei empfiehlt es sich, das Rakelstreichverfahren zu wählen, damit die großen Poren des Vliesstoffes sich schließen.In a conventional coating slip for organic solvents, a 3.5% by weight suspension of the organophilic complex according to Example 6, which is blended with a further 5% by weight of a fine calcium carbonate and contains a 2% by weight polyvinyl acetate additive, spread out. It is advisable to choose the knife coating process so that the large pores of the nonwoven material close.
Während eine toluolhaltige Siebdruckfarbe bei einem unbehandelten Vliesstoff einen Toluol-Holdout von 10 bis 15 sec. hat, wird der Holdout durch den Strich auf etwa 40 sec. verbessert. Der erzielbare Druckglanz wird erhöht und der Verbrauch an Siebdruckfarbe wird vermindert.While a toluene-containing screen printing ink has a toluene holdout of 10 to 15 seconds for an untreated nonwoven, the holdout is improved by the line to about 40 seconds. The print gloss that can be achieved is increased and the consumption of screen printing ink is reduced.
Einer Suspension von gebleichtem Nadelsulfat-Zellstoff von 4,5 Gew.-% Stoffdichte und einem Mahlgrad von 23°SR wird eine ausgequollene Na-Mg-Bentonit-Slurry mit 5 Gew.-% Feststoff zugemischt bis, auf den Zellstoff bezogen, ein 10 gew.-%iger Anteil erreicht ist.A swollen Na-Mg-bentonite slurry with 5% by weight solids is mixed into a suspension of bleached needle sulfate pulp of 4.5% by weight consistency and a freeness of 23 ° SR until a 10th, based on the pulp wt .-% share is reached.
Dann wird ein gebleichter Birkensulfatzellstoff von ebenfalls 4,5 Gew.-% Stoffdichte mit einem Mahlgrad von 40°SR dazugemischt, und zwar im Verhältnis 1:2 Nadelzellstoff zu Birkenzellstoff. Der Gehalt an Na-Mg-Bentonit beträgt nunmehr, auf Gesamtfasern berechnet, 3,3 Gew.-%.Then a bleached birch sulfate pulp of 4.5% by weight consistency with a freeness of 40 ° S R is mixed in, namely in a ratio of 1: 2 needle pulp to birch pulp. The content of Na-Mg bentonite, calculated on total fibers, is now 3.3% by weight.
In einem getrennten Lösegefäß wird eine 3 gew.-%ige Lösung der quaternären Ammoniumverbindung gemäß Beispiel 1 hergestellt.A 3% by weight solution of the quaternary ammonium compound according to Example 1 is prepared in a separate dissolving vessel.
Diese Lösung wird in einer Menge, die zum Austausch von 30 % der austauschfähigen Kationen ausreicht, unter intensiver Vermischung der Faser-Bentonit-Mischung zugerührt. Das so nach Standardmethoden erzeugte holzfreie Papier hat bei 80 g/m2 eine Bekk-Glätte von 1100 sec., eine Dichte von 1,35 g/cm2 und einen Toluol-Holdout nach der Tropfenmethode (mit Ceresrot gefärbtes Toluol) von 15 sec. gegenüber 3 sec. bei nichtbehandeltem Papier.This solution is added in an amount sufficient to exchange 30% of the exchangeable cations, with intensive mixing of the fiber-bentonite mixture. The wood-free paper thus produced using standard methods has a Bekk smoothness of 1100 sec. At 80 g / m 2 , a density of 1.35 g / cm 2 and a toluene holdout by the drop method (toluene colored with Ceres red) of 15 sec compared to 3 seconds for untreated paper.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86102140T ATE41684T1 (en) | 1985-02-22 | 1986-02-19 | PROCESS FOR IMPROVING THE HOLDOUT OF PRINTING INKS, COATINGS AND COATING COMPOUNDS ON SHEET STRUCTURES MADE OF FIBERS AND FOR IMPROVING THE DE-INKING OF THE FIBERS AND COMPOSITION FOR CARRYING OUT THE PROCESS AND SHEET STRUCTURES PRODUCED THEREFORE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3506278 | 1985-02-22 | ||
DE19853506278 DE3506278A1 (en) | 1985-02-22 | 1985-02-22 | METHOD FOR IMPROVING THE HOLDOUT OF PRINT INKS, VARNISHES AND COATING MEASURES ON FABRIC MATERIALS OF FIBERS, AND MEASURES FOR IMPLEMENTING THE METHOD AND AREA PRODUCED BY IT |
Publications (2)
Publication Number | Publication Date |
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EP0192252A1 true EP0192252A1 (en) | 1986-08-27 |
EP0192252B1 EP0192252B1 (en) | 1989-03-22 |
Family
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EP86102140A Expired EP0192252B1 (en) | 1985-02-22 | 1986-02-19 | Method for improving the holdout of printing inks, lacquers and coating compositions on sheetlike structures made of fibers and for improving the deinking of the fibers composition for implementing the method, and sheetlike structures produced therewith |
Country Status (14)
Country | Link |
---|---|
US (1) | US4867844A (en) |
EP (1) | EP0192252B1 (en) |
JP (1) | JPH0718119B2 (en) |
AT (1) | ATE41684T1 (en) |
BR (1) | BR8600732A (en) |
CA (1) | CA1273759A (en) |
DE (2) | DE3506278A1 (en) |
DK (1) | DK167939B1 (en) |
ES (1) | ES8708153A1 (en) |
FI (1) | FI84382C (en) |
GR (1) | GR860225B (en) |
NO (1) | NO171121C (en) |
YU (1) | YU26586A (en) |
ZA (1) | ZA861316B (en) |
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EP0279313A1 (en) * | 1987-02-10 | 1988-08-24 | Institut für Papier-,Zellstoff-und Fasertechnik der Technischen Universität Graz | Process for preparing a pigmentary agent suited for use in the paper-making industry, said agent improving the printability of paper or board, the agent and its use |
EP0283300A1 (en) * | 1987-03-20 | 1988-09-21 | Ecc International Limited | Paper coating |
WO1988007603A1 (en) * | 1987-04-01 | 1988-10-06 | Henkel Kommanditgesellschaft Auf Aktien | Use of lamellar silicates charged with quaternary ammonium compounds as saponifying agents in saponification processes for fixing dyes |
EP0337771A1 (en) * | 1988-04-12 | 1989-10-18 | Ecc International Limited | Paper coating |
EP0542215A1 (en) * | 1991-11-12 | 1993-05-19 | Hoechst Aktiengesellschaft | Aqueous dispersion of lamellar silicate |
DE4217779A1 (en) * | 1992-05-29 | 1993-12-02 | Sued Chemie Ag | Coating pigment |
US5298064A (en) * | 1990-12-06 | 1994-03-29 | Hoechst Aktiengesellschaft | Water-containing organophilic phylloisilicates |
EP0592789A2 (en) * | 1992-09-14 | 1994-04-20 | Rheox International, Inc. | Process for deinking wastepaper utilizing organoclays formed in situ |
EP0622490A2 (en) * | 1993-04-26 | 1994-11-02 | Rheox International, Inc. | Process for removing inorganic components that form ash on ignition and oily waste from paper during recycling |
EP0632161A1 (en) * | 1993-06-26 | 1995-01-04 | Hoechst Aktiengesellschaft | Aqueous dispersion of organophilic lamellar silicate |
EP0811719A1 (en) * | 1996-06-07 | 1997-12-10 | United Catalysts, Inc. | Coating composition for paper and paper boards containing starch and smectite clay |
EP0685539B1 (en) * | 1994-06-01 | 2001-08-29 | Clariant GmbH | Process for preparing a fine aqueous dispersion of an organophilic layered silicate |
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JP2002173892A (en) * | 2000-09-27 | 2002-06-21 | Nippon Paper Industries Co Ltd | Coated paper for gravure printing |
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US20070292569A1 (en) * | 2005-06-29 | 2007-12-20 | Bohme Reinhard D | Packaging material for food items containing permeating oils |
WO2007002896A2 (en) * | 2005-06-29 | 2007-01-04 | Graphic Packaging International, Inc. | Packaging material for food items containing permeating oils |
US8753012B2 (en) | 2006-06-29 | 2014-06-17 | Graphic Flexible Packaging, Llc | High strength packages and packaging materials |
US8826959B2 (en) | 2006-06-29 | 2014-09-09 | Graphic Packaging International, Inc. | Heat sealing systems and methods, and related articles and materials |
FR2954361B1 (en) | 2009-12-23 | 2012-06-15 | Arjo Wiggins Fine Papers Ltd | ULTRA SMOOTH AND RECYCLABLE PRINTING SHEET AND METHOD OF MANUFACTURING THE SAME |
JP6378093B2 (en) | 2012-01-13 | 2018-08-22 | アルジョ ウイグギンス フイネ パペルス リミテッド | Method for manufacturing a sheet |
EP3156540A1 (en) * | 2015-10-12 | 2017-04-19 | Omya International AG | Process for the deinking of coated paper or paperboard |
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EP0279313A1 (en) * | 1987-02-10 | 1988-08-24 | Institut für Papier-,Zellstoff-und Fasertechnik der Technischen Universität Graz | Process for preparing a pigmentary agent suited for use in the paper-making industry, said agent improving the printability of paper or board, the agent and its use |
EP0283300A1 (en) * | 1987-03-20 | 1988-09-21 | Ecc International Limited | Paper coating |
WO1988007603A1 (en) * | 1987-04-01 | 1988-10-06 | Henkel Kommanditgesellschaft Auf Aktien | Use of lamellar silicates charged with quaternary ammonium compounds as saponifying agents in saponification processes for fixing dyes |
EP0337771A1 (en) * | 1988-04-12 | 1989-10-18 | Ecc International Limited | Paper coating |
WO1989009852A1 (en) * | 1988-04-12 | 1989-10-19 | Ecc International Limited | Paper coating |
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EP0632161A1 (en) * | 1993-06-26 | 1995-01-04 | Hoechst Aktiengesellschaft | Aqueous dispersion of organophilic lamellar silicate |
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EP0685539B1 (en) * | 1994-06-01 | 2001-08-29 | Clariant GmbH | Process for preparing a fine aqueous dispersion of an organophilic layered silicate |
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Also Published As
Publication number | Publication date |
---|---|
DK82986A (en) | 1986-08-23 |
CA1273759A (en) | 1990-09-11 |
JPH0718119B2 (en) | 1995-03-01 |
ATE41684T1 (en) | 1989-04-15 |
DK167939B1 (en) | 1994-01-03 |
FI84382C (en) | 1991-11-25 |
DE3662539D1 (en) | 1989-04-27 |
FI860769A0 (en) | 1986-02-21 |
DK82986D0 (en) | 1986-02-21 |
NO171121C (en) | 1993-01-27 |
YU26586A (en) | 1987-12-31 |
BR8600732A (en) | 1986-11-04 |
EP0192252B1 (en) | 1989-03-22 |
ZA861316B (en) | 1986-10-29 |
GR860225B (en) | 1986-05-28 |
NO860662L (en) | 1986-08-25 |
ES8708153A1 (en) | 1987-09-16 |
FI84382B (en) | 1991-08-15 |
JPS6440695A (en) | 1989-02-10 |
NO171121B (en) | 1992-10-19 |
US4867844A (en) | 1989-09-19 |
ES552236A0 (en) | 1987-09-16 |
FI860769A (en) | 1986-08-23 |
DE3506278A1 (en) | 1986-08-28 |
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