EP0098368B1 - Metallized paper and process for its production - Google Patents
Metallized paper and process for its production Download PDFInfo
- Publication number
- EP0098368B1 EP0098368B1 EP19830104741 EP83104741A EP0098368B1 EP 0098368 B1 EP0098368 B1 EP 0098368B1 EP 19830104741 EP19830104741 EP 19830104741 EP 83104741 A EP83104741 A EP 83104741A EP 0098368 B1 EP0098368 B1 EP 0098368B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pigment
- coating
- weight
- parts
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000049 pigment Substances 0.000 claims abstract description 81
- 238000000576 coating method Methods 0.000 claims abstract description 78
- 239000011248 coating agent Substances 0.000 claims abstract description 75
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 19
- 239000011707 mineral Substances 0.000 claims abstract description 19
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 19
- 229920000126 latex Polymers 0.000 claims abstract description 14
- 239000004816 latex Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000008199 coating composition Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 10
- 238000001465 metallisation Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 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 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000416 hydrocolloid Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 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 1
- 239000002346 layers by function Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KMNONFBDPKFXOA-UHFFFAOYSA-N prop-2-enamide;styrene Chemical compound NC(=O)C=C.C=CC1=CC=CC=C1 KMNONFBDPKFXOA-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000004924 water-based lacquer Substances 0.000 description 1
- 239000003232 water-soluble binding agent 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
- D21H19/02—Metal coatings
- D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31703—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31989—Of wood
Definitions
- the invention relates to a metal-coated paper, in which the metal layer is applied to a cast-coated paper by direct vapor deposition, and a process for its production.
- a firmly adhering metal layer can be applied to a cast-coated paper without pre-coating by vapor deposition in a vacuum if the pigmented coating composition for the cast coating has a pH ⁇ 7 and a polymer in it as a binder Amount of at least 5% by weight is contained, in the polymerization of which at least 8% by weight, based on total monomers, was used as acrylic acid or methacrylic acid.
- the acidic pH range of the coating compound and the special polymer are indispensable for dispensing with the pre-coating during the metallization.
- the coating composition can contain 15-90% by weight of polymer containing carboxyl groups and 10-85% by weight of mineral pigment with a total solids content of 25-50% by weight.
- the applied weight is 8-12 g / m 2 , with 12 g / m 2 achieving better coverage of the paper than with 16 g / m 2 of a coating composition which contains casein and a butadiene styrene latex as a binder.
- the chrome cylinder is smoothed at temperatures of 165 ° C-212 ° C at a working speed of around 37 m / min.
- the base coating of the paper contains 52-88% by weight of inorganic pigment, 2-20% by weight of thermoplastic pigment, 5-25% by weight of a soft polymer latex with a glass transition temperature (Tg) ⁇ 21 ° C. and 5-25% by weight of one natural water-soluble binder.
- the object of the invention is to provide a metallized paper with a mirror-like metallic surface, for the metallization of which a pre-coating of the paper surface provided with a pigmented coating is not necessary and which can be produced without difficulty on the systems customary in paper finishing.
- a metallized paper the metal layer of which is applied to a cast-coated paper by evaporation in a vacuum
- the paper optionally has a pigmented layer under the casting line containing mineral pigments, latex binders and conventional additives, and is characterized in that the casting line , which was produced with a coating material having a pH value> 7, is present in an amount of 15-30 g / m 2 , at least 5 out of 100 parts by weight of the pigment contained in the cast coating are synthetic polymer pigment, the average particle diameter of 0.1 to 30 is 11 m, and for every 100 parts by weight of pigment there are 5-25 parts by weight of film-forming binder.
- the invention also encompasses a process for producing a metallized paper with a mirror-like surface, in which a pigmented coating is optionally first applied to a paper and a cast coating containing mineral pigments, latex binders and customary other additives is applied to the paper, and a metal layer is then evaporated directly in vacuo , which is characterized by the application of a pH> 7 aqueous coating composition which contains at least 5 out of 100 parts by weight of the pigments contained as syn thetic polymer pigment with an average particle diameter of 0.1-30 1 1m and for 100 parts by weight of pigment 5-25 parts by weight of film-forming binder in such an amount that after drying 10-30 g / m 2 casting line are present, drying the coating a moisture content of 5% to 15%, pressing the coated paper surface onto a drum with a high-gloss surface at a temperature of 100 ° C to 160 ° C by means of a roller and a line pressure of> 1,000 N / cm.
- the metallized paper according to the invention may have a pigmented layer under the cast coating containing mineral pigments, latex binders and conventional additives.
- This cast coat differs from the known coatings in that at least 5 out of 100 parts by weight of the pigment contained in the cast coat is synthetic polymer pigment, the average particle diameter of which is 0.1 to 30 11 m, and 5 to 25 parts by weight of film-forming binder are present per 100 parts by weight of pigment.
- the coating composition having a pH> 7 is applied in an amount such that a coating weight of 10-30 g / m 2 is present after drying.
- the combination of 93-75 parts by weight of mineral pigment with 7-25 parts by weight of synthetic polymer pigment has also proven to be suitable.
- the cast coating is preferably present in an amount of 15-26 g / m 2 , very particularly preferably a coating weight of 18-25 g / m 2. Coating amounts of 20-25 g / m 2 are also possible.
- a pigmented coating is optionally first applied to a paper, and a cast coating containing mineral pigments, latex binders and customary additives is applied to this paper, and a metal layer is then evaporated directly in vacuo.
- the aqueous coating composition has a pH> 7 and contains at least 5 out of 100 parts by weight of the pigments contained as a synthetic polymer pigment with an average particle diameter of 0.1-30 1 1m and for 100 parts by weight pigment 5-25 parts by weight of film-forming binder and customary others Additives. It is applied in such an amount that 10-30 g / m 2 casting line are present after drying.
- the coating is dried to a moisture content of 5% to 15% and then pressed with the coated paper surface onto a drum with a high-gloss surface at a temperature of 100 ° C to 160 ° C by means of a roller with a line pressure of> 1,000 N / cm.
- a procedure with drum temperatures of 120 ° C-140 ° C is particularly suitable.
- DE-A 2603155 describes a cast coating process in which a tough porous coating is first produced, which is then smoothed on the hot chrome cylinder after rewetting.
- Synthetic polymers which can be plasticized with water and have a specific ratio of film formation temperature T f to glass transition temperature Tg are therefore used as binders.
- the description states that the properties of the coating can be influenced by using hard latices with a Tg> 45 ° C.
- Polymer pigments are mentioned among the pigments and in one example a part of the mineral pigment is replaced by a polystyrene pigment with an average particle diameter of 0.5 ⁇ m in order to increase the volume of the coating for a given coat weight.
- Plastic pigments are offered in the form of stable aqueous dispersions with average particle diameters of 0.1-30 ⁇ m of the plastic pigment in certain grades by the relevant chemical industry. Plastic pigments whose average particle diameter is 0.1-1.5 ⁇ m have proven particularly successful, and particle diameters of> 0.5-1.0 ⁇ m are very particularly preferred.
- the polymer pigments are polystyrene, styrene-acrylamide copolymers, graft copolymers from styrene and acrylic acid derivatives, terpolymers from styrene, acrylonitrile and acrylic acid or derivatives, polyvinyl chloride, polyvinyl chloride copolymers, polyvinyl acetate, polyvinyl acetate copolymers, homopolymers of olefins such as ethylene, propylene, copolymers of two or more olefins, copolymers of olefins with other monomers such as styrene or unsaturated carboxylic acids such as maleic acid and the like.
- the polymer pigments can also be used in mixtures.
- urea-formaldehyde resins or melamine-formaldehyde resins are also suitable.
- the dispersions generally have a solids content of 40-60% by weight and are stabilized by means of suitable emulsifiers.
- the stabilizing auxiliaries should indeed be compatible with the customary compositions of pigmented coating compositions, so that incorporation should be possible without particular difficulty.
- coating compositions for the cast coating of paper have the property of forming a gel and solidifying under certain conditions, for example elevated temperature or pH shift.
- the gelation conditions of the paper coating composition are influenced to a considerable extent by the stabilizing agents of the plastic pigment dispersions, so that special precautions are necessary in order to be able to use plastic pigments when casting.
- An aqueous, mineral and plastic pigment which can be gelled by heat, and a coating color containing latex and possibly protein binders, is used which spontaneously coagulates or gels at and above a defined temperature without the need to substantially remove water, e.g. by evaporation or penetration into the base paper.
- peptizing and dispersing agents in the form of protective hydrocolloids, which can simultaneously perform binding tasks, and in the form of known polyelectrolytes (e.g. polyacrylates, polyphosphates, citrates, tartrates), possibly supported synergistically by the use of two- or polyvalent metal cations , in combination with the use of a suitable [OH] ion concentration, which also has a synergistic effect, can be used individually or in combination with one another to generate the coagulation readiness of the coating composition.
- polyelectrolytes e.g. polyacrylates, polyphosphates, citrates, tartrates
- plastic pigments can also be used alone or in combination with mineral pigments in coating compositions intended for cast coating of paper.
- a small, but also a high proportion of plastic pigment is possible, although under the conditions of casting, the requirement to avoid temperatures at which the plastic pigment softens is not met.
- Plasticizers which can be used in the coating composition are conventional plasticizers, such as dibutyl phthalate, dioctyl phthalate, epoxy plasticizers and other substances suitable for plasticizing synthetic polymers.
- the cast coating may contain up to 25% by weight, based on synthetic polymer pigment, preferably up to 15% by weight of plasticizer. Plasticizer contents of 5 to 10% by weight, based on synthetic polymer pigment, are very particularly preferred.
- the partially dried paper coating is applied to a hot cylinder with a high-gloss surface and pressed on by means of a roller, the coating being plasticized under the temperature and pressure conditions, so that the surface is an image of the highly polished surface of the cylinder.
- the cast-coated paper surface can be improved to such an extent that direct vapor deposition of this surface is possible and a metallized paper results that has a mirror-gloss surface with a metallic character having. This result is completely surprising.
- a plasticizer additive is not required per se, however, the plasticizability of the coating can be improved by using plasticizer, so that at a given temperature and a given line pressure, a higher web speed on the hot chrome cylinder is possible due to the higher plasticity of the coating.
- the addition of plasticizers also allows the temperature of the chrome cylinder to be chosen lower and / or the pressure exerted by a roller on the web to be reduced.
- the composition of the cast coating slip according to the invention makes it possible to adapt the actual casting coating process to the conditions of existing systems in such a way that the smooth and closed surface required for direct metal vapor deposition is achieved.
- metals are suitable as metals for metallizing, such as aluminum, nickel, chromium, copper, but also nobler metals such as gold or silver can be applied by vacuum evaporation.
- metals for metallizing such as aluminum, nickel, chromium, copper, but also nobler metals such as gold or silver can be applied by vacuum evaporation.
- aluminum, nickel or copper are preferably used for reasons of cost.
- the known, frequently described systems are used for direct metallization, in which the coating is applied by depositing metal vapors which are generated in a high vacuum.
- the thickness of the precipitate depends on the flow rate and metal evaporation capacity and is extremely ge ring. Usually, coating thicknesses of 0.01-0.05gm are expected.
- the metal layer can also be covered with a protective, color or functional layer. Due to the lack of a lacquer layer under the metal, the paper according to the invention retains the paper character and properties such as rigidity and behavior in the event of climate change correspond to those of paper. In contrast, the existing lacquer layer which has been customary in the case of known papers metallized in the direct process, on the other hand, changes the paper properties, in particular the flatness behavior, significantly.
- the paper according to the invention can also be printed better than pre-coated papers because the blocking lacquer layer does not delay the drying of the ink. When used as labels for bottles, the detachability in cleaning systems is better than that of pre-coated papers because the paper moistens more easily and quickly.
- a pigmented precoat is first applied to a paper web of a conventional base paper with a composition of 50 g / m 2 and dried.
- This base coating with an application weight of 8 g / m 2 has a customary composition of 80-90 parts by weight of mineral pigment and 10-20 parts by weight of conventional binders such as polymer latices, casein, starch, polyvinyl alcohol or the like. Clay, calcium carbonate serve as pigments. Zinc oxide, BaS0 4 .
- a coating composition of the following composition is applied to this dried coating in a quantity of 20 g / m2 (after drying):
- the coating composition applied by means of conventional aggregates is dried to a moisture content of 8% and then pressed onto a cylinder with a high-gloss chrome-plated surface at a temperature of 150 ° C. and a line pressure of 1200 N / cm by means of a roller.
- the web speed is 150 m / min.
- the web running from the chrome cylinder is wound up and then provided with an aluminum layer in a vacuum metallization system.
- the moisture content before metallizing the paper is 2.5%. After metallizing, the moisture content is adjusted to 6-7% by conditioning.
- the paper obtained has a mirror-like metallic surface.
- mineral pigments such as kaolin, Ca Co 3 , BaS0 4 , ZnO, satin white and the like can also be used as mineral pigments in the cast coating instead of clay.
- a coating slip of the following composition is applied in a quantity of 25 g / m2 to a coating base paper of conventional composition with a weight per unit area of 5 g / m2:
- the coating composition applied by means of conventional aggregates is dried to a moisture content of 8% and then pressed onto a cylinder with a high-gloss chrome-plated surface at a temperature of 150 ° C. and a line pressure of 1200 N / cm by means of a roller.
- the web speed is 150 m / min.
- the web running from the chrome cylinder is wound up and then provided with an aluminum layer in a vacuum metallization system.
- the moisture content before metallizing the paper was 2.5%. After metallizing, the moisture content is adjusted to 6-7% by conditioning.
- the paper obtained has a mirror-like metallic surface.
Landscapes
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Gegenstand der Erfindung ist ein metallbeschichtetes Papier, bei dem die Metallschicht durch direktes Aufdampfen auf ein gussgestrichenes Papier aufgebracht ist und ein Verfahren zu seiner Herstellung.The invention relates to a metal-coated paper, in which the metal layer is applied to a cast-coated paper by direct vapor deposition, and a process for its production.
In US A 23113888 ist beschrieben, dass man ein Papier, auf das eine unpigmentierte Beschichtung aus einem Polymerlatex, der bei Raumtemperatur nicht filmbildend ist, jedoch bei erhöhter Temperatur einen Film ausbildet, mittels Gussstreichens aufgebracht worden ist, direkt metallisieren kann. Das Polymere weist eine Glasumwandlungstemperatur (Tg) von 0-93°C auf und bei 88°C bis 99°C wird die Schicht unter leichtem Druck klebend (Blocken). Das Auftragsgewicht beträgt 7,3-14,5 g/m2. Über den pH-Wert des für das Gussstreichen verwendeten Polymerlateces sind keine Angaben enthalten. Die zum Glätten der Beschichtung am Chromzylinder angewandte Temperatur beträgt 71-99°C. Im Grunde genommen handelt es sich um eine Vorlackierung unter Verwendung eines unpigmentierten Lackes auf wässriger Basis, dessen Oberfläche durch die Gussstreichtechnik geglättet wird, insbesondere dann, wenn vorher noch eine pigmentierte Grundbeschichtung aufgebracht wurde.It is described in US Pat. No. 2,311,3888 that a paper to which an unpigmented coating made of a polymer latex, which does not form a film at room temperature but forms a film at elevated temperature, can be metallized directly by means of cast coating. The polymer has a glass transition temperature (Tg) of 0-93 ° C and at 88 ° C to 99 ° C the layer becomes tacky under pressure (blocking). The application weight is 7.3-14.5 g / m 2 . No information is given on the pH of the polymer latex used for cast coating. The temperature used to smooth the coating on the chrome cylinder is 71-99 ° C. Basically, it is a pre-coating using an unpigmented water-based lacquer, the surface of which is smoothed by the cast coating technique, especially if a pigmented base coat has been applied beforehand.
Aus GB-A 992320 ist es bekannt, dass auf ein gussgestrichenes Papier ohne Vorlackierung durch Bedampfen im Vakuum eine festhaftende Metallschicht aufgebracht werden kann, wenn die pigmentierte Beschichtungsmasse für den Gussstrich einen pH-Wert <7 aufweist und in ihr als Bindemittel ein Polymer in einer Menge von mindestens 5 Gew.% enthalten ist, bei dessen Polymerisation mindestens 8 Gew.% bezogen auf Gesamtmonomere als Acrylsäure oder Methacrylsäure verwendet wurde. Der saure pH-Bereich der Beschichtungsmasse und das spezielle Polymere sind unabdingbar für den Verzicht auf die Vorlackierung bei dem Metallisieren. Die Beschichtungszusammensetzung kann an Feststoffen 15-90 Gew.% carboxylguppenhaltiges Polymer und 10-85 Gew.% mineralisches Pigment enthalten bei einem Gesamtfeststoffgehalt von 25-50 Gew.%. Als Auftragsgewicht sind 8-12 g/m2 angegeben, wobei mit 12 g/m2 eine bessere Abdeckung des Papieres erreicht wird als mit 16 g/m2 einer Beschichtungsmasse, die als Bindemittel Casein und einen Butadien-Styrollatex enthält. Die Glättung am Chromzylinder erfolgt bei Temperaturen von 165°C-212°C bei einer Arbeitsgeschwindigkeit von etwa 37 m/min.From GB-A 992320 it is known that a firmly adhering metal layer can be applied to a cast-coated paper without pre-coating by vapor deposition in a vacuum if the pigmented coating composition for the cast coating has a pH <7 and a polymer in it as a binder Amount of at least 5% by weight is contained, in the polymerization of which at least 8% by weight, based on total monomers, was used as acrylic acid or methacrylic acid. The acidic pH range of the coating compound and the special polymer are indispensable for dispensing with the pre-coating during the metallization. The coating composition can contain 15-90% by weight of polymer containing carboxyl groups and 10-85% by weight of mineral pigment with a total solids content of 25-50% by weight. The applied weight is 8-12 g / m 2 , with 12 g / m 2 achieving better coverage of the paper than with 16 g / m 2 of a coating composition which contains casein and a butadiene styrene latex as a binder. The chrome cylinder is smoothed at temperatures of 165 ° C-212 ° C at a working speed of around 37 m / min.
Diese metallisierten Papiere, bei denen die Metallschicht direkt auf ein gussgestrichenes Papier aufgebracht wurde, haben sich in der Praxis nicht durchgesetzt, weil trotz der scheinbar glatten gussgestrichenen Oberfläche nach dem Bedampfen mit Metall der geforderte Spiegelglanz der Oberfläche nicht erreicht werden konnte.These metallized papers, in which the metal layer was applied directly to a cast-coated paper, have not prevailed in practice because, despite the seemingly smooth cast-coated surface, the required mirror finish of the surface could not be achieved after vapor deposition with metal.
In US-A 3463659 ist beschrieben, dass eine Vorlackierung eines scharf satinierten gestrichenen Papieres vor dem Aufdampfen des Metalles erforderlich ist, um die, trotz Satinage des gestrichenen Papieres, noch vorhandene Oberflächenrauhigkeit der Beschichtung auszugleichen. Die Grundbeschichtung des Papiers enthält 52-88 Gew.% anorganisches Pigment, 2-20 Gew.% thermoplastisches Pigment, 5-25 Gew.% eines weichen Polymerlatex mit einer Glasumwandungstemperatur (Tg) <21°C und 5-25 Gew.% eines natürlichen wasserlöslichen Bindemittels.In US-A 3463659 it is described that a pre-coating of a sharply satined coated paper is required before the metal is evaporated in order to compensate for the surface roughness of the coating that is still present, despite the coated paper being satinized. The base coating of the paper contains 52-88% by weight of inorganic pigment, 2-20% by weight of thermoplastic pigment, 5-25% by weight of a soft polymer latex with a glass transition temperature (Tg) <21 ° C. and 5-25% by weight of one natural water-soluble binder.
O. Helgesson hat in seiner Veröffentlichung über metallisierte Papiere in Coating 13/10; Seite 258/59 (1980), die Direktmetallisierung und die Transfermetallisierung verglichen und darauf hingewiesen, dass die auch bei Verwendung hochwertiger gestrichener Papiere erforderliche Lackierung wegen der Umweltbelastung durch die Lösungsmittel ein erheblicher Nachteil ist.In his publication on metallized papers in coating 13/10, O. Helgesson; Page 258/59 (1980), compared the direct metallization and the transfer metallization and pointed out that the coating required even when using high-quality coated paper is a considerable disadvantage because of the environmental impact of the solvents.
Der Verfahrensschritt des Lackierens der Papieroberfläche vor dem Metallisieren stellt aber nicht nur einen kostenaufwendigen zusätzlichen Schritt dar, sondern es ist in der Vakuumanlage auch eine erhöhte Pumpleistung erforderlich, weil bei Evakuieren aus dem gestrichenen und lackierten Papier stets noch Lösungsmittelreste ausgasen. Ausserdem sind besondere Vorkehrungen notwendig, um diese Lösungsmittel zu beseitigen, denn die früher übliche Emission in die Atmosphäre ist durch die verschärften gesetzlichen Bestimmungen untersagt.The process step of varnishing the paper surface before metallizing is not only a costly additional step, but also an increased pumping capacity is required in the vacuum system, because solvent residues always outgas from the coated and varnished paper during evacuation. In addition, special precautions are necessary to remove these solvents, because the previously common emission into the atmosphere is prohibited by the stricter legal provisions.
Aufgabe der Erfindung ist es, ein metallisiertes Papier mit spiegelglänzender metallischer Oberfläche zu schaffen, für dessen Metallisierung eine Vorlackierung der mit einer pigmentierten Beschichtung versehenen Papieroberfläche nicht erforderlich ist und das auf den bei der Papierveredlung üblichen Anlagen ohne Schwierigkeiten herstellbar ist.The object of the invention is to provide a metallized paper with a mirror-like metallic surface, for the metallization of which a pre-coating of the paper surface provided with a pigmented coating is not necessary and which can be produced without difficulty on the systems customary in paper finishing.
Diese Aufgabe wird gelöst durch ein metallisiertes Papier, dessen Metallschicht durch Aufdampfen im Vakuum auf ein gussgestrichenes Papier aufgebracht ist, das Papier ggf. eine pigmentierte Schicht unter dem mineralische Pigmente, Latexbindemittel und übliche Zusatzstoffe enthaltenden Gussstrich aufweist und das dadurch gekennzeichnet ist, dass der Gussstrich, der mit einer einen pH-Wert >7 aufweisenden Beschichtungsmasse hergestellt wurde, in einer Menge von 15-30 g/m2 vorhanden ist, mindestens 5 von 100 Gewichtsteilen des im Gussstrich enthaltenen Pigments synthetisches Polymerpigment sind, dessen durschnittlicher Teilchendurchmesser 0,1 bis 30 11m beträgt, und auf 100 Gewichtsteile Pigment 5-25 Gewichtsteile filmbildendes Bindemittel vorhanden sind.This object is achieved by a metallized paper, the metal layer of which is applied to a cast-coated paper by evaporation in a vacuum, the paper optionally has a pigmented layer under the casting line containing mineral pigments, latex binders and conventional additives, and is characterized in that the casting line , which was produced with a coating material having a pH value> 7, is present in an amount of 15-30 g / m 2 , at least 5 out of 100 parts by weight of the pigment contained in the cast coating are synthetic polymer pigment, the average particle diameter of 0.1 to 30 is 11 m, and for every 100 parts by weight of pigment there are 5-25 parts by weight of film-forming binder.
Die Erfindung umfasst auch ein Verfahren zum Herstellen eines metallisierten Papiers mit spiegelglänzender Oberfläche, bei dem man auf ein Papier ggf. zunächst eine pigmentierte Beschichtung und auf diese einen mineralische Pigmente, Latexbindemittel und übliche weitere Zusatzstoffe enthaltenden Gussstrich aufbringt und dann im Vakuum eine Metallschicht direkt aufdampft, das gekennzeichnet ist durch Aufbringen einer einen pH-Wert >7 aufweisenden wässrigen Beschichtungsmasse, die mindestens 5 von 100 Gewichtsteilen der enthaltenen Pigmente als synthetisches Polymerpigment mit einem durchschnittlichen Teilchendurchmesser von 0,1-30 11m und auf 100 Gewichtsteile Pigment 5-25 Gewichtsteile filmbildendes Bindemittel enthält in einer solchen Menge, dass nach dem Trocknen 10-30 g/m2 Gussstrich vorhanden sind, Trocknen der Beschichtung auf einen Feuchtigkeitsgehalt von 5% bis 15%, Anpressen der beschichteten Papieroberfläche an eine Trommel mit hochglänzender Oberfläche bei einer Temperatur von 100°C bis 160°C mittels einer Walze und einem Liniendruck von > 1.000 N/cm.The invention also encompasses a process for producing a metallized paper with a mirror-like surface, in which a pigmented coating is optionally first applied to a paper and a cast coating containing mineral pigments, latex binders and customary other additives is applied to the paper, and a metal layer is then evaporated directly in vacuo , which is characterized by the application of a pH> 7 aqueous coating composition which contains at least 5 out of 100 parts by weight of the pigments contained as syn thetic polymer pigment with an average particle diameter of 0.1-30 1 1m and for 100 parts by weight of pigment 5-25 parts by weight of film-forming binder in such an amount that after drying 10-30 g / m 2 casting line are present, drying the coating a moisture content of 5% to 15%, pressing the coated paper surface onto a drum with a high-gloss surface at a temperature of 100 ° C to 160 ° C by means of a roller and a line pressure of> 1,000 N / cm.
Völlig überraschend wurde gefunden, dass entgegen der in jüngsten Veröffentlichungen immer wieder vertretenen Auffassung, dass bei der Direktmetallisierung von Papier eine Vorlackierung der Papieroberfläche erforderlich ist, es möglich ist, eine Oberfläche mit Spiegelglanz und metallischem Charakter zu schaffen, ohne eine Vorlackierung der Papieroberfläche mit Lakken auf Basis organischer Lösungsmittel.Completely surprisingly, it was found that, contrary to the view that has repeatedly been used in recent publications, that in the direct metallization of paper, a pre-coating of the paper surface is required, it is possible to create a surface with a mirror finish and metallic character, without pre-coating the paper surface with lacquers based on organic solvents.
Das erfindungsgemässe metallisierte Papier, dessen Metallschicht durch Aufdampfen im Vakuum auf ein gussgestrichenes Papier aufgebracht ist, weist ggf. eine pigmentierte Schicht unter dem mineralischen Pigmente, Latexbindemittel und übliche Zusatzstoffe enthaltenden Gussstrich auf.The metallized paper according to the invention, the metal layer of which is applied to a cast-coated paper by evaporation in vacuo, may have a pigmented layer under the cast coating containing mineral pigments, latex binders and conventional additives.
Dieser Gussstrich unterscheidet sich von den bekannten Beschichtungen dadurch, dass mindestens 5 von 100 Gewichtsteilen des im Gussstrich enthaltenen Pigmentes synthetisches Polymerpigment, dessen durchschnittlicher Teilchendurchmesser 0,1 bis 30 11m beträgt, und auf 100 Gewichtsteile Pigment 5-25 Gewichtsteile filmbildendes Bindemittel vorhanden sind.This cast coat differs from the known coatings in that at least 5 out of 100 parts by weight of the pigment contained in the cast coat is synthetic polymer pigment, the average particle diameter of which is 0.1 to 30 11 m, and 5 to 25 parts by weight of film-forming binder are present per 100 parts by weight of pigment.
Die einen pH-Wert >7 aufweisende Beschichtungsmasse wird in einer solchen Menge aufgetragen, dass nach dem Trocknen ein Beschichtungsgewichtvon 10-30 g/m2 vorhanden ist.The coating composition having a pH> 7 is applied in an amount such that a coating weight of 10-30 g / m 2 is present after drying.
Vorzugsweise sind 95-20 Gewichtsteile mineralisches Pigment und 5-80 Gewichtsteile synthetisches Polymerpigment miteinander kombiniert. Als geeignet hat sich auch die Kombination von 93-75 Gewichtsteilen mineralisches Pigment mit 7-25 Gewichtsteilen synthetisches Polymerpigment erwiesen.Preferably 95-20 parts by weight of mineral pigment and 5-80 parts by weight of synthetic polymer pigment are combined. The combination of 93-75 parts by weight of mineral pigment with 7-25 parts by weight of synthetic polymer pigment has also proven to be suitable.
Vorzugsweise ist der Gussstrich in einer Menge von 15-26 g/m2 vorhanden, ganz besonders bevorzugt ist ein Beschichtungsgewicht von 18-25 g/m2. Auch Beschichtungsmengen von 20-25 g/m2 sind möglich.The cast coating is preferably present in an amount of 15-26 g / m 2 , very particularly preferably a coating weight of 18-25 g / m 2. Coating amounts of 20-25 g / m 2 are also possible.
Bei den erfindungsgemässen Verfahren zum Herstellen eines metallisierten Papieres mit spiegelglänzender Oberfläche bringt man auf ein Papier ggf. zunächst eine pigmentierte Beschichtung und auf diese einen mineralische Pigmente, Latexbindemittel und übliche Zusatzstoffe enthaltenden Gussstrich auf und dampft dann im Vakuum eine Metallschicht direkt auf.In the method according to the invention for producing a metallized paper with a mirror-like surface, a pigmented coating is optionally first applied to a paper, and a cast coating containing mineral pigments, latex binders and customary additives is applied to this paper, and a metal layer is then evaporated directly in vacuo.
Die wässrige Beschichtungsmasse weist einen pH-Wert >7 auf und enthält mindestens 5 von 100 Gewichtsteilen der enthaltenen Pigmente als synthetisches Polymerpigment mit einem durchschnittlichen Teilchendurchmesser von 0,1-30 11m und auf 100 Gewichtsteile Pigment 5-25 Gewichtsteile filmbildendes Bindemittel und übliche weitere Zusatzstoffe. Sie wird in einer solchen Menge aufgetragen, dass nach dem Trocknen 10-30 g/m2 Gussstrich vorhanden sind. Die Beschichtung wird auf einen Feuchtigkeitsgehalt von 5% bis 15% getrocknet und dann mit der beschichteten Papieroberfläche an eine Trommel mit hochglänzender Oberfläche bei einer Temperatur von 100°C bis 160°C mittels einer Walze mit einem Liniendruck von > 1.000 N/cm angepresst. Besonders geeignet ist eine Verfahrensweise mit Trommeltemperaturen von 120°C-140°C.The aqueous coating composition has a pH> 7 and contains at least 5 out of 100 parts by weight of the pigments contained as a synthetic polymer pigment with an average particle diameter of 0.1-30 1 1m and for 100 parts by weight pigment 5-25 parts by weight of film-forming binder and customary others Additives. It is applied in such an amount that 10-30 g / m 2 casting line are present after drying. The coating is dried to a moisture content of 5% to 15% and then pressed with the coated paper surface onto a drum with a high-gloss surface at a temperature of 100 ° C to 160 ° C by means of a roller with a line pressure of> 1,000 N / cm. A procedure with drum temperatures of 120 ° C-140 ° C is particularly suitable.
Der Ersatz von mineralischen Pigmenten durch sogenannte Plastikpigmente (synthetische Polymere in Teilchenform) ist bekannt. So ist in DE-B 1926853 eine Papierstreichmasse beschrieben, die ein Pigment und ein Pigmentbindemittel in wässriger Dispersion enthält, wobei wenigstens ein Teil des Pigments in Form diskreter kugelförmiger Teilchen aus einem synthetischen organischen Polymeren vorliegt. Das Polymerpigment ist unter den Bedingungen des Aufbringens der Beschichtung und des Fertigbearbeitens nicht filmbildend. In US-A 3 819 557 ist für ein Polymerpigment auf Styrolbasis ausdrücklich angegeben, dass eine Verbesserung der Opazität, Weisse, Glanz und Bedruckbarkeit nur dann erreicht werden kann, wenn das Glätten des Striches durch Satinage unterhalb der Erweichungstemperatur des Polymerpigmentes erfolgt.The replacement of mineral pigments with so-called plastic pigments (synthetic polymers in particle form) is known. DE-B 1926853 describes a paper coating slip which contains a pigment and a pigment binder in aqueous dispersion, at least part of the pigment being in the form of discrete spherical particles made from a synthetic organic polymer. The polymer pigment is not film-forming under the conditions of applying the coating and finishing. For a styrene-based polymer pigment, US Pat. No. 3,819,557 expressly states that an improvement in opacity, whiteness, gloss and printability can only be achieved if the coating is smoothed by satinizing below the softening temperature of the polymer pigment.
In DE-A 2603155 ist ein Gussstreichverfahren beschrieben, bei dem zunächst ein zäher poröser Strich erzeugt wird, der nach Rückfeuchten dann am heissen Chromzylinder geglättet wird. Als Bindemittel werden deshalb mit Wasser plastifizierbare synthetische Polymere, die ein bestimmtes Verhältnis von Filmbildungstemperatur Tf zu Glasumwandlungstemperatur Tg aufweisen, verwendet. In der Beschreibung ist angegeben, dass man die Eigenschaften der Beschichtung durch Mitverwendung harter Latices mit einem Tg>45°C beeinflussen kann. Unter den Pigmenten sind Polymerpigmente erwähnt und in einem Beispiel wird ein Teil des mineralischen Pigments durch ein Polystyrolpigment mit einem durchschnittlichen Teilchendurchmesser von 0,5 µm ersetzt, um das Volumen der Beschichtung bei gegebenen Strichgewicht zu erhöhen.DE-A 2603155 describes a cast coating process in which a tough porous coating is first produced, which is then smoothed on the hot chrome cylinder after rewetting. Synthetic polymers which can be plasticized with water and have a specific ratio of film formation temperature T f to glass transition temperature Tg are therefore used as binders. The description states that the properties of the coating can be influenced by using hard latices with a Tg> 45 ° C. Polymer pigments are mentioned among the pigments and in one example a part of the mineral pigment is replaced by a polystyrene pigment with an average particle diameter of 0.5 μm in order to increase the volume of the coating for a given coat weight.
Plastikpigmente werden in Form stabiler wässriger Dispersionen mit durchschnittlichen Teilchendurchmessern von 0,1-30 µm des Plastikpigments in bestimmten Abstufungen von der einschlägigen chemischen Industrie angeboten. Besonders bewährt haben sich Plastikpigmente, deren durchschnittlicher Teilchendurchmesser 0,1-1,5 11m beträgt, ganz besonders bevorzugt sind Teilchendurchmesser von >0,5-1,0 µm. Bei den Polymerpigmenten handelt es sich um Polystyrol, Styrol-Acrylamid-Copolymere, Pfropf-Copolymere aus Styrol und Acrylsäurederivaten, Terpolymere aus Styrol, Acrylnitril und Acrylsäure oder -derivaten, Polyvinylchlorid, Polyvinylchlorid-Copolymeren, Polyvinylacetat, Polyvinylacetat-Copolymere, Homopolymere von Olefinen wie Äthylen, Propylen, Copolymere von zwei oder mehr Olefinen, Copolymere von Olefinen mit anderen Monomeren wie Styrol oder ungesättigten Carbonsäuren wie Maleinsäure und dergl. Die Polymerpigmente können auch in Mischungen verwendet werden. Neben den Thermoplastischen Polymerpigmenten sich auch Harnstoff-Formaldehydharze oder Melamin-Formaldehydharze geeignet.Plastic pigments are offered in the form of stable aqueous dispersions with average particle diameters of 0.1-30 µm of the plastic pigment in certain grades by the relevant chemical industry. Plastic pigments whose average particle diameter is 0.1-1.5 μm have proven particularly successful, and particle diameters of> 0.5-1.0 μm are very particularly preferred. The polymer pigments are polystyrene, styrene-acrylamide copolymers, graft copolymers from styrene and acrylic acid derivatives, terpolymers from styrene, acrylonitrile and acrylic acid or derivatives, polyvinyl chloride, polyvinyl chloride copolymers, polyvinyl acetate, polyvinyl acetate copolymers, homopolymers of olefins such as ethylene, propylene, copolymers of two or more olefins, copolymers of olefins with other monomers such as styrene or unsaturated carboxylic acids such as maleic acid and the like. The polymer pigments can also be used in mixtures. In addition to the thermoplastic polymer pigments, urea-formaldehyde resins or melamine-formaldehyde resins are also suitable.
Die Dispersionen haben in der Regel einen Feststoffgehalt von 40-60 Gew.% und sind mittels geeigneter Emulgatoren stabilisiert. Die stabilisierenden Hilfsstoffe sollen zwar mit den üblichen Zusammensetzungen von pigmentierten Beschichtungszusammensetzungen verträglich sein, so dass ein Einarbeiten ohne besondere Schwierigkeiten möglich sein soll.The dispersions generally have a solids content of 40-60% by weight and are stabilized by means of suitable emulsifiers. The stabilizing auxiliaries should indeed be compatible with the customary compositions of pigmented coating compositions, so that incorporation should be possible without particular difficulty.
Beschichtungszusammensetzungen für das Gussstreichen von Papier haben jedoch die Eigenschaft, unter bestimmten Bedingungen, beispielsweise erhöhter Temperatur oder pH-Wertverschiebung ein Gel zu bilden und sich zu verfestigen. Die Gelierungsbedingungen der Papierbeschichtungsmasse werden jedoch in erheblichem Masse durch die Stabilisierungsmittel der Plastikpigmentdispersionen beeinflusst, so dass besondere Vorkehrungen erforderlich sind, um Plastikpigmente beim Gussstreichen verwenden zu können.However, coating compositions for the cast coating of paper have the property of forming a gel and solidifying under certain conditions, for example elevated temperature or pH shift. However, the gelation conditions of the paper coating composition are influenced to a considerable extent by the stabilizing agents of the plastic pigment dispersions, so that special precautions are necessary in order to be able to use plastic pigments when casting.
Es wird eine durch Wärme gelierbare wässrige, mineralische und Plastikpigment sowie Latex-und ggf. Proteinbindemittel enthaltende, Streichfarbe verwendet, die spontan koaguliert oder geliert bei und oberhalb einer definierten Temperatur, ohne dass Wasser substantiell entzogen werden muss, z.B. durch Verdampfung oder Penetration in das Basispapier.An aqueous, mineral and plastic pigment which can be gelled by heat, and a coating color containing latex and possibly protein binders, is used which spontaneously coagulates or gels at and above a defined temperature without the need to substantially remove water, e.g. by evaporation or penetration into the base paper.
Die massvollen Anwendungen von Peptisations- und Dispergiermitteln in Form von Schutz-Hydrokolloiden, die gleichzeitig Binderaufgaben erfüllen können, sowie in Form von Polyelektrolyten bekannter Art (z.B. Polyacrylate Polyphosphate, Citrate, Tartrate), ggf. synergistisch unterstützt durch die Anwendung zwei- oder polyvalenter Metallkationen, in Kombination mit der Anwendung eines ebenfalls synergistisch wirkenden geeigneten [OH]-lonenkonzentration können jeweils einzeln oder in Kombination miteinander zur Erzeugung der Koagulationsbereitschaft der Beschichtungszusammensetzung genutzt werden.The moderate applications of peptizing and dispersing agents in the form of protective hydrocolloids, which can simultaneously perform binding tasks, and in the form of known polyelectrolytes (e.g. polyacrylates, polyphosphates, citrates, tartrates), possibly supported synergistically by the use of two- or polyvalent metal cations , in combination with the use of a suitable [OH] ion concentration, which also has a synergistic effect, can be used individually or in combination with one another to generate the coagulation readiness of the coating composition.
Es wurde gefunden, dass sich bestimmte Plastikpigmente auch in zum Gussstreichen von Papier bestimmten Beschichtungszusammensetzungen allein oder in Kombination mit mineralischen Pigmenten verwenden lassen. Es ist ein geringer, aber auch ein hoher Anteil an Plastikpigment möglich, obwohl unter den Bedingungen des Gussstreichens die Forderung, nach Vermeidung von Temperaturen, bei denen das Plastikpigment erweicht, nicht erfüllt sind.It has been found that certain plastic pigments can also be used alone or in combination with mineral pigments in coating compositions intended for cast coating of paper. A small, but also a high proportion of plastic pigment is possible, although under the conditions of casting, the requirement to avoid temperatures at which the plastic pigment softens is not met.
Im Gegenteil, es hat sich als geeignet erwiesen, der Papierbeschichtungsmasse noch, die Plastikpigmente weichmachende Substanzen zuzusetzen, um die Filmbildungstemperatur der in der Beschichtung enthaltenen Kombination Bindemittel und Plastikpigmente zu erniedrigen.On the contrary, it has proven to be suitable to add plasticizing substances to the paper coating composition in order to lower the film-forming temperature of the combination of binder and plastic pigments contained in the coating.
Als Weichmacher können in der Beschichtungsmasse übliche Weichmacher wie Dibutylphthalat, Dioctylphthalat, Epoxyweichmacher und andere für das Weichmachen von synthetischen Polymeren geeignete Stoffe eingesetzt werden.Plasticizers which can be used in the coating composition are conventional plasticizers, such as dibutyl phthalate, dioctyl phthalate, epoxy plasticizers and other substances suitable for plasticizing synthetic polymers.
Der Gussstrich kann bis zu 25 Gew.%, bezogen auf synthetisches Polymerpigment, bevorzugt bis zu 15 Gew.% Weichmacher enthalten. Ganz besonders bevorzugt sind Weichmachergehalte von 5 bis 10 Gew.% bezogen auf synthetisches Poiymerpigment.The cast coating may contain up to 25% by weight, based on synthetic polymer pigment, preferably up to 15% by weight of plasticizer. Plasticizer contents of 5 to 10% by weight, based on synthetic polymer pigment, are very particularly preferred.
Beim Gussstreichen wird die teilweise getrocknete Papierbeschichtung an einen heissen Zylinder mit hochglänzender Oberfläche angelegt und mittels einer Walze angepresst, wobei unter den Temperatur- und Druckbedingungen eine Plastifizierung der Beschichtung erfolgt, so dass die Oberfläche eine Abbildung der hochglanzpolierten Oberfläche des Zylinders ist. Durch den Einsatz eines Polymerpigmentes in der Papierbeschichtung und Anwendung von Temperaturen oberhalb des Erweichungspunktes der Polymerpigmente und entsprechendem Druck lässt sich die gussgestrichene Papieroberfläche so stark verbessern, dass ein direktes Bedampfen dieser Oberfläche möglich ist und ein metallisiertes Papier resultiert, das eine spiegelglänzende Oberfläche mit metallischem Charakter aufweist. Dieses Ergebnis ist völlig überraschend.When casting, the partially dried paper coating is applied to a hot cylinder with a high-gloss surface and pressed on by means of a roller, the coating being plasticized under the temperature and pressure conditions, so that the surface is an image of the highly polished surface of the cylinder. By using a polymer pigment in the paper coating and applying temperatures above the softening point of the polymer pigments and appropriate pressure, the cast-coated paper surface can be improved to such an extent that direct vapor deposition of this surface is possible and a metallized paper results that has a mirror-gloss surface with a metallic character having. This result is completely surprising.
Ein Weichmacherzusatz ist an sich nicht erforderlich, jedoch lässt sich durch den Einsatz von Weichmacher die Plastifizierbarkeit des Striches verbessern, so dass bei vorgegebener Temperatur und vorgegebenem Liniendruck in Folge der höheren Plastizität des Striches eine höhere Bahngeschwindigkeit am heissen Chromzylinder möglich ist. Andererseits ermöglicht der Zusatz von Weichmachern auch, die Temperatur des Chromzylinders niedriger zu wählen und/oder den von einer Walze ausgeübten Druck auf die Bahn zu verringern. Durch die erfindungsgemässe Zusammensetzung der Gussstreichmasse ist es also möglich, das eigentliche Gussstreichverfahren an die Gegebenheiten bestehender Anlagen so anzupassen, dass die für die direkte Metallbedampfung erforderliche glatte und geschlossene Oberfläche erreicht wird.A plasticizer additive is not required per se, however, the plasticizability of the coating can be improved by using plasticizer, so that at a given temperature and a given line pressure, a higher web speed on the hot chrome cylinder is possible due to the higher plasticity of the coating. On the other hand, the addition of plasticizers also allows the temperature of the chrome cylinder to be chosen lower and / or the pressure exerted by a roller on the web to be reduced. The composition of the cast coating slip according to the invention makes it possible to adapt the actual casting coating process to the conditions of existing systems in such a way that the smooth and closed surface required for direct metal vapor deposition is achieved.
Als Metalle zum Metallisieren sind verschiedene Metalle geeignet, wie Aluminium, Nickel, Chrom, Kupfer, aber auch edlere Metalle wie Gold oder Silber können durch Aufdampfen im Vakuum aufgebracht werden. Aus Kostengründen werden vorzugsweise jedoch Aluminium, Nickel oder Kupfer verwendet.Various metals are suitable as metals for metallizing, such as aluminum, nickel, chromium, copper, but also nobler metals such as gold or silver can be applied by vacuum evaporation. However, aluminum, nickel or copper are preferably used for reasons of cost.
Für die direkte Metallisierung werden die bekannten, häufig beschriebenen Anlagen verwendet, bei denen man die Beschichtung durch Niederschlagen von Metalldämpfen, die im Hochvakuum erzeugt werden, aufbringt.The known, frequently described systems are used for direct metallization, in which the coating is applied by depositing metal vapors which are generated in a high vacuum.
Die Dicke des Niederschlages hängt von der Durchlaufgeschwindigkeit und Metallverdampfungskapazität ab und ist ausserordentlich gering. Normalerweise rechnet man mit Beschichtungsstärken von 0,01-0,05gm.The thickness of the precipitate depends on the flow rate and metal evaporation capacity and is extremely ge ring. Usually, coating thicknesses of 0.01-0.05gm are expected.
Die Metallschicht kann noch zusätzlich mit einer Schutz-, Farb- oder Funktionsschicht abgedeckt werden. Das erfindungsgemässe Papier behält durch das Fehlen der Lackschicht unter dem Metall den Papiercharakter und Eigenschaften wie Steifigkeit, Verhalten bei Klimaänderung entsprechen denen von Papier. Die bei bekannten, im Direktverfahren metallisierten Papieren bisher übliche, vorhandene Lackschicht verändert dagegen die Papiereigenschaften, insbesondere das Planlageverhalten, wesentlich. Das erfindungsgemässe Papier lässt sich auch besser bedrucken als vorlackierte Papiere, weil die sperrende Lackschicht die Farbtrocknung nicht verzögert. Bei Verwendung als Etiketten für Flaschen ist die Wiederablösbarkeit in Reinigungsanlagen besser als die von vorlackierten Papieren, weil das Papier leichter und schneller durchfeuchtet.The metal layer can also be covered with a protective, color or functional layer. Due to the lack of a lacquer layer under the metal, the paper according to the invention retains the paper character and properties such as rigidity and behavior in the event of climate change correspond to those of paper. In contrast, the existing lacquer layer which has been customary in the case of known papers metallized in the direct process, on the other hand, changes the paper properties, in particular the flatness behavior, significantly. The paper according to the invention can also be printed better than pre-coated papers because the blocking lacquer layer does not delay the drying of the ink. When used as labels for bottles, the detachability in cleaning systems is better than that of pre-coated papers because the paper moistens more easily and quickly.
Auf eine Papierbahn eines Streichrohpapiers üblicher Zusammensetzung mit einem Flächengewicht von 50 g/m2 wird zunächst eine pigmentierte Vorbeschichtung aufgebracht und getrocknet. Diese Grundbeschichtung mit einem Auftragsgewicht von 8 g/m2 hat eine übliche Zusammensetzung aus 80-90 Gewichtsteilen mineralischem Pigment und 10-20 Gewichtsteile übliche Bindemittel wie Polymerlatices, Casein, Stärke, Polyvinylalkohol oder dergleichen. Als Pigmente dienen Clay, Calciumcarbonat. Zinkoxyd, BaS04. Auf diese getrocknete Beschichtung wird mittels Gussstreichtechnik eine Streichmasse folgender Zusammensetzung aufgebracht in einer Menge von 20 g/qm (nach dem Trocknen):
Die mittels üblicher Aggregate aufgebrachte Beschichtungsmasse wird auf einen Feuchtigkeitsgehalt von 8% getrocknet und dann an einen Zylinder mit einer hochglanzverchromten Oberfläche bei einer Temperatur von 150°C und einem Liniendruck von 1.200 N/cm mittels einer Walze angepresst. Die Bahngeschwindigkeit beträgt 150 m/min. Die vom Chromzylinder ablaufende Bahn wird aufgewickelt und anschliessend in einer Vakuummetallisierungsanlage mit einer Aluminiumschicht versehen.The coating composition applied by means of conventional aggregates is dried to a moisture content of 8% and then pressed onto a cylinder with a high-gloss chrome-plated surface at a temperature of 150 ° C. and a line pressure of 1200 N / cm by means of a roller. The web speed is 150 m / min. The web running from the chrome cylinder is wound up and then provided with an aluminum layer in a vacuum metallization system.
Der Feuchtigkeitsgehalt vor der Metallisierung des Papiers beträgt 2,5%. Nach dem Metallisieren wird durch Konditionieren der Feuchtigkeitsgehalt auf 6-7% eingestellt.The moisture content before metallizing the paper is 2.5%. After metallizing, the moisture content is adjusted to 6-7% by conditioning.
Das erhaltene Papier weist eine spiegelglänzende metallische Oberfläche auf.The paper obtained has a mirror-like metallic surface.
Als mineralische Pigmente können im Gussstrich an Stelle von Clay auch andere übliche Pigmente wie Kaolin, Ca Co3, BaS04, ZnO, Satinweiss und dergl. verwendet werden.Other mineral pigments such as kaolin, Ca Co 3 , BaS0 4 , ZnO, satin white and the like can also be used as mineral pigments in the cast coating instead of clay.
Auf ein Streichrohpapier üblicher Zusammensetzung mit einem Flächengewicht von 5 g/qm wird mittels Gussstreichtechnik eine Streichmasse folgender Zusammensetzung in einer Menge von 25 g/qm aufgebracht:
Die mittels üblicher Aggregate aufgebrachte Beschichtungsmasse wird auf einen Feuchtigkeitsgehalt von 8% getrocknet und dann an einen Zylinder mit einer hochglanzverchromten Oberfläche bei einer Temperatur von 150°C und einem Liniendruck von 1.200 N/cm mittels einer Walze angepresst. Die Bahngeschwindigkeit beträgt 150 m/min. Die vom Chromzylinder ablaufende Bahn wird aufgewickelt und anschliessend in einer Vakuummetallisierungsanlage mit einer Aluminiumschicht versehen.The coating composition applied by means of conventional aggregates is dried to a moisture content of 8% and then pressed onto a cylinder with a high-gloss chrome-plated surface at a temperature of 150 ° C. and a line pressure of 1200 N / cm by means of a roller. The web speed is 150 m / min. The web running from the chrome cylinder is wound up and then provided with an aluminum layer in a vacuum metallization system.
Der Feuchtigkeitsgehalt vor der Metallisierung des Papiers betrug 2,5%. Nach dem Metallisieren wird durch Konditionieren der Feuchtigkeitsgehalt auf 6-7% eingestellt.The moisture content before metallizing the paper was 2.5%. After metallizing, the moisture content is adjusted to 6-7% by conditioning.
Das erhaltene Papier weist eine spiegelglänzende metallische Oberfläche auf.The paper obtained has a mirror-like metallic surface.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83104741T ATE22712T1 (en) | 1982-07-09 | 1983-05-13 | METALLIZED PAPER AND PROCESS OF PRODUCTION. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3225658A DE3225658C1 (en) | 1982-07-09 | 1982-07-09 | Metallized paper and process for making and using same |
| DE3225658 | 1982-07-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0098368A2 EP0098368A2 (en) | 1984-01-18 |
| EP0098368A3 EP0098368A3 (en) | 1984-03-28 |
| EP0098368B1 true EP0098368B1 (en) | 1986-10-08 |
Family
ID=6167996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19830104741 Expired EP0098368B1 (en) | 1982-07-09 | 1983-05-13 | Metallized paper and process for its production |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4567098A (en) |
| EP (1) | EP0098368B1 (en) |
| JP (1) | JPS5921795A (en) |
| AT (1) | ATE22712T1 (en) |
| DE (2) | DE3225658C1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4029491A1 (en) * | 1990-09-18 | 1992-03-19 | Feldmuehle Ag | Paper with satinised overcoat and top coat on one side - contg. synthetic resin binder, natural binder and opt. pigment, useful for label |
| US20230150755A1 (en) * | 2020-12-29 | 2023-05-18 | Mondi Kale Nobel Ambalaj Sanayi Ve Ticaret Anonim Sirketi | Aluminum-free cornet cone package |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02190330A (en) * | 1989-01-19 | 1990-07-26 | Toppan Printing Co Ltd | Oxidized silver-like deposition sheet |
| US4929470A (en) * | 1989-02-24 | 1990-05-29 | James River Corporation | Method of making decorative cast-coated paper |
| DE4139386C1 (en) * | 1991-11-29 | 1993-04-22 | Stora Feldmuehle Ag, 4000 Duesseldorf, De | |
| US5562994A (en) * | 1994-09-21 | 1996-10-08 | Kimberly-Clark Corporation | Un-coated paper-making sludge substrate for metallizing |
| DE9419333U1 (en) * | 1994-12-02 | 1995-01-26 | Lefatex Chemie GmbH, 41379 Brüggen | Coating agents for paper surfaces |
| AUPO484797A0 (en) * | 1997-01-29 | 1997-02-20 | Securency Pty Ltd | Printed matter producing reflective intaglio effect |
| GB9823499D0 (en) * | 1998-10-27 | 1998-12-23 | Proman Chem Ltd | Barrier coatings |
| AUPQ095899A0 (en) | 1999-06-11 | 1999-07-08 | Securency Pty Ltd | Security document or device having an intaglio contrast effect |
| US6818269B2 (en) | 2002-09-27 | 2004-11-16 | Dot Packaging Group, Inc. | Metallic board |
| ITUD20030221A1 (en) * | 2003-11-11 | 2005-05-12 | Metalpack Srl | PROCEDURE FOR THE PRODUCTION OF METALLIC PAPER AND METALLIC PAPER PRODUCED BY SUCH PROCEDURE. |
| US20060040091A1 (en) * | 2004-08-23 | 2006-02-23 | Bletsos Ioannis V | Breathable low-emissivity metalized sheets |
| EP1860235A1 (en) * | 2006-05-23 | 2007-11-28 | M-real Oyj | Coated paper with improved labelling properties |
| EP1892112A1 (en) * | 2006-08-22 | 2008-02-27 | M-real Oyj | Glossy ink-jet recording medium |
| US20100154613A1 (en) * | 2008-12-19 | 2010-06-24 | Multi-Color Corporation | Label that is Removable or Having a Removable Section |
| EP2289703A1 (en) * | 2009-08-26 | 2011-03-02 | M-real Oyj | Thermosensitive recording material containing nanoparticles |
| NL2006977C2 (en) * | 2011-06-21 | 2012-12-28 | Ar Metallizing N V | Method for producing coated vacuum metallized substrates with high vapour and oxygen barrier properties. |
| JP6707833B2 (en) * | 2015-10-15 | 2020-06-10 | 凸版印刷株式会社 | Manufacturing method of vapor-deposited paper |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2685538A (en) * | 1946-01-16 | 1954-08-03 | Warren S D Co | Coated paper and process of making |
| US3113888A (en) * | 1961-03-03 | 1963-12-10 | Nat Starch Chem Corp | Direct method for metalization of cast-coated paper |
| NL272262A (en) * | 1961-12-01 | |||
| US3411948A (en) * | 1964-04-08 | 1968-11-19 | Hewlett Packard Co | Electrosensitive recording medium |
| US3355348A (en) * | 1964-09-02 | 1967-11-28 | Du Pont | Heat sealable-aluminum foil paper laminate |
| US3463659A (en) * | 1965-10-22 | 1969-08-26 | Oxford Paper Co | Vacuum metallized paper |
| US3714107A (en) * | 1968-05-29 | 1973-01-30 | Scott Paper Co | High solids coating composition |
| GB1483441A (en) * | 1975-01-31 | 1977-08-17 | Star Paper Ltd | Cast coated paper and its production and compositions for making it |
| JPS5336574A (en) * | 1976-09-17 | 1978-04-04 | Fuji Photo Film Co Ltd | Method of manufacturing thin plated material with layer of evaporated metal |
| DE2636797B2 (en) * | 1976-08-16 | 1981-06-04 | Basf Ag, 6700 Ludwigshafen | Aqueous coating, impregnating and bonding agent |
| US4293595A (en) * | 1979-03-28 | 1981-10-06 | International Paper Company | Aqueous process for making a conductive medium for electrostatic printing |
| AU5961680A (en) * | 1979-06-29 | 1981-01-08 | Mitsui Petrochemical Industries, Ltd. | Metallised paper |
| JPS56140197A (en) * | 1980-03-31 | 1981-11-02 | Mitsui Petrochemical Ind | Aluminum laminated paper |
-
1982
- 1982-07-09 DE DE3225658A patent/DE3225658C1/en not_active Expired
-
1983
- 1983-05-13 AT AT83104741T patent/ATE22712T1/en not_active IP Right Cessation
- 1983-05-13 EP EP19830104741 patent/EP0098368B1/en not_active Expired
- 1983-05-13 DE DE8383104741T patent/DE3366720D1/en not_active Expired
- 1983-07-06 US US06/511,216 patent/US4567098A/en not_active Expired - Lifetime
- 1983-07-08 JP JP58123584A patent/JPS5921795A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4029491A1 (en) * | 1990-09-18 | 1992-03-19 | Feldmuehle Ag | Paper with satinised overcoat and top coat on one side - contg. synthetic resin binder, natural binder and opt. pigment, useful for label |
| US20230150755A1 (en) * | 2020-12-29 | 2023-05-18 | Mondi Kale Nobel Ambalaj Sanayi Ve Ticaret Anonim Sirketi | Aluminum-free cornet cone package |
| US12091234B2 (en) * | 2020-12-29 | 2024-09-17 | Mondi Kale Nobel Ambalaj Sanayi Ve Ticaret Anonim Sirketi | Aluminum-free cornet cone package |
Also Published As
| Publication number | Publication date |
|---|---|
| US4567098A (en) | 1986-01-28 |
| JPS5921795A (en) | 1984-02-03 |
| ATE22712T1 (en) | 1986-10-15 |
| DE3225658C1 (en) | 1984-01-05 |
| EP0098368A3 (en) | 1984-03-28 |
| EP0098368A2 (en) | 1984-01-18 |
| DE3366720D1 (en) | 1986-11-13 |
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