EP0262569B2 - Druckempfindliches Aufzeichnungsmaterial - Google Patents
Druckempfindliches Aufzeichnungsmaterial Download PDFInfo
- Publication number
- EP0262569B2 EP0262569B2 EP87113877A EP87113877A EP0262569B2 EP 0262569 B2 EP0262569 B2 EP 0262569B2 EP 87113877 A EP87113877 A EP 87113877A EP 87113877 A EP87113877 A EP 87113877A EP 0262569 B2 EP0262569 B2 EP 0262569B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- recording material
- sensitive recording
- material according
- colour former
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000003921 oil Substances 0.000 claims abstract description 17
- 239000003094 microcapsule Substances 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019198 oils Nutrition 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 7
- 235000019486 Sunflower oil Nutrition 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 239000002600 sunflower oil Substances 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 244000215068 Acacia senegal Species 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 5
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- -1 C1-C4-alkoxy radical Chemical class 0.000 claims 1
- 235000019483 Peanut oil Nutrition 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 239000004359 castor oil Substances 0.000 claims 1
- 235000019438 castor oil Nutrition 0.000 claims 1
- 239000003240 coconut oil Substances 0.000 claims 1
- 235000019864 coconut oil Nutrition 0.000 claims 1
- 235000005687 corn oil Nutrition 0.000 claims 1
- 239000002285 corn oil Substances 0.000 claims 1
- 235000012343 cottonseed oil Nutrition 0.000 claims 1
- 239000002385 cottonseed oil Substances 0.000 claims 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000004006 olive oil Substances 0.000 claims 1
- 235000008390 olive oil Nutrition 0.000 claims 1
- 239000000312 peanut oil Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000010499 rapseed oil Substances 0.000 claims 1
- 239000010496 thistle oil Substances 0.000 claims 1
- 239000010698 whale oil Substances 0.000 claims 1
- 241001465754 Metazoa Species 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 3
- 239000002775 capsule Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical class C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BDEIYMXBPHSOSG-UHFFFAOYSA-N 1-ethyl-4-(2-phenylethyl)benzene Chemical compound C1=CC(CC)=CC=C1CCC1=CC=CC=C1 BDEIYMXBPHSOSG-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
Definitions
- the invention is based on an object according to the preamble of claim 1.
- Color formers based on triphenylmethane leuco dyes have been described in DE-A-2750283. These color formers provide excellent color formation when in contact with acidic reactants. In order to be able to use this class of color formers in pressure-sensitive recording materials, these substances are dissolved in suitable solvents, of which DE-A-2750283 names partially hydrogenated terphenyl, alkylated naphthalenes or dibuthyl phthalate. The dissolved color formers are then enclosed in microcapsules in accordance with known methods. Microcapsules given as examples contain chlorinated biphenyl and dimethylnaphthalene, the wall material consisting of pig skin gelatin .
- EP-A-24898 proposes a solvent mixture of aromatic hydrocarbon and ester components in a certain ratio, the solvent for the dye precursor mixture advantageously consisting of at least 50% by weight of the solvent mixture and only in exceptional cases with higher proportions of inert diluent, e.g. Mineral or vegetable oils can be blended.
- inert diluent e.g. Mineral or vegetable oils
- EP-A-86636 in which aromatic hydrocarbons are preferred over oils of animal or vegetable origin and mineral oils among a large number of high-boiling solvents, expresses the generally prevailing view that the naturally occurring oils are based on mineral, animal or plant-based are less suitable because, despite their known physiological harmlessness, they are known as bad solvents for the usual color formers and their use in significant amounts would result in a lower color-forming capacity, in particular a lower color intensity.
- EP-A-234 394 which falls under Article 54 (3) EPC and applies to the contracting states CH, DE, FR, GB and LI, discloses, among other things, as a solvent for the triphenylmethane type color formers described therein.
- vegetable oils e.g. Sesame oil or sunflower oil, however, teaches the use of vegetable oils, kerosene and white oil in their examples as solvents only for diluting the main solvents: chlorinated paraffin, dodecylbenzene and diisopropylnaphthalene.
- interfacial reaction processes and polyaddition products of polyisocyanates and polyamines are given as the preferred capsule wall material. Water soluble wall materials are also disclosed, but not for encapsulating color former solutions containing vegetable oils or white oil as the predominant solvent component.
- the present invention is based on the object of providing a pressure-sensitive recording material in which the color formers enclosed in microcapsules are dissolved in a physiologically largely harmless solvent.
- the present invention overcomes this disadvantage of the known vegetable and animal oils as well as paraffin oil by using a color former based on a triphenylmethane leuco dye as defined in the claims, which is dissolved in the above-mentioned solvents.
- the solvent for the color former consists entirely of e.g. vegetable oils. To achieve the greatest possible harmlessness, however, it has proven sufficient if at least 80% by weight of the solvent used consists of the oils proposed according to the invention.
- the solvents known per se for color formers such as alkylated naphthalenes, hydrogenated terphenyls, alkylated biphenyls, diphenylethanes, alkylbenzenes, chlorinated paraffins, or mixtures of these compounds can be used as residual solvents. If more than 20% by weight of such solvents is added, there are increased concerns about the safety.
- capsule wall material which must be present in the dissolved state for the production of the microcapsules, is also of considerable importance in the context of the present invention.
- water-soluble polymers for the production of capsule wall materials have proven to be suitable for encapsulating the droplets consisting of solvent and color former dissolved therein.
- the invention also provides mixtures of the color formers mentioned, which are particularly advantageous for achieving a specific color tone.
- mineral oils white oil and spindle oil in particular, and also paraffinum liquidum known from the medical field according to DAB 8 (German Pharmaceutical Book, 8th edition) have proven to be particularly suitable.
- microcapsules are produced by methods known per se, such as the coacervation processes described in DE-B-1122495 and DE-A-2225274.
- suitable water-soluble polymeric substances e.g. Pig skin gelatin, gum arabic, cellulose compounds and polyvinyl alcohol are described.
- the production of microcapsules from urea-formaldehyde resins is specified in US Pat. No. 3,516,941.
- the invention is not restricted to the use of the encapsulation processes and capsule wall materials described in the above documents.
- the recording material according to the invention can be produced with all microcapsules, the walls of which are formed from a material initially dissolved in water, additional hardening steps possibly being used to form a dense and stable capsule wall, or such substances are added that further harden the Can cause capsule walls.
- solutions of color formers were prepared at temperatures of 25 to 40 ° C. and the solutions prepared were encapsulated in a melamine-formaldehyde precondensate.
- the finished microcapsules were applied to the back of a wood-free paper.
- a good color reaction and an excellent color intensity were observed, in particular in Examples 1 to 4.
- Examples 5 to 9 also showed good results with regard to color intensity. Satisfactory results were obtained with Examples 10 to 17 .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87113877T ATE64340T1 (de) | 1986-09-30 | 1987-09-23 | Druckempfindliches aufzeichnungsmaterial. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3633116 | 1986-09-30 | ||
| DE19863633116 DE3633116A1 (de) | 1986-09-30 | 1986-09-30 | Druckempfindliches aufzeichnungsmaterial |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0262569A2 EP0262569A2 (de) | 1988-04-06 |
| EP0262569A3 EP0262569A3 (en) | 1989-06-07 |
| EP0262569B1 EP0262569B1 (de) | 1991-06-12 |
| EP0262569B2 true EP0262569B2 (de) | 1994-03-02 |
Family
ID=6310630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87113877A Expired - Lifetime EP0262569B2 (de) | 1986-09-30 | 1987-09-23 | Druckempfindliches Aufzeichnungsmaterial |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4859650A (es) |
| EP (1) | EP0262569B2 (es) |
| JP (1) | JPS6395980A (es) |
| AT (1) | ATE64340T1 (es) |
| DE (2) | DE3633116A1 (es) |
| DK (1) | DK167384B1 (es) |
| ES (1) | ES2022247T5 (es) |
| FI (1) | FI88900C (es) |
| GR (1) | GR3002214T3 (es) |
| IL (1) | IL83870A (es) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3707548A1 (de) * | 1987-03-10 | 1988-10-06 | Bayer Ag | Farbbildner, ihre herstellung und verwendung |
| DE3727878A1 (de) * | 1987-08-21 | 1989-03-02 | Bayer Ag | Triarylmethan-farbbildner |
| GB9113086D0 (en) * | 1991-06-18 | 1991-08-07 | Wiggins Teape Group Ltd | Solvent compositions for use in pressure-sensitive copying paper |
| ES2125306T5 (es) * | 1992-06-04 | 2006-04-01 | Arjo Wiggins Limited | Material de registro piezosensible. |
| GB9221621D0 (en) * | 1992-10-15 | 1992-11-25 | Wiggins Teape Group Ltd | Solvents for use in pressure-sensitive record material |
| GB9313790D0 (en) * | 1993-07-03 | 1993-08-18 | Wiggins Teape Group The Ltd | Pressure-sensitive copying material |
| GB9318369D0 (en) * | 1993-09-04 | 1993-10-20 | Carrs Paper Ltd | Pressure-sensitive record materials |
| DE4409265A1 (de) * | 1994-03-18 | 1995-09-21 | Bayer Ag | Druckempfindliches Aufzeichnungsmaterial, das natürliche Öle und/oder Derivate davon enthält |
| US5462597A (en) * | 1994-06-30 | 1995-10-31 | Minnesota Mining And Manufacturing | System for inkless fingerprinting |
| GB9414637D0 (en) * | 1994-07-20 | 1994-09-07 | Wiggins Teape Group The Limite | Presure-sensitive copying material |
| FR2723032B1 (fr) | 1994-07-26 | 1996-11-22 | Copigraph Sa | Nouveau solvant organique pour microcapsules utiles notamment pour la realisation de papier autocopiant sensible a la pression et papier sensible a lapression revetu de telles microcapsules |
| FR2727633A1 (fr) | 1994-12-02 | 1996-06-07 | Copigraph | Microcapsules contenant a titre de solvant un derive terpenique ou d'acide abietique et papiers sensibles a la pression revetus de ces microcapsules |
| EP1539340B8 (de) * | 2002-09-20 | 2007-11-07 | Papierfabrik August Koehler AG | Verfahren zum einkapseln gelöster farbreaktionspartner von farbreaktionssystemen, die danach erhältlichen kapseln sowie deren verwendung in farbreaktionspapieren |
| US8053494B2 (en) * | 2003-10-06 | 2011-11-08 | Nocopi Technologies, Inc. | Invisible ink and scratch pad |
| US20050075420A1 (en) * | 2003-10-06 | 2005-04-07 | Terry Stovold | Invisible ink |
| US20050165131A1 (en) * | 2003-10-06 | 2005-07-28 | Terry Stovold | Invisible ink |
| US7815723B2 (en) * | 2006-04-19 | 2010-10-19 | Crayola Llc | Water-based ink system |
| US7727319B2 (en) * | 2006-04-19 | 2010-06-01 | Crayola Llc | Water-based ink system |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR408465A (es) * | 1900-01-01 | |||
| US3516941A (en) * | 1966-07-25 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsules and process of making |
| JPS5312473B1 (es) * | 1971-05-24 | 1978-05-01 | ||
| US3886085A (en) * | 1971-08-31 | 1975-05-27 | Fuji Photo Film Co Ltd | Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby |
| BE790321A (fr) * | 1971-10-20 | 1973-04-19 | Monsanto Co | Solvants pour colorants de materiaux d'enregistrement sensiblesa la pression |
| BE795255A (fr) * | 1972-02-11 | 1973-08-09 | Monsanto Co | Materiau d'enregistrement sensible a la pression, et solvants de colorants pour celui-ci |
| US3968301A (en) * | 1972-02-11 | 1976-07-06 | Monsanto Company | Pressure-sensitive record material and dye solvents therefor |
| JPS5318921B2 (es) * | 1972-07-28 | 1978-06-17 | ||
| JPS5321328B2 (es) * | 1973-10-31 | 1978-07-01 | ||
| FR2294055A1 (fr) * | 1974-12-10 | 1976-07-09 | Ciba Geigy Ag | Materiel d'enregistrement sensible a la pression ou a la chaleur |
| GB1517647A (en) * | 1976-06-16 | 1978-07-12 | Monsanto Europe Sa | Solvents |
| DE2750283C2 (de) * | 1977-11-10 | 1985-08-22 | Bayer Ag, 5090 Leverkusen | Druck- und wärmeempfindliches Aufzeichnungsmaterial |
| US4343652A (en) * | 1979-08-24 | 1982-08-10 | Monsanto Europe S.A. | Chromogen solutions for pressure-sensitive mark-recording systems |
| US4335013A (en) * | 1979-08-24 | 1982-06-15 | Monsanto Company | Solvents useful in pressure-sensitive mark-recording systems |
| US4398753A (en) * | 1980-12-26 | 1983-08-16 | Mitsui Toatsu Chemicals, Incorporated | Pressure sensitive recording unit |
| JPS57197192A (en) * | 1981-05-29 | 1982-12-03 | Fuji Photo Film Co Ltd | Microcapsule-containing sheet for pressure sensitive copying paper |
| JPS58138689A (ja) * | 1982-02-13 | 1983-08-17 | Mitsubishi Paper Mills Ltd | 感圧記録系 |
| JPS6027589A (ja) * | 1983-07-26 | 1985-02-12 | Kanzaki Paper Mfg Co Ltd | 記録体 |
| JPS615982A (ja) * | 1984-06-21 | 1986-01-11 | Nippon Petrochem Co Ltd | 感圧複写材料 |
| DE3447298C1 (de) * | 1984-12-24 | 1986-04-24 | Papierfabrik August Koehler AG, 7602 Oberkirch | Verfahren zur Mikroverkapselung von Ölen mit darin gelösten Farbreaktionspartnern und danach hergestellte Mikrokapseln |
| US4730057A (en) * | 1985-01-17 | 1988-03-08 | Kanzaki Paper Manufacturing Co., Ltd. | Phthalide derivatives useful as colorless chromogenic material |
| US4737587A (en) * | 1985-11-25 | 1988-04-12 | Mitsubishi Paper Mills, Ltd. | Colorless carbazole dyes for recording materials |
-
1986
- 1986-09-30 DE DE19863633116 patent/DE3633116A1/de not_active Withdrawn
-
1987
- 1987-09-11 IL IL83870A patent/IL83870A/xx not_active IP Right Cessation
- 1987-09-23 ES ES87113877T patent/ES2022247T5/es not_active Expired - Lifetime
- 1987-09-23 DE DE8787113877T patent/DE3770735D1/de not_active Expired - Fee Related
- 1987-09-23 EP EP87113877A patent/EP0262569B2/de not_active Expired - Lifetime
- 1987-09-23 AT AT87113877T patent/ATE64340T1/de not_active IP Right Cessation
- 1987-09-25 FI FI874231A patent/FI88900C/fi not_active IP Right Cessation
- 1987-09-30 DK DK514287A patent/DK167384B1/da active
- 1987-09-30 US US07/103,115 patent/US4859650A/en not_active Expired - Fee Related
- 1987-09-30 JP JP62244449A patent/JPS6395980A/ja active Pending
-
1991
- 1991-06-27 GR GR91400896T patent/GR3002214T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0262569B1 (de) | 1991-06-12 |
| DK514287D0 (da) | 1987-09-30 |
| JPS6395980A (ja) | 1988-04-26 |
| DK167384B1 (da) | 1993-10-25 |
| FI88900B (fi) | 1993-04-15 |
| FI874231A0 (fi) | 1987-09-25 |
| ES2022247B3 (es) | 1991-12-01 |
| FI88900C (fi) | 1993-07-26 |
| DE3633116A1 (de) | 1988-04-07 |
| DE3770735D1 (de) | 1991-07-18 |
| US4859650A (en) | 1989-08-22 |
| IL83870A0 (en) | 1988-02-29 |
| FI874231A (fi) | 1988-03-31 |
| GR3002214T3 (en) | 1992-12-30 |
| IL83870A (en) | 1991-12-15 |
| EP0262569A3 (en) | 1989-06-07 |
| DK514287A (da) | 1988-03-31 |
| ATE64340T1 (de) | 1991-06-15 |
| EP0262569A2 (de) | 1988-04-06 |
| ES2022247T5 (es) | 1995-08-16 |
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