EP2326992A1 - Recording material for laser printing methods - Google Patents
Recording material for laser printing methodsInfo
- Publication number
- EP2326992A1 EP2326992A1 EP09783066A EP09783066A EP2326992A1 EP 2326992 A1 EP2326992 A1 EP 2326992A1 EP 09783066 A EP09783066 A EP 09783066A EP 09783066 A EP09783066 A EP 09783066A EP 2326992 A1 EP2326992 A1 EP 2326992A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording material
- material according
- toner
- layer
- pigment
- 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
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000007648 laser printing Methods 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 19
- 239000000057 synthetic resin Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 238000012876 topography Methods 0.000 claims abstract description 7
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920001903 high density polyethylene Polymers 0.000 claims description 13
- 239000004700 high-density polyethylene Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007765 extrusion coating Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 229940093876 calcium carbonate / kaolin Drugs 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 5
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 239000010954 inorganic particle Substances 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000012463 white pigment Substances 0.000 claims 1
- 239000000123 paper Substances 0.000 description 43
- 239000010410 layer Substances 0.000 description 36
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005422 blasting Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 241000785681 Sander vitreus Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/002—Organic components thereof
- G03G7/0026—Organic components thereof being macromolecular
- G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/002—Organic components thereof
- G03G7/0026—Organic components thereof being macromolecular
- G03G7/0046—Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
- G03G7/0073—Organic components thereof
- G03G7/008—Organic components thereof being macromolecular
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the invention relates to a recording material for electrophotographic recording methods, in particular the laser printing method, comprising a resin-coated paper carrier and a toner-receiving layer and the use of the recording material for the production of photobooks.
- the laser printer is based on the principle of electrophotography. Electrophotography, by imaging a photoconductor with the optical image of an original, produces a latent image of electrical charges, which is subsequently used to selectively apply a toner (development) and an image (copy) of the original, for example, on paper. to create.
- a toner development
- a copy image
- the wet processes use as a developer a suspension of a low dielectric constant aliphatic solvent and the toner, while the dry process uses a powder.
- an image of the desired side is drawn on the photosensitive drum.
- the drum is initially negatively charged, with the charge being reversed at the points where the laser beam strikes.
- the shape of the discharged areas on the drum corresponds to the later expression.
- the paper is then passed over the image drum. It just brushes past the drum. Behind the paper a potential field is built up.
- the toner is transferred to the paper, where it is initially loose. Then the toner is fixed by means of a hot roller and under pressure.
- the drum is unloaded and excess toner collected.
- electrophotographic images are produced on substrates that have the haptics and look of a typical silver salt photo. These include properties such as gloss, stiffness and opacity, high resolution and sharpness, and good light resistance.
- an image-receiving material for electrophotography which comprises a thermoplastic-coated base paper and a toner-receiving layer and an antistatic backing layer.
- a disadvantage of this material is that it can only be printed on one side and still in need of improvement in terms of toner fixation and behavior in the printer.
- the resin-coated base papers used as support material in the recording materials usually consist of a glued base paper, which is preferably coated on both sides with polyolefin by means of (co) extrusion.
- thermoplastic polymers such as low density polyethylene
- LDPE ethylene / cc-olefin copolymer
- HDPE high density polyethylene
- polypropylene used.
- toner-printed recording papers are masked immediately after printing, undesirable smudging of the toner particles on the back side of the material lying thereon often occurs. Covering the printed papers is done in practice, for example, when storing the early expression in film packaging, albums or when stacking multiple prints in the printer.
- photo books that can be customized.
- design of such photo books is a wide selection of printing techniques and the recording materials used for this purpose, in particular the photographic paper available.
- a photo-base paper coated with photographic emulsions is used, on the front side of which images are produced wet-chemically according to the conventional silver salt process.
- the sheets of paper illustrated on the front side are glued together on the backs in the next step and bound together in a book.
- This is expensive and associated with higher production costs. Therefore, both sides of the printable coated satin-finished papers are used to produce the photo books, which can be printed in an electrophotographic process.
- the images generated in this procedure are in terms of color density, the light and ozone stabilizer.
- a recording material which contains a base paper coated on both sides with a synthetic resin and a toner-receiving layer, the synthetic resin-coated paper having a specific surface topography, expressed by a roughness value Rz of 1.5 to 13 ⁇ m and a mean Ra Value of 0.05 to 2 ⁇ m, the toner-receiving layer contains a polymer combination of a toner-receiving ethylene-acrylic acid copolymer (A), a carboxylated acrylic copolymer (B) and a polymer (C), and the polymer (C) has a middle one Particle size d 5 o of 5 to 20 microns and a melting point aud- points, which is above the melting range of the copolymer (A) and below the melting range of the copolymer (B).
- base paper is understood to mean an uncoated or surface-sized paper.
- sizing agents such as alkylknime dimers, fatty acids and / or fatty acid salts, epoxidized fatty acid amides, alkenyl or alkylsuccinic anhydride, wet strength agents such as polyamine-polyamide
- Epichlorohydrin dry strength agents such as anionic, cationic or amphoteric polyamides, optical brighteners, fillers,
- the base paper can be surface-sized. Examples of suitable sizing agents are polyvinyl alcohol or oxidized starch.
- the base paper can be produced on a Fourdrinier or a Yankee paper machine (cylinder paper machine).
- the weight per unit area of the base paper may be 50 to 250 g / m 2 , in particular 80 to 180 g / m 2 .
- the raw paper can be used in uncompacted or compacted form (smoothed).
- Particularly suitable are base papers having a density of 0.8 to 1.2 g / cm 3 , in particular 0.90 to 1.1 g / cm 3 .
- bleached hardwood kraft pulp LLKP
- bleached softwood kraft pulp NKP
- bleached hardwood sulphite pulp LBSP
- bleached softwood sulphite pulp NBSP
- pulp fibers made from 100% hardwood pulp are used.
- the mean fiber length of the unground pulp is preferably 0.6 to 0.85 mm (Kajaani measurement).
- the pulp has a lignin content of less than 0.05 wt.%, In particular 0.01 to 0.03 wt.%, Based on the mass of the pulp.
- kaolins calcium carbonate in its natural forms such as limestone, marble or dolomite stone, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, aluminum oxide and mixtures thereof in the base paper can be used as filler.
- Particularly suitable is calcium carbonate with a particle size distribution in which at least 60% of the particles are smaller than 2 microns and
- calcite having a particle size distribution is used in which about 25% of the particles have a particle size of less than 1 ⁇ m and about 85% of the particles have a particle size of less than 2 ⁇ m.
- the resin layers (front and back resin layers) disposed on both sides of the base paper may preferably contain a thermoplastic polymer.
- a thermoplastic polymer Particularly suitable for this purpose are polyolefins, for example low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, 4-methylpentene-1 and mixtures thereof and polyesters, for example polycarbonates.
- the front and rear synthetic resin layer contains at least 40 wt.% HDPE having a density of more than 0.935 g / cm 3 , in particular 50 to 70 wt.%.
- Particularly preferred is a composition consisting of 50% by weight HDPE having a density greater than 0.935 g / cm 3 and 50% by weight LDPE having a density of less than 0.935 g / cm 3 .
- the synthetic resin layers may contain white pigments such as titanium dioxide as well as other auxiliaries such as optical brighteners, dyes and dispersing aids.
- the coating weight of the synthetic resin layers may be 5 to 50 g / m 2 , in particular 5 to 30 g / m 2 , but preferably 10 to 20 g / m 2 .
- the synthetic resin layer can be extruded in one layer or coextruded in a multilayered manner. The extrusion coating can be carried out at machine speeds up to 600 m / min.
- the synthetic resin layers are applied symmetrically on both sides of the base paper, ie, the front and back resin layers have the same composition. These layers are also identical in terms of surface topography.
- the surface structure (topography) is generated by means of the cooling cylinders used in the extrusion coating. It can be characterized by roughness values.
- the surface of the synthetic resin layer on both sides has roughness values Rz of 1.8 to 11 ⁇ m and an average Ra value of 0.1 to 1.8 ⁇ m.
- the cooling cylinders used to produce the surface structure are produced in a known manner.
- the surface of a steel cylinder can be treated by blasting with sand, glass or other blasting material and then chrome-plated.
- the surface of the cylinder can also be built up in a conventional manner in a chromium bath electrolytic.
- the polymer (A) of the polymer combination in the ink-receiving layer preferably has a melting range of 70 to 100 0 C and the polymer (B) has a melting range of 160 to 210 0 C.
- the polymer (B) can be characterized by a so-called acid number.
- An acid number defines the amount of free carboxyl groups in the polymer. she
- MI / co 081540EP September 11, 2009 indicates the amount (mg) of 0.1 molar KOH solution needed to neutralize the free acid groups in 1 g of polymer.
- the polymer (B) used according to the invention has an acid number of more than 100. Particularly suitable are polymers having an acid number of 120 to 160.
- the polymers (A) and (B) are preferably used in a quantitative ratio of 70:30 to 30:70. Particularly good effects were achieved at a ratio of 60:40 to 40:60.
- the polymer (C) preferably has a melting point in a temperature range of 120 to 150 0 C.
- a melting point in a temperature range of 120 to 150 0 C.
- the polymer (C) is preferably used in an amount of 0.1 to 5.0% by weight, more preferably 1.0 to 4.0% by weight, based on the dried layer.
- an antistatic agent is contained in the toner-receiving layer in an amount of from 0.1 to 5.0% by weight, in particular from 1.0 to 4.0% by weight, based on the dried layer.
- the toner-receiving layer additionally contains anionic or nonionic surfactants in an amount of from 0.1 to 4.0% by weight, in particular from 0.5 to 2.5% by weight, based on the dried layer.
- the toner-receiving layer may also contain other auxiliaries, for example matting agents, pigments, dyes, crosslinking agents, lubricants and other conventional additives.
- auxiliaries for example matting agents, pigments, dyes, crosslinking agents, lubricants and other conventional additives.
- the coating composition for forming the toner-receiving layer can be applied in-line or off-line with all customary in papermaking application units, wherein the amount is chosen so that after drying the order weight not more than 3 g / m 2 , in particular 0.1 to 2 g / m 2 , or in a particularly preferred embodiment 0.3 to 0.7 g / m 2 .
- the coating composition is applied as a line with the aid of a custom applicator integrated within the extrusion coating line.
- a 3-roller application or a squeegee device is particularly well suited for this purpose.
- the pigment may be a metal oxide, silicate, carbonate, sulfide or sulfate. Particularly suitable are pigments such as kaolins, talc, calcium carbonate and / or barium sulfate.
- a pigment having a narrow particle size distribution in which at least 70% of the pigment particles have a size of less than 1 ⁇ m.
- the proportion of the pigment with the narrow particle size distribution of the total amount of pigment is at least 5% by weight, in particular 10 to 90% by weight. Particularly good results can be achieved with a proportion of 30 to 80% by weight of the total pigment.
- a pigment having a narrow particle size distribution is also understood as meaning pigments having a particle size distribution in which at least about 70% by weight of the pigment particles have a size of less than about 1 ⁇ m and 40 to 80% by weight of these pigment particles the pigment having the largest grain size (diameter) and the pigment of the smallest grain size is smaller than about 0.4 ⁇ m.
- Particularly advantageous is a carbonate Calciumcar- proved with a d o 5% value of about 0.7 microns.
- a pigment mixture consisting of the abovementioned calcium carbonate and kaolin can be used in the pigment-containing layer.
- the quantitative ratio calcium carbonate / kaolin is preferably 30:70 to 70:30.
- the amount ratio of binder / pigment in the pigment-containing layer may be 0.1 to 2.5, preferably 0.2 to 1.5, but especially about 0.9 to 1.3.
- Any known water-soluble and / or water-dispersible binder can be used in the pigment-containing layer.
- Particularly suitable for this purpose are film-forming starches such as thermally modified starches, in particular corn starches or hydroxypropylated starches.
- the pigment-containing layer can be applied in-line or off-line with all customary in papermaking application units, the amount is chosen so that after drying the application weight 0.1 to 30 g / m 2 , in particular 1 to 20 g / m 2 , or according to a particularly preferred embodiment
- the pigment-containing layer is applied with a size press or film press integrated within the paper machine.
- further layers such as protective layers or gloss-improving layers can be applied to the toner-receiving layer.
- the application weight is preferably less than 1 g / m 2 .
- a eucalyptus pulp was used. For milling, the pulp was milled as an approximately 5% aqueous suspension (thick material) using a refiner to a freeness of 35 0 SR. The mean fiber length was 0.65 mm. The concentration of the pulp fibers in the thin material was 1% by weight, based on the mass of the pulp suspension.
- the thin stock additives were added as a neutral sizing agent alkylketene dimer (AKD) is present in an amount of from 0.48.%, Wet strength agents polyamine-polyamide epichlorohydrin resin (Kymene ®) is present in an amount of from 0.36.% And a natural CaCO 3 in an amount of 20% by weight. The quantities are based on the pulp mass.
- the thinness whose pH was adjusted to about 7.5, was brought from the head box to the wire of the paper machine, followed by sheet formation while dewatering the web in the paper machine
- LDPE low density polyethylene
- HDPE high density polyethylene
- the coating was carried out in a laminator (tandem extruder) at an extrusion speed of 250 m / min using a cooling cylinder from the company BEP Service Technology whose surface has an average Rz value of 11.03 ⁇ m and an Ra value of 1.87 ⁇ m.
- the surface of the cooling cylinder was produced by sandblasting or blasting with other blasting material and chrome plated.
- the application weights on both sides were 15 g / m 2 each.
- aqueous coating compositions having a solids content of 19% by weight and having the following composition were used:
- the coated weight of the dried toner-receiving layer was 0.5 g / m 2 on both sides.
- the material produced according to the invention was tested for image quality, light and ozone resistance.
- the tests were based on color prints made with the HP Color Laser Jet 2605dn laser printer (wet toner) and the Konica Minolta MC5550 color copier. Bar-like areas in cyan, magenta, yellow, red, green, blue, and black were printed at 100% saturation.
- the samples were stored for 24 hours in an ozone chamber at an ozone concentration of 3.5 ppm, a temperature of 20 to 22 ° C and a relative humidity of 40 to 50%. Subsequently, again
- MI / co 081540EP September 11, 2009 measured the colorimetric L * a * b * values of the color areas and determined the degree of bleaching ⁇ E.
- the printed paper samples were held under xenon lamp for 50 hours, at a temperature of 26 ° C and a relative humidity of 60%.
- the evaluation was carried out according to the CIE L * a * b * system described above.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
Description
MI/co 081540EPMI / co 081540EP
11. September 2009September 11, 2009
Aufzeichnungsmaterial für LaserdruckverfahrenRecording material for laser printing processes
Die Erfindung betrifft ein Aufzeichnungsmaterial für elektro- fotografische Aufzeichnungsverfahren, insbesondere das Laserdruckverfahren, mit einem harzbeschichteten Papierträger und einer toneraufnehmenden Schicht sowie die Verwendung des Aufzeichnungsmaterials zur Herstellung von Fotobüchern.The invention relates to a recording material for electrophotographic recording methods, in particular the laser printing method, comprising a resin-coated paper carrier and a toner-receiving layer and the use of the recording material for the production of photobooks.
Dem Laserdrucker liegt das Prinzip der Elektrofotografie zugrunde. Die Elektrofotografie erzeugt durch eine Abbildung bzw. Belichtung eines Fotoleiters mit dem optischen Abbild einer Vorlage ein latentes Bild aus elektrischen Ladungen, welches nachfolgend dazu benutzt wird, selektiv einen Toner aufzutragen (Entwicklung) und ein Abbild (Kopie) der Vorlage, beispielsweise auf Papier, zu erzeugen. Man unterscheidet direkte und indirekte sowie nasse und trockene Elektrofotogra- fie. Die Nassverfahren nutzen als Entwickler eine Suspension aus einem aliphatischen Lösungsmittel mit geringer Dielektri- zitätskonstante und dem Toner, während das Trockenverfahren ein Pulver verwendet.The laser printer is based on the principle of electrophotography. Electrophotography, by imaging a photoconductor with the optical image of an original, produces a latent image of electrical charges, which is subsequently used to selectively apply a toner (development) and an image (copy) of the original, for example, on paper. to create. One differentiates between direct and indirect as well as wet and dry electrophotography. The wet processes use as a developer a suspension of a low dielectric constant aliphatic solvent and the toner, while the dry process uses a powder.
Mit Hilfe eines gebündelten Laserstrahles und eines rotierenden Spiegels wird auf die lichtempfindliche Bildtrommel ein Abbild der gewünschten Seite gezeichnet. Die Trommel ist zunächst negativ aufgeladen, wobei die Ladung an den Stellen wieder aufgehoben wird, auf die der Laserstrahl trifft. Die Form der entladenen Flächen auf der Trommel entspricht dem späteren Ausdruck. Über eine Rolle mit negativ geladenem Toner, der an den entladenen Stellen auf der Bild-trommel haften bleibt wird der Toner auf die Trommel gebracht. Das Papier wird anschließend über die Bildtrommel geführt. Es Streift nur an der Trommel vorbei. Hinter dem Papier wird ein Potenzialfeld aufgebaut. Der Toner wird auf das Papier übertragen und ist dort zunächst lose. Anschließend wird der Toner mit Hilfe einer heißen Walze und unter Druck fixiert. Die Trommel wird entladen und überflüssiger Toner aufgesammelt.With the aid of a focused laser beam and a rotating mirror, an image of the desired side is drawn on the photosensitive drum. The drum is initially negatively charged, with the charge being reversed at the points where the laser beam strikes. The shape of the discharged areas on the drum corresponds to the later expression. About a role with negatively charged Toner, which sticks to the unloaded areas on the image drum, the toner is placed on the drum. The paper is then passed over the image drum. It just brushes past the drum. Behind the paper a potential field is built up. The toner is transferred to the paper, where it is initially loose. Then the toner is fixed by means of a hot roller and under pressure. The drum is unloaded and excess toner collected.
Die mit Hilfe eines Laser-Druckers erzeugten Bilder sollten eine mit einem Foto vergleichbare Qualität erreichen. Um dem Ziel näher zu kommen, werden elektrofotografisch erzeugte Bilder auf Trägermaterialien produziert, die die Hap- tik und das Aussehen eines typischen Silbersalz-Fotos aufwei- sen. Hierzu gehören Eigenschaften wie Glanz, Steifigkeit und Opazität, eine hohe Auflösung und Bildschärfe sowie eine gute Lichtresistenz .The images produced with the help of a laser printer should achieve a quality comparable to a photograph. To get closer to the goal, electrophotographic images are produced on substrates that have the haptics and look of a typical silver salt photo. These include properties such as gloss, stiffness and opacity, high resolution and sharpness, and good light resistance.
In der DE 44 35 350 C2 ist ein Bildempfangsmaterial für Elektrofotografie beschrieben, das ein mit Thermoplasten beschichtetes Basispapier und eine Toner-Empfangsschicht sowie eine antistatische Rückseitenschicht umfasst. Nachteilig an diesem Material ist, dass es nur einseitig bedruckbar und hinsichtlich der Tonerfixierung und des Verhaltens im Drucker noch verbesserungsbedürftig ist.In DE 44 35 350 C2 an image-receiving material for electrophotography is described, which comprises a thermoplastic-coated base paper and a toner-receiving layer and an antistatic backing layer. A disadvantage of this material is that it can only be printed on one side and still in need of improvement in terms of toner fixation and behavior in the printer.
Die als Trägermaterial in den Aufzeichnungsmaterialien verwendeten harzbeschichteten Basispapiere bestehen üblicherweise aus einem geleimten Rohpapier, das beidseitig vorzugsweise mit Polyolefin mittels (Co-) Extrusion beschichtet ist. Für die Extrusionsbeschichtung des Rohpapiers werden üblicherweise thermoplastische Polymere wie Polyethylen niedriger DichteThe resin-coated base papers used as support material in the recording materials usually consist of a glued base paper, which is preferably coated on both sides with polyolefin by means of (co) extrusion. For the extrusion coating of the base paper are usually thermoplastic polymers such as low density polyethylene
MI/co 081540EP 11. September 2009 (LDPE), Ethylen/cc-Olefin-Copolymer (sogenanntes lineares Po- lyethylen niedriger Dichte (LLDPE) , Polyethylen hoher Dichte (HDPE) und Polypropylen eingesetzt.MI / co 081540EP September 11, 2009 (LDPE), ethylene / cc-olefin copolymer (so-called linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and polypropylene used.
Werden die mit Toner bedruckten Aufzeichnungspapiere direkt nach dem Druck abgedeckt, so tritt oft ein unerwünschtes Abklatschen der Tonerpartikel auf der Rückseite des darauf liegenden Materials auf. Das Abdecken der bedruckten Papiere geschieht in der Praxis beispielsweise bei Lagerung des fri- sehen Ausdrucks in Folienverpackungen, Alben oder beim Stapeln mehrerer Ausdrucke im Drucker.If the toner-printed recording papers are masked immediately after printing, undesirable smudging of the toner particles on the back side of the material lying thereon often occurs. Covering the printed papers is done in practice, for example, when storing the early expression in film packaging, albums or when stacking multiple prints in the printer.
Zu den neuesten, einen guten Absatz findenden Entwicklungen im Bereich der Bilderzeugung gehören sogenannte Fotobücher, die individuell gestaltet werden können. Zur Gestaltung solcher Fotobücher steht eine breite Auswahl an Drucktechniken und den hierzu verwendbaren Aufzeichnungsmaterialien, insbesondere das Fotopapier, zur Verfügung.The latest developments in the field of image production, which are in good shape, include so-called photo books that can be customized. For the design of such photo books is a wide selection of printing techniques and the recording materials used for this purpose, in particular the photographic paper available.
Zur Herstellung solcher Fotobücher wird ein mit fotografischen Emulsionen beschichtetes Fotobasispapier verwendet, auf dem vorderseitig Bilder gemäß konventionellem Silbersalzverfahren nasschemisch erzeugt werden. Die auf der Vorderseite bebilderten Papierbögen werden im nächsten Schritt auf den Rückseiten miteinander verklebt und zu einem Buch zusammengebunden. Dies ist aufwendig und mit höheren Herstellungskosten verbunden. Daher werden zur Herstellung der Fotobücher beidseitig bedruckbare gestrichene satinierte Papiere verwendet, die in einem elektrofotografischen Prozess bedruckt werden können. Die bei dieser Vorgehensweise erzeugten Bilder sind jedoch hinsichtlich der Farbdichte, der Licht- und Ozonstabi-For producing such photobooks, a photo-base paper coated with photographic emulsions is used, on the front side of which images are produced wet-chemically according to the conventional silver salt process. The sheets of paper illustrated on the front side are glued together on the backs in the next step and bound together in a book. This is expensive and associated with higher production costs. Therefore, both sides of the printable coated satin-finished papers are used to produce the photo books, which can be printed in an electrophotographic process. However, the images generated in this procedure are in terms of color density, the light and ozone stabilizer.
MI/co 081540EP 11. September 2009 lität sowie des Verhaltens in der Druckeinrichtung (Einzug, Transport und Ausbildung von Stapeln) verbesserungsbedürftig.MI / co 081540EP September 11, 2009 quality and behavior in the printing device (feeder, transport and training of stacks) need improvement.
Es ist daher Aufgabe der Erfindung, ein Aufzeichnungsmaterial bereit zu stellen, welches beidseitig bedruckbar ist, eine gute Bildqualität, eine gute Licht- und Ozonresistenz bei Lagerung sowie ein gutes Einzugs- und Transport-Verhalten im Drucker und eine gute Stapelfähigkeit aufweist.It is therefore an object of the invention to provide a recording material which is printable on both sides, has a good image quality, good light and ozone resistance during storage and a good collection and transport behavior in the printer and good stackability.
Gelöst wird diese Aufgabe durch ein Aufzeichnungsmaterial, das ein auf beiden Seiten mit einem Kunstharz beschichtetes Rohpapier und eine toneraufnehmende Schicht enthält, wobei das kunstharzbeschichtete Papier eine spezifische Oberflä- chentopografie, ausgedrückt durch einen Rauhigkeitswert Rz von 1,5 bis 13 μm und einen mittleren Ra-Wert von 0,05 bis 2 μm aufweist, die toneraufnehmende Schicht eine Polymerkombination aus einem toneraufnehmenden Ethylen-Acrylsäure- Copolymer (A), einem carboxylierten Acrylcopolymer (B) und einem Polymer (C) enthält, und das Polymer (C) eine mittlere Partikelgröße d5o von 5 bis 20 μm und einen Schmelzpunkt aud- weist, der oberhalb des Schmelzbereiches des Copolymers (A) und unterhalb des Schmelzbereichs des Copolymers (B) liegt .This object is achieved by a recording material which contains a base paper coated on both sides with a synthetic resin and a toner-receiving layer, the synthetic resin-coated paper having a specific surface topography, expressed by a roughness value Rz of 1.5 to 13 μm and a mean Ra Value of 0.05 to 2 μm, the toner-receiving layer contains a polymer combination of a toner-receiving ethylene-acrylic acid copolymer (A), a carboxylated acrylic copolymer (B) and a polymer (C), and the polymer (C) has a middle one Particle size d 5 o of 5 to 20 microns and a melting point aud- points, which is above the melting range of the copolymer (A) and below the melting range of the copolymer (B).
Für die Zwecke der Erfindung versteht man unter dem Begriff Rohpapier ein unbeschichtetes oder oberflächengeleimtes Papier. Ein Rohpapier kann neben Zellstofffasern, Leimungsmittel wie Alkylkentendimere, Fettsäuren und/oder Fettsäuresalze, epoxydierte Fettsäureamide, Alkenyl- oder Alkylbernstein- säureanhydrid, Nassfestmittel wie Polyamin-Polyamid-For the purposes of the invention, the term base paper is understood to mean an uncoated or surface-sized paper. In addition to pulp fibers, sizing agents such as alkylknime dimers, fatty acids and / or fatty acid salts, epoxidized fatty acid amides, alkenyl or alkylsuccinic anhydride, wet strength agents such as polyamine-polyamide
Epichlorhydrin, Trockenfestmittel wie anionische, kationische oder amphotere Polyamide, optische Aufheller, Füllstoffe,Epichlorohydrin, dry strength agents such as anionic, cationic or amphoteric polyamides, optical brighteners, fillers,
MI/co 081540EP 11. September 2009 Pigmente, Farbstoffe, Entschäumer und weitere in der Papierindustrie bekannte Hilfsmittel enthalten kann. Das Rohpapier kann oberflächengeleimt sein. Hierzu geeignete Leimmittel sind beispielsweise Polyvinylalkohol oder oxydierte Stärke. Das Rohpapier kann auf einer Fourdrinier- oder einer Yankee- Papiermaschine (Zylinder-Papiermaschine) hergestellt werden. Das Flächengewicht des Rohpapiers kann 50 bis 250 g/m2, insbesondere 80 bis 180 g/m2, betragen. Das Rohpapier kann in unverdichteter oder verdichteter Form (geglättet) eingesetzt werden. Besonders gut geeignet sind Rohpapiere mit einer Dichte von 0,8 bis 1,2 g/cm3, insbesondere 0,90 bis 1,1 g/cm3.MI / co 081540EP September 11, 2009 Pigments, dyes, defoamers and other known in the paper industry tools may contain. The base paper can be surface-sized. Examples of suitable sizing agents are polyvinyl alcohol or oxidized starch. The base paper can be produced on a Fourdrinier or a Yankee paper machine (cylinder paper machine). The weight per unit area of the base paper may be 50 to 250 g / m 2 , in particular 80 to 180 g / m 2 . The raw paper can be used in uncompacted or compacted form (smoothed). Particularly suitable are base papers having a density of 0.8 to 1.2 g / cm 3 , in particular 0.90 to 1.1 g / cm 3 .
Als Zellstofffasern können beispielsweise gebleichter Hart- holz-Kraftzellstoff (LBKP) , gebleichter Nadelholz- Kraftzellstoff (NBKP) , gebleichter Laubholzsulfitzellstoff (LBSP) oder gebleichter Nadelholzsulfitzellstoff (NBSP) eingesetzt werden. Diese können auch gemischt eingesetzt werden. Insbesondere jedoch werden Zellstofffasern aus 100% Laubholz- zellstoff eingesetzt. Die mittlere Faserlänge des ungemahlenen Zellstoffs beträgt vorzugsweise 0,6 bis 0,85 mm (Kajaani- Messung) . Ferner weist der Zellstoff einen Ligningehalt von weniger als 0,05 Gew.% auf, insbesondere 0,01 bis 0,03 Gew.%, bezogen auf die Masse des Zellstoffs.For example, bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), bleached hardwood sulphite pulp (LBSP) or bleached softwood sulphite pulp (NBSP) can be used as pulp fibers. These can also be used mixed. In particular, however, pulp fibers made from 100% hardwood pulp are used. The mean fiber length of the unground pulp is preferably 0.6 to 0.85 mm (Kajaani measurement). Furthermore, the pulp has a lignin content of less than 0.05 wt.%, In particular 0.01 to 0.03 wt.%, Based on the mass of the pulp.
Als Füllstoff können beispielsweise Kaoline, Calciumcarbonat in seinen natürlichen Formen wie Kalkstein, Marmor oder Dolomitstein, gefälltes Calciumcarbonat, Calciumsulfat, Bariumsulfat, Titaniumdioxid, Talkum, Silica, Aluminiumoxid und de- ren Gemische im Rohpapier eingesetzt werden. Besonders geeignet ist Calciumcarbonat mit einer Korngrößenverteilung, bei der mindestens 60 % der Teilchen kleiner sind als 2 μm undFor example, kaolins, calcium carbonate in its natural forms such as limestone, marble or dolomite stone, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, aluminum oxide and mixtures thereof in the base paper can be used as filler. Particularly suitable is calcium carbonate with a particle size distribution in which at least 60% of the particles are smaller than 2 microns and
MI/co 081540EP 11. September 2009 höchstens 40 % kleiner sind als 1 μm. In einer besonderen Ausgestaltung der Erfindung wird Calcit mit einer Korngrößenverteilung eingesetzt, bei der etwa 25 % der Teilchen eine Teilchengrößen von weniger als 1 μm und etwa 85 % der Teil- chen eine Teilchengröße von weniger als 2 μm aufweisen.MI / co 081540EP September 11, 2009 at most 40% are smaller than 1 micron. In a particular embodiment of the invention, calcite having a particle size distribution is used in which about 25% of the particles have a particle size of less than 1 μm and about 85% of the particles have a particle size of less than 2 μm.
Die auf beiden Seiten des Rohpapiers angeordneten Kunstharzschichten (vorderseitige und rückseitige Kunstharzschicht) können vorzugsweise ein thermoplastisches Polymer enthalten. Insbesondere geeignet hierfür sind Polyolefine, beispielsweise Polyethylen niedriger Dichte (LDPE) , Polyethylen hoher Dichte (HDPE) , Polypropylen, 4-Methylpenten-l und deren Gemische sowie Polyester, beispielsweise Polycarbonate .The resin layers (front and back resin layers) disposed on both sides of the base paper may preferably contain a thermoplastic polymer. Particularly suitable for this purpose are polyolefins, for example low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, 4-methylpentene-1 and mixtures thereof and polyesters, for example polycarbonates.
In einer besonderen Ausgestaltung der Erfindung enthält die vorderseitige und rückseitige Kunstharzschicht mindestens 40 Gew.% HDPE mit einer Dichte von mehr als 0,935 g/cm3, insbesondere 50 bis 70 Gew.%. Besonders bevorzugt ist eine Zusammensetzung, die aus 50 Gew.% HDPE mit einer Dichte von mehr als 0,935 g/cm3und 50 Gew.% LDPE mit einer Dichte von weniger als 0,935 g/cm3besteht .In a particular embodiment of the invention, the front and rear synthetic resin layer contains at least 40 wt.% HDPE having a density of more than 0.935 g / cm 3 , in particular 50 to 70 wt.%. Particularly preferred is a composition consisting of 50% by weight HDPE having a density greater than 0.935 g / cm 3 and 50% by weight LDPE having a density of less than 0.935 g / cm 3 .
Die Kunstharzschichten können Weißpigmente wie Titandioxid sowie weitere Hilfsstoffe wie optische Aufheller, Farbstoffe und Dispergierhilfsmittel enthalten. Das Auftragsgewicht der Kunstharzschichten kann 5 bis 50 g/m2, insbesondere 5 bis 30 g/m2, bevorzugt jedoch 10 bis 20 g/m2 betragen. Die Kunstharzschicht kann einschichtig extrudiert oder mehrschichtig coextrudiert werden. Die Extrusionsbeschichtung kann mit Maschinengeschwindigkeiten bis 600 m/min erfolgen.The synthetic resin layers may contain white pigments such as titanium dioxide as well as other auxiliaries such as optical brighteners, dyes and dispersing aids. The coating weight of the synthetic resin layers may be 5 to 50 g / m 2 , in particular 5 to 30 g / m 2 , but preferably 10 to 20 g / m 2 . The synthetic resin layer can be extruded in one layer or coextruded in a multilayered manner. The extrusion coating can be carried out at machine speeds up to 600 m / min.
MI/co 081540EP 11. September 2009 Erfindungsgemäß werden die Kunstharzschichten symmetrisch auf beiden Seiten des Rohpapiers aufgetragen, d. h. die vorderseitige und die rückseitige Kunstharzschicht weisen dieselbe Zusammensetzung auf. Auch hinsichtlich der Oberflächentopo- grafie sind diese Schichten identisch.MI / co 081540EP September 11, 2009 According to the invention, the synthetic resin layers are applied symmetrically on both sides of the base paper, ie, the front and back resin layers have the same composition. These layers are also identical in terms of surface topography.
Die Oberflächenstruktur (Topografie) wird mit Hilfe von den bei der Extrusionsbeschichtung eingesetzten Kühlzylindern erzeugt. Sie lässt sich durch Rauhigkeitswerte charakterisie- ren.The surface structure (topography) is generated by means of the cooling cylinders used in the extrusion coating. It can be characterized by roughness values.
In einer besonderen Ausgestaltung weist die Oberfläche der Kunstharzschicht auf beiden Seiten Rauhigkeitswerte Rz von 1,8 bis 11 μm und einen mittleren Ra-Wert von 0,1 bis 1,8 μm auf.In a particular embodiment, the surface of the synthetic resin layer on both sides has roughness values Rz of 1.8 to 11 μm and an average Ra value of 0.1 to 1.8 μm.
Die zur Erzeugung der Oberflächenstruktur verwendeten Kühlzy- linder werden auf bekannte Weise hergestellt. Hierzu kann die Oberfläche eines Stahlzylinders durch Strahlen mit Sand, Glas oder anderem Strahlgut behandelt und anschließend verchromt werden. Die Oberfläche des Zylinders kann aber auch auf herkömmliche Weise in einem Chrombad elektrolytisch aufgebaut werden .The cooling cylinders used to produce the surface structure are produced in a known manner. For this purpose, the surface of a steel cylinder can be treated by blasting with sand, glass or other blasting material and then chrome-plated. The surface of the cylinder can also be built up in a conventional manner in a chromium bath electrolytic.
Das Polymer (A) der Polymerkombination in der tintenaufnehmenden Schicht weist vorzugsweise einen Schmelzbereich von 70 bis 1000C und das Polymer (B) einen Schmelzbereich von 160 bis 2100C auf.The polymer (A) of the polymer combination in the ink-receiving layer preferably has a melting range of 70 to 100 0 C and the polymer (B) has a melting range of 160 to 210 0 C.
Das Polymer (B) kann durch eine sogenannte Säurezahl charakterisiert werden. Über eine Säurezahl wird die Menge der im Polymer enthaltenen freien Carboxyl-Gruppen definiert. SieThe polymer (B) can be characterized by a so-called acid number. An acid number defines the amount of free carboxyl groups in the polymer. she
MI/co 081540EP 11. September 2009 gibt an, welche Menge (mg) einer 0,1 molaren KOH-Lösung benötigt wird, um die freien Säuregruppen in 1 g Polymer zu neutralisieren. Das erfindungsgemäß eingesetzte Polymer (B) weist eine Säurezahl von mehr als 100 auf. Besonders gut geeignet sind Polymere mit einer Säurezahl von 120 bis 160.MI / co 081540EP September 11, 2009 indicates the amount (mg) of 0.1 molar KOH solution needed to neutralize the free acid groups in 1 g of polymer. The polymer (B) used according to the invention has an acid number of more than 100. Particularly suitable are polymers having an acid number of 120 to 160.
Die Polymere (A) und (B) werden vorzugsweise in einem Mengenverhältnis von 70:30 bis 30:70 eingesetzt. Besonders gute Effekte wurden bei einem Mengenverhältnis von 60:40 bis 40:60 erreicht.The polymers (A) and (B) are preferably used in a quantitative ratio of 70:30 to 30:70. Particularly good effects were achieved at a ratio of 60:40 to 40:60.
Das Polymer (C) hat vorzugsweise einen Schmelzpunkt in einem Temperaturbereich von 120 bis 1500C. Hierfür besonders gut geeignet sind Polyethylenwachse, Polyamide und Mischungen da- von.The polymer (C) preferably has a melting point in a temperature range of 120 to 150 0 C. For this purpose, are particularly well suited polyethylene waxes, polyamides, and mixtures of DA.
Das Polymer (C) wird vorzugsweise in einer Menge von 0,1 bis 5,0 Gew.%, insbesondere von 1,0 bis 4,0 Gew.% eingesetzt, bezogen auf die getrocknete Schicht.The polymer (C) is preferably used in an amount of 0.1 to 5.0% by weight, more preferably 1.0 to 4.0% by weight, based on the dried layer.
In einer bevorzugten Ausführungsform der Erfindung ist ein antistatisches Mittel in einer Menge von 0,1 bis 5,0 Gew.%, insbesondere 1,0 bis 4,0 Gew.%, bezogen auf die getrocknete Schicht, in der toneraufnehmenden Schicht enthalten.In a preferred embodiment of the invention, an antistatic agent is contained in the toner-receiving layer in an amount of from 0.1 to 5.0% by weight, in particular from 1.0 to 4.0% by weight, based on the dried layer.
In einer weiteren Ausgestaltungsform der Erfindung enthält die toneraufnehmende Schicht zusätzlich anionische oder nichtionische oberflächenaktive Mittel in einer Menge von 0,1 bis 4,0 Gew.%, insbesondere 0,5 bis 2,5 Gew.%, bezogen auf die getrocknete Schicht.In a further embodiment of the invention, the toner-receiving layer additionally contains anionic or nonionic surfactants in an amount of from 0.1 to 4.0% by weight, in particular from 0.5 to 2.5% by weight, based on the dried layer.
MI/co 081540EP 11. September 2009 Die toneraufnehmende Schicht kann gegebenenfalls auch weitere Hilfsmittel enthalten, beispielsweise Mattierungsmittel, Pigmente, Farbstoffe, Vernetzungsmittel, Gleitmittel und andere übliche Additive.MI / co 081540EP September 11, 2009 Optionally, the toner-receiving layer may also contain other auxiliaries, for example matting agents, pigments, dyes, crosslinking agents, lubricants and other conventional additives.
Die Beschichtungsmasse zur Bildung der toneraufnehmenden Schicht kann mit allen in der Papierherstellung üblichen Auftragsaggregaten inline oder offline aufgebracht werden, wobei die Menge so gewählt wird, dass nach dem Trocknen das Auf- tragsgewicht höchstens 3 g/m2, insbesondere 0,1 bis 2 g/m2, oder gemäß einer besonders bevorzugten Ausführungsform 0,3 bis 0,7 g/m2 beträgt. In einer bevorzugten Ausführungsform wird die Beschichtungsmasse als Strich mit Hilfe eines üblichen, innerhalb der Extrusionsbeschichtungsanlage integrier- ten Auftragswerkes aufgetragen. Hierzu besonders gut geeignet ist beispielsweise ein 3-Walzenauftrag oder eine Rakelvorrichtung.The coating composition for forming the toner-receiving layer can be applied in-line or off-line with all customary in papermaking application units, wherein the amount is chosen so that after drying the order weight not more than 3 g / m 2 , in particular 0.1 to 2 g / m 2 , or in a particularly preferred embodiment 0.3 to 0.7 g / m 2 . In a preferred embodiment, the coating composition is applied as a line with the aid of a custom applicator integrated within the extrusion coating line. For example, a 3-roller application or a squeegee device is particularly well suited for this purpose.
In einer weiteren Ausführungsform der Erfindung kann zwischen dem Rohpapier und der Kunstharzschicht eine pigmenthaltigeIn a further embodiment of the invention, between the base paper and the synthetic resin layer, a pigment-containing
Schicht angeordnet sein. Das Pigment kann ein Metalloxid, Silikat, Carbonat, Sulfid oder Sulfat sein. Besonders gut geeignet sind Pigmente wie Kaoline, Talkum, Calciumcarbonat und/oder Bariumsulfat.Layer can be arranged. The pigment may be a metal oxide, silicate, carbonate, sulfide or sulfate. Particularly suitable are pigments such as kaolins, talc, calcium carbonate and / or barium sulfate.
Besonders bevorzugt ist ein Pigment mit einer engen Korngrößenverteilung, bei der mindestens 70% der Pigmentpartikeln eine Größe von kleiner als lμm aufweisen. Der Anteil des Pigments mit der engen Korngrößenverteilung an der gesamten Pig- mentmenge beträgt mindestens 5 Gew.% , insbesondere 10 bis 90 Gew. %. Besonders gute Ergebnisse sind mit einem Anteil von 30 bis 80 Gew. % des Gesamtpigments zu erreichen.Particularly preferred is a pigment having a narrow particle size distribution, in which at least 70% of the pigment particles have a size of less than 1 μm. The proportion of the pigment with the narrow particle size distribution of the total amount of pigment is at least 5% by weight, in particular 10 to 90% by weight. Particularly good results can be achieved with a proportion of 30 to 80% by weight of the total pigment.
MI/co 081540EP 11. September 2009 Unter einem Pigment mit einer engen Korngrößenverteilung werden erfindungsgemäß auch Pigmente mit einer Korngrößenverteilung verstanden, bei der mindestens etwa 70 Gew.% der Pig- mentpartikel eine Größe von kleiner als etwa 1 μm aufweist und bei 40 bis 80 Gew.% dieser Pigmentpartikeln die Differenz zwischen dem Pigment mit der größten Korngröße (Durchmesser) und dem Pigment der kleinsten Korngröße kleiner als etwa 0,4 μm ist. Als besonders vorteilhaft erwies sich ein Calciumcar- bonat mit einem d5o%-Wert von etwa 0,7 μm.MI / co 081540EP September 11, 2009 According to the invention, a pigment having a narrow particle size distribution is also understood as meaning pigments having a particle size distribution in which at least about 70% by weight of the pigment particles have a size of less than about 1 μm and 40 to 80% by weight of these pigment particles the pigment having the largest grain size (diameter) and the pigment of the smallest grain size is smaller than about 0.4 μm. Particularly advantageous is a carbonate Calciumcar- proved with a d o 5% value of about 0.7 microns.
In einer besonderen Ausführungsform der Erfindung kann in der pigmenthaltigen Schicht eine Pigmentmischung eingesetzt werden, die aus dem oben genannten Calciumcarbonat und Kaolin besteht. Das Mengenverhältnis Calciumcarbonat/Kaolin beträgt vorzugsweise 30:70 bis 70:30.In a particular embodiment of the invention, a pigment mixture consisting of the abovementioned calcium carbonate and kaolin can be used in the pigment-containing layer. The quantitative ratio calcium carbonate / kaolin is preferably 30:70 to 70:30.
Das Mengenverhältnis Bindemittel/Pigment in der pigmenthaltigen Schicht kann 0,1 bis 2,5, vorzugsweise 0,2 bis 1,5, insbesondere jedoch etwa 0,9 bis 1,3 betragen.The amount ratio of binder / pigment in the pigment-containing layer may be 0.1 to 2.5, preferably 0.2 to 1.5, but especially about 0.9 to 1.3.
In der pigmenthaltigen Schicht kann jedes bekannte wasserlösliche und/oder wasserdispergierbare Bindemittel eingesetzt werden. Besonders geeignet sind hierzu filmbildende Stärken wie thermisch modifizierte Stärken, insbesondere Maisstärken oder hydroxypropylierte Stärken.Any known water-soluble and / or water-dispersible binder can be used in the pigment-containing layer. Particularly suitable for this purpose are film-forming starches such as thermally modified starches, in particular corn starches or hydroxypropylated starches.
Die pigmenthaltige Schicht kann mit allen in der Papierherstellung üblichen Auftragsaggregaten inline oder offline auf- gebracht werden, wobei die Menge so gewählt wird, dass nach dem Trocknen das Auftragsgewicht 0,1 bis 30 g/m2, insbesondere 1 bis 20 g/m2, oder gemäß einer besonders bevorzugten Aus-The pigment-containing layer can be applied in-line or off-line with all customary in papermaking application units, the amount is chosen so that after drying the application weight 0.1 to 30 g / m 2 , in particular 1 to 20 g / m 2 , or according to a particularly preferred embodiment
MI/co 081540EP 11. September 2009 führungsform 2 bis 8 g/m2 beträgt. In einer bevorzugten Ausführungsform wird die pigmenthaltige Schicht mit einer innerhalb der Papiermaschine integrierten Leimpresse oder Filmpresse aufgetragen.MI / co 081540EP September 11, 2009 guide form 2 to 8 g / m 2 . In a preferred embodiment, the pigment-containing layer is applied with a size press or film press integrated within the paper machine.
In einer weiteren Ausgestaltung der Erfindung können auf die toneraufnehmende Schicht weitere Schichten wie Schutzschichten oder glanzverbessernde Schichten aufgetragen werden. Das Auftragsgewicht ist vorzugsweise kleiner als 1 g/m2.In a further embodiment of the invention, further layers such as protective layers or gloss-improving layers can be applied to the toner-receiving layer. The application weight is preferably less than 1 g / m 2 .
Die folgenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to explain the invention in more detail:
BeispieleExamples
Herstellung des RohpapiersProduction of the raw paper
Zur Herstellung des Rohpapiers wurde ein Eukalyptus-Zellstoff eingesetzt. Zur Mahlung wurde der Zellstoff als etwa 5 %ige wässrige Suspension (Dickstoff) mit Hilfe eines Refiners auf einen Mahlgrad von 35 0SR gemahlen. Die mittlere Faserlänge betrug 0,65 mm. Die Konzentration der Zellstofffasern im Dünnstoff betrug 1 Gew. %, bezogen auf die Masse der ZellstoffSuspension . Dem Dünnstoff wurden Zusatzstoffe zugesetzt wie ein neutrales Leimungsmittel Alkylketendimer (AKD) in ei- ner Menge von 0,48 Gew.%, Nassfestmittel Polyamin-Polyamid- Epichlorhydrinharz (Kymene®) in einer Menge von 0,36 Gew.% und ein natürliches CaCθ3 in einer Menge von 20 Gew.%. Die Mengenangaben beziehen sich auf die Zellstoffmasse. Der Dünnstoff, dessen pH-Wert auf etwa 7,5 eingestellt wurde, wurde vom Stoffauflauf auf das Sieb der Papiermaschine gebracht, worauf die Blattbildung unter Entwässerung der Bahn in derTo prepare the base paper, a eucalyptus pulp was used. For milling, the pulp was milled as an approximately 5% aqueous suspension (thick material) using a refiner to a freeness of 35 0 SR. The mean fiber length was 0.65 mm. The concentration of the pulp fibers in the thin material was 1% by weight, based on the mass of the pulp suspension. The thin stock additives were added as a neutral sizing agent alkylketene dimer (AKD) is present in an amount of from 0.48.%, Wet strength agents polyamine-polyamide epichlorohydrin resin (Kymene ®) is present in an amount of from 0.36.% And a natural CaCO 3 in an amount of 20% by weight. The quantities are based on the pulp mass. The thinness, whose pH was adjusted to about 7.5, was brought from the head box to the wire of the paper machine, followed by sheet formation while dewatering the web in the paper machine
MI/co 081540EP 11. September 2009 Siebpartie der Papiermaschine erfolgte. In der Pressenpartie erfolgte die weitere Entwässerung der Papierbahn auf einen Wassergehalt von 60 Gew. %, bezogen auf das Bahngewicht. Die weitere Trocknung erfolgte in der Trocken-partie der Papier- maschine mit beheizten Trockenzylindern. Es entstand ein Rohpapier mit einem Flächengewicht von 163 g/m2 und einer Feuchte von etwa 6%.MI / co 081540EP September 11, 2009 Wire section of the paper machine was done. In the press section, the further dewatering of the paper web was carried out to a water content of 60% by weight, based on the web weight. Further drying took place in the drying section of the paper machine with heated drying cylinders. The result was a base paper with a basis weight of 163 g / m 2 and a humidity of about 6%.
Beispiele Bl und B2 Das Rohpapier wurde in herkömmlicherweise Weise auf beidenExamples Bl and B2 The base paper was conventionally applied to both
Seiten mit einem Kunstharzgemisch folgender Zusammensetzung beschichtet: 50 Gew. eines Polyethylens niedriger Dichte (LDPE, d=0,923 g/m2) und 50 Gew. % eines Polyethylens hoher Dichte (HDPE, d=0,964 g/cm3). Die Beschichtung erfolgte in einem Laminator (Tandemextruder) bei einer Extrusions- geschwindigkeit von 250 m /min unter dem Einsatz eines Kühl- zylinders der Fa. BEP Service Technology, dessen Oberfläche einen mittleren Rz-Wert von 11,03 μm und einen Ra-Wert von 1,87 μm aufwies. Die Oberfläche des Kühlzylinders wurde durch Sandstrahlen bzw. Strahlen mit anderem Strahlgut erzeugt und verchromt. Die Auftragsgewichte auf beiden Seiten betrugen jeweils 15 g/m2.50% by weight of a low density polyethylene (LDPE, d = 0.923 g / m 2 ) and 50% by weight of a high density polyethylene (HDPE, d = 0.964 g / cm 3 ). The coating was carried out in a laminator (tandem extruder) at an extrusion speed of 250 m / min using a cooling cylinder from the company BEP Service Technology whose surface has an average Rz value of 11.03 μm and an Ra value of 1.87 μm. The surface of the cooling cylinder was produced by sandblasting or blasting with other blasting material and chrome plated. The application weights on both sides were 15 g / m 2 each.
Der anschließende Auftrag der toneraufnehmenden Schicht er- folgte mit Hilfe eines innerhalb der Extrusionsanlage integrierten Walzenauftragswerkes. Hierzu wurde wässrige Beschich- tungsmassen mit einem Feststoffgehalt von 19 Gew.% mit folgender Zusammensetzung verwendet:The subsequent application of the toner-receiving layer was carried out with the aid of a roll applicator integrated within the extrusion line. For this purpose, aqueous coating compositions having a solids content of 19% by weight and having the following composition were used:
MI/co 081540EP 11. September 2009 MI / co 081540EP September 11, 2009
erhältlich als eine wässrige Dispersion mit einemavailable as an aqueous dispersion with a
Feststoffanteil von 32 Gew.% erhältlich als eine wässrige Emulsion mit einem Feststoff¬ anteil von 50 Gew.% erhältlich als eine wässrige Dispersion mit einem Feststoffanteil von 60 Gew.%Solids content of 32 wt.% By weight available as an aqueous emulsion having a solids content of 50 ¬.% Available as an aqueous dispersion having a solid content of 60 wt.%
' erhältlich als eine wässrige Dispersion mit einem Feststoffgehalt von 45 Gew.%'Available as an aqueous dispersion having a solids content of 45% by weight.
Das Auftragsgewicht der getrockneten toneraufnehmenden Schicht betrug auf beiden Seiten jeweils 0,5 g/m2.The coated weight of the dried toner-receiving layer was 0.5 g / m 2 on both sides.
MI/co 081540EP 11. September 2009 VergleichsbeispieleMI / co 081540EP September 11, 2009 Comparative Examples
Vergleichsbeispiel 1Comparative Example 1
Als Vergleich diente ein marktübliches Aufzeichnungsmaterial für elektrofotografische Anwendungen Zander Silver Digital.As a comparison, a commercially available recording material for electrophotographic applications Zander Silver Digital was used.
Vergleichsbeispiel 2Comparative Example 2
Als Vergleich diente ein marktübliches Aufzeichnungsmaterial für elektrofotografische Anwendungen Zander Profi Gloss.As a comparison, a commercially available recording material for electrophotographic applications Zander Profi Gloss was used.
Prüfung der gemäß den Beispielen und den Vergleichsbeispielen hergestellten AufzeichnungsmaterialienExamination of the recording materials prepared according to the examples and the comparative examples
Das erfindungsgemäß hergestellte Material wurde auf Bildqua- lität, Licht- und Ozonbeständigkeit geprüft.The material produced according to the invention was tested for image quality, light and ozone resistance.
Grundlage der Prüfungen waren Farbdrucke, die mit dem Laser- Drucker HP Color Laser Jet 2605dn (Nasstoner) und dem Farbkopierer Konica Minolta MC5550 erzeugt wurden. Gedruckt wurden balkenartige Flächen in den Farben Cyan, Magenta, Gelb, Rot, Grün, Blau, und Schwarz, bei 100%iger Farbsättigung.The tests were based on color prints made with the HP Color Laser Jet 2605dn laser printer (wet toner) and the Konica Minolta MC5550 color copier. Bar-like areas in cyan, magenta, yellow, red, green, blue, and black were printed at 100% saturation.
Ozon-ResistenzOzone resistance
Die bedruckten Papierproben wurden unter Ausschuss von Licht- , Gas- und Feuchtigkeitsauswirkung 24 Stunden lang aufbewahrt. Anschließend wurden die colorimetrischen L*a*b*-Werte der Farbflächen ermittelt.The printed paper samples were stored under light, gas and moisture impact for 24 hours. Subsequently, the colorimetric L * a * b * values of the color areas were determined.
Im nächsten Schritt wurden die Proben 24 Stunden lang in ei- ner Ozon-Kammer bei einer Ozonkonzentration von 3,5 ppm, einer Temperatur von 20 bis 22°C und einer relativen Luftfeuchtigkeit von 40 bis 50% gelagert. Anschließend wurden nochmalsIn the next step, the samples were stored for 24 hours in an ozone chamber at an ozone concentration of 3.5 ppm, a temperature of 20 to 22 ° C and a relative humidity of 40 to 50%. Subsequently, again
MI/co 081540EP 11. September 2009 die colorimetrischen L*a*b*-Werte der Farbflächen gemessen und der Grad des Ausbleichens ΔE ermittelt.MI / co 081540EP September 11, 2009 measured the colorimetric L * a * b * values of the color areas and determined the degree of bleaching ΔE.
L*a*b*-Werte wurden mit einem X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA) gemessen. Die Berechnung der Farbtondifferenz ΔE erfolgt gemäß der Gleichung: ΔE = ((ΔL*)2 + (Δa*)2 + (Δb*)2)1/2. Die Prüfergebnisse sind in Tabelle 1 zusammengestellt.L * a * b * values were measured with an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA). The color tone difference ΔE is calculated according to the equation: ΔE = ((ΔL *) 2 + (Δa *) 2 + (Δb *) 2 ) 1/2 . The test results are summarized in Table 1.
Lichtbeständigkeitlight resistance
Die bedruckten Papierproben wurden unter Xenon-Lampe 50 Stunden lang, bei einer Temperatur von 26°C und einer relativen Luftfeuchtigkeit von 60% gehalten. Die Bewertung erfolgte nach dem oben beschriebenen CIE L*a*b*-System.The printed paper samples were held under xenon lamp for 50 hours, at a temperature of 26 ° C and a relative humidity of 60%. The evaluation was carried out according to the CIE L * a * b * system described above.
MI/co 081540EP 11. September 2009 PrüfergebnisseMI / co 081540EP September 11, 2009 test results
Tabelle 1 LichtresistenzTable 1 Light resistance
MI/co 081540EP 11. September 2009 Tabelle 2MI / co 081540EP September 11, 2009 Table 2
Ozonresistenzozone resistance
MI /co 081540EP 11 . September 2009 MI / co 081540EP 11. September 2009
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20090783066 EP2326992B1 (en) | 2008-09-19 | 2009-09-16 | Recording material for laser printing methods |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08105391 | 2008-09-19 | ||
| EP20090783066 EP2326992B1 (en) | 2008-09-19 | 2009-09-16 | Recording material for laser printing methods |
| PCT/EP2009/061988 WO2010031782A1 (en) | 2008-09-19 | 2009-09-16 | Recording material for laser printing methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2326992A1 true EP2326992A1 (en) | 2011-06-01 |
| EP2326992B1 EP2326992B1 (en) | 2015-04-22 |
Family
ID=41202285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20090783066 Active EP2326992B1 (en) | 2008-09-19 | 2009-09-16 | Recording material for laser printing methods |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110163528A1 (en) |
| EP (1) | EP2326992B1 (en) |
| JP (1) | JP5394489B2 (en) |
| CN (1) | CN102159998B (en) |
| WO (1) | WO2010031782A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011203672A (en) * | 2010-03-26 | 2011-10-13 | Fuji Xerox Co Ltd | Electrophotographic paper |
| JP5545540B2 (en) * | 2010-07-23 | 2014-07-09 | 株式会社リコー | Recording paper and image forming method |
| EP2428840A1 (en) * | 2010-09-10 | 2012-03-14 | Felix Schoeller jr Foto- und Spezialpapiere GmbH & Co. KG | Support material for photographic silver halide double coated paper |
| JP2018002187A (en) * | 2016-06-28 | 2018-01-11 | 三菱ケミカル株式会社 | Colored sheet for ptp, and ptp package |
| CN112482085B (en) * | 2020-11-16 | 2022-05-17 | 乐凯胶片股份有限公司 | Pearlescent printing material and method for preparing pearlescent printing material |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306863A (en) * | 1964-01-02 | 1967-02-28 | Geigy Chem Corp | Non-ionic polyoxyethylene surfactantethylene-maleic anhydride copolymer printing compositions |
| NL7305261A (en) * | 1973-04-16 | 1974-10-18 | ||
| US4938506A (en) * | 1987-07-31 | 1990-07-03 | Daimatsu Kagaku Kogyo Co., Ltd. | Postcard with revealable indicia and manufacturing method thereof |
| SE466259B (en) * | 1990-05-31 | 1992-01-20 | Arne Forsgren | PROTEIN D - AN IGD BINDING PROTEIN FROM HAEMOPHILUS INFLUENZAE, AND THE USE OF THIS FOR ANALYSIS, VACCINES AND PURPOSE |
| US5244714A (en) * | 1991-12-09 | 1993-09-14 | Xerox Corporation | Coated recording sheets for electrostatic printing processes |
| CA2139932A1 (en) * | 1992-07-22 | 1994-02-03 | James H. Thirtle | Nonimpact printing element |
| US5698333A (en) * | 1994-06-27 | 1997-12-16 | Mobil Oil Corporation | Multilayer film structures for use in the production of banknotes or the like |
| DE4435350C2 (en) * | 1994-09-21 | 1998-04-23 | Schoeller Felix Jun Papier | Image-receiving material for electrophotographic processes |
| AU9807098A (en) * | 1997-10-21 | 1999-05-10 | Northstar Print Group | A peelable label, method of use of the label, and method of making the label |
| JP2000010327A (en) * | 1998-06-22 | 2000-01-14 | Fuji Photo Film Co Ltd | Electrophotographic image receiving paper |
| JP2002341580A (en) * | 2001-04-27 | 2002-11-27 | Three M Innovative Properties Co | Image recording sheet |
| US20080224462A1 (en) * | 2001-05-01 | 2008-09-18 | Dubner Andrew D | Transparent tamper-indicating data sheet |
| EP1445096A4 (en) * | 2001-07-16 | 2009-01-14 | Yupo Corp | ANTI-FALSIFICATION FILM |
| JP2004070265A (en) * | 2002-06-12 | 2004-03-04 | Fuji Photo Film Co Ltd | Electrophotographic image receiving sheet, and image forming method |
| US7776413B2 (en) * | 2002-09-10 | 2010-08-17 | Yupo Corporation | Melt thermal transfer recording paper |
| JP2005148138A (en) * | 2003-11-11 | 2005-06-09 | Fuji Xerox Co Ltd | Electrophotographic label sheet and image forming method using the same |
| JP4432612B2 (en) * | 2004-05-19 | 2010-03-17 | 富士ゼロックス株式会社 | Electrophotographic transfer paper and image forming method |
| JP2006098910A (en) * | 2004-09-30 | 2006-04-13 | Nippon Paper Industries Co Ltd | Electrophotographic transfer paper manufacturing method |
| WO2006059561A1 (en) * | 2004-11-30 | 2006-06-08 | Tomoegawa Co., Ltd. | Electrophotographic image receiving sheet with water resistance |
| JP4382018B2 (en) * | 2005-09-02 | 2009-12-09 | 株式会社巴川製紙所 | Water-resistant electrophotographic image-receiving paper |
| JP4728658B2 (en) * | 2005-02-18 | 2011-07-20 | 日本製紙株式会社 | Laminated sheet |
| JP2006250979A (en) * | 2005-03-08 | 2006-09-21 | Fuji Xerox Co Ltd | Image forming apparatus |
| JP2006284685A (en) * | 2005-03-31 | 2006-10-19 | Nippon Paper Industries Co Ltd | Stacked sheet |
| JP2007199465A (en) * | 2006-01-27 | 2007-08-09 | Konica Minolta Holdings Inc | Electrophotographic image transfer medium |
| JP4678339B2 (en) * | 2006-06-06 | 2011-04-27 | 富士ゼロックス株式会社 | Electrophotographic recording medium and image forming method |
| JP2008083642A (en) * | 2006-09-29 | 2008-04-10 | Fuji Xerox Co Ltd | Transfer paper sheet for electrophotography |
| ATE465020T1 (en) * | 2006-12-07 | 2010-05-15 | Agfa Gevaert | METHOD FOR PRODUCING AN INFORMATION CARRIER |
| JP2008175890A (en) * | 2007-01-16 | 2008-07-31 | Oji Paper Co Ltd | Electrophotographic sheet and electrophotographic adhesive sheet |
| US20090084014A1 (en) * | 2007-10-01 | 2009-04-02 | Sloan Dale A | Personalized Photo Costuming Toy |
| US20090295142A1 (en) * | 2008-06-02 | 2009-12-03 | Alan William Maule | Repositionable label and related method |
-
2009
- 2009-09-16 JP JP2011519193A patent/JP5394489B2/en active Active
- 2009-09-16 US US13/119,465 patent/US20110163528A1/en not_active Abandoned
- 2009-09-16 CN CN2009801368111A patent/CN102159998B/en active Active
- 2009-09-16 WO PCT/EP2009/061988 patent/WO2010031782A1/en active Application Filing
- 2009-09-16 EP EP20090783066 patent/EP2326992B1/en active Active
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2010031782A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2326992B1 (en) | 2015-04-22 |
| CN102159998A (en) | 2011-08-17 |
| JP2011528811A (en) | 2011-11-24 |
| JP5394489B2 (en) | 2014-01-22 |
| US20110163528A1 (en) | 2011-07-07 |
| WO2010031782A1 (en) | 2010-03-25 |
| CN102159998B (en) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69120096T2 (en) | Treated papers | |
| EP2861429B1 (en) | Receiving layer for digital printing methods having nanofibrillated cellulose | |
| EP1126081B1 (en) | Support for recording layers | |
| DE19807209A1 (en) | High gloss resin-coated paper base for copying material with good surface, stiffness and curling resistance | |
| EP2010712B1 (en) | Layer support for recording materials | |
| EP2326992B1 (en) | Recording material for laser printing methods | |
| US8986818B2 (en) | Recording material for electrophotographic printing methods | |
| DE112005003537T5 (en) | Laminated bow | |
| DE602005000415T2 (en) | Ink-jet recording sheet | |
| DE69920218T2 (en) | INK JET RECORDING PAPER | |
| DE69907390T2 (en) | PAPER FOR THE INK JET RECORDING METHOD AND THE ELECTROPHOTOGRAPHIC RECORDING METHOD | |
| EP2076398B1 (en) | Inkjet recording material having a perforated rear-side synthetic resin layer | |
| EP2506078B1 (en) | Recording material for electrophotographic printing | |
| EP2431809B1 (en) | Recording material for electrophotographic printing | |
| EP1065070A2 (en) | Ink-jet recording material containing a thermoplastic copolymer having polyether groups | |
| EP3028866B1 (en) | Recording material for thermal printing method | |
| DE112015003454T5 (en) | Coated printing paper for an industrial ink jet printing press and method of making printing material | |
| EP4288293A1 (en) | Recording material for dye sublimation printing having improved transport properties | |
| JP5374557B2 (en) | Support material for photographic paper with silver halide treatment on both sides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20100830 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: STEINBECK, RAINER Inventor name: KOZLOWSKI, CHRISTOPH Inventor name: OVERBERG, ANDREAS |
|
| DAX | Request for extension of the european patent (deleted) | ||
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SCHOELLER TECHNOCELL GMBH & CO. KG |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTG | Intention to grant announced |
Effective date: 20141114 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 723576 Country of ref document: AT Kind code of ref document: T Effective date: 20150515 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502009010945 Country of ref document: DE Effective date: 20150528 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150824 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150722 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150723 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150822 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502009010945 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150422 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| 26N | No opposition filed |
Effective date: 20160125 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150916 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150916 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150930 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20090916 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150422 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20220920 Year of fee payment: 14 Ref country code: AT Payment date: 20220921 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220922 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20220926 Year of fee payment: 14 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20231001 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 723576 Country of ref document: AT Kind code of ref document: T Effective date: 20230916 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231001 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231001 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230916 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230930 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230916 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240918 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240919 Year of fee payment: 16 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230916 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230916 |