US3085898A - Paper product with watermark and process therefor - Google Patents
Paper product with watermark and process therefor Download PDFInfo
- Publication number
- US3085898A US3085898A US832148A US83214859A US3085898A US 3085898 A US3085898 A US 3085898A US 832148 A US832148 A US 832148A US 83214859 A US83214859 A US 83214859A US 3085898 A US3085898 A US 3085898A
- Authority
- US
- United States
- Prior art keywords
- paper
- weight
- watermark
- percent
- sucrose acetate
- 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
- 238000000034 method Methods 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 claims description 39
- 238000013461 design Methods 0.000 claims description 33
- UVGUPMLLGBCFEJ-SWTLDUCYSA-N sucrose acetate isobutyrate Chemical compound CC(C)C(=O)O[C@H]1[C@H](OC(=O)C(C)C)[C@@H](COC(=O)C(C)C)O[C@@]1(COC(C)=O)O[C@@H]1[C@H](OC(=O)C(C)C)[C@@H](OC(=O)C(C)C)[C@H](OC(=O)C(C)C)[C@@H](COC(C)=O)O1 UVGUPMLLGBCFEJ-SWTLDUCYSA-N 0.000 claims description 29
- 239000001797 sucrose acetate isobutyrate Substances 0.000 claims description 28
- 235000010983 sucrose acetate isobutyrate Nutrition 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 11
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 24
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 24
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 22
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 21
- 239000000126 substance Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 description 8
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 6
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 6
- JSFATNQSLKRBCI-NLORQXDXSA-N 73945-47-8 Chemical compound CCCCCC(O)\C=C\C=C\C\C=C\C\C=C\CCCC(O)=O JSFATNQSLKRBCI-NLORQXDXSA-N 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- RXNSHAMUSHFNMJ-UHFFFAOYSA-N 2-ethoxyethanol;2-(2-methoxyethoxy)ethanol Chemical compound CCOCCO.COCCOCCO RXNSHAMUSHFNMJ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 241000529895 Stercorarius Species 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 241000746181 Therates Species 0.000 description 1
- QXNIBPDSSDVBQP-UHFFFAOYSA-N acetic acid;2-methylpropanoic acid Chemical compound CC(O)=O.CC(C)C(O)=O QXNIBPDSSDVBQP-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- DUIHIDNLDMIFPA-UHFFFAOYSA-N ethanol;2-ethoxyethanol Chemical compound CCO.CCOCCO DUIHIDNLDMIFPA-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/10—Watermarks
-
- 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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
-
- 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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
Definitions
- This invention relates to a paper product having a watermark therein and means for making same. More in particular this invention relates to means for forming a watermark in otherwise finished paper products.
- the present practice of watermarking is usually performed during the paper-making process by providing embossed rolls interposed usually at a point before the wet paper Web enters the dryers.
- the fibres in the web are displaced in horizontal position and the paper is thus rendered thinner and consequently more transparent at the area of the watermark.
- the embossed rolls form the mark in the damp or wet paper which upon drying remains permanent.
- the finished paper is cut into sheets of various sizes, such as those established for stationery and the like.
- Another known method of forming a watermark involves the employment of a band fitted about a roll and carrying the design of the Watermark in relief.
- the design is brought into contact with the wet paper web at the wet presses beyond the Fourdrinier or wet end. At that point the paper is still plastic and compresses readily.
- the resulting compression of fibres, reducing entrapped air and light refraction, increases the transparency of the area of the watermark.
- Watermarked paper made as above described has several disadvantages.
- Second, the cost of the embossed or banded rolls for the paper making machine is obviously extremely high and could therefore not be aiforded by smaller industrial users.
- the cost of setting up the embossed or banded rolls involves both labor as Well as loss of production on the paper making machinery which must be taken into account in the net cost to the purchaser.
- the purchaser finds that his private watermark is not positioned uniformly in the finished cut stationery unless he assumes the additional labor cost and paper waste involved in constantly positioning relatively the rolled paper and cut-01f knife. While private watermarks may be formed by presently known methods, it is thus clear that orders for paper products so marked must be large if the cost thereof is to be economically justified and orders in small quantities are of such cost as to he rarely justilied.
- the present invention contemplates the elimination of the above mentioned disadvantages. It is therefore one object of this invention to convert blank paper into a paper product having a uniformly positioned watermark therein.
- Another object of this invention is to form in a blank cut sheet paper product a visible watermark.
- a further object of this invention is to form by impregnation of blank paper an effective watermark.
- a still further object of this invention is to provide blank paper intended for use as paper sheet products with a satisfactory watermark, according to the preceding objects, wherein the watermark may be positioned uniformly on all sheets.
- a yet further object of this invention is to provide such paper products, according to the preceding objects, in small qu-antieties at low cost.
- Another important object of this invention is to provide a particular means for converting opaque or translucent paper into a substantially more transparent paper.
- Another object is to provide a method of forming a watermark in paper involving the adequate displacement of entrained air.
- Another purpose is to provide a method of forming a watermark by replacing air in a paper product with a material having an index of refraction similar to that of cellulose.
- Another purpose is to provide a method of forming a watermarked paper product by impregnation thereof to replace entrapped air in a localized area.
- blank paper i.e. having no watermark
- a watermark by employing a novel chemical composition whereby after drying transparent areas are created in the paper sheet conforming to the desired configuration of the watermark.
- the resulting watermark possesses for all practical purposes the same general characteristics in use as that of a watermark formed by the earlier, known processes above described.
- a chemical composition suitable for forming a watermark as above mentioned must have the ability to mark the paper in a manner to render it more translucent or substantially transparent in the impregnated area. Further the chemical composition should not alter the surface of the paper adversely. For example, it must not render the surface glossy in the impregnated area and must not alter the erasability characteristic of the paper. In addition the chemical composition must withstand aging without discoloration and must not become indistinct through migration of the chemicals or otherwise. And of course, aside from low cost, the watermarked area must accept typing, penciling, printing and writing inks without adverse effects such as feathering or skipping. Certain chemical compositions of this invention have been successfully employed in the formation of watermarks which conform to the above mentioned requirements as hereinafter described.
- a Watermark from a fundamental viewpoint, possesses a translucency of higher degree of transparency in the marked area than that possessed by the paper in the unmarked areas. The most common type of watermark appears more transparent than the surrounding unmarked paper.
- sucrose acetate isobutyrate the isobutyrate radicals may well be substituted with normal butyrate radicals, the chemical and physical analogy between these two radicals being substantially the same.
- Sucrose acetate isobutyrate may be prepared by the procedure set out in US. 2,931,802. Furthermore it appears that none of these organic chemicals enter into chemical reaction with the constituents of the paper. Rather it appears to be a matter of obtaining proper displacement of entrained air with these organic compounds to create a satisfactory mark in the paper.
- the thickness, composition and weight (density) of the paper sheet are variables and must be considered. Surprisingly, however, it was found that such variables were largely overcome by adjusting the concentration of the above described chemicals in selected organic solvents.
- the selection of the organic solvent as a carrier is important for if the solvent evaporates at an excessive rate the penetration of the paper is insufficient to result in proper impregnation by the organic solutes employed. On the other hand if the solvent evaporates too slowly, the organic solutes tend to migrate in the paper resulting in an indistinct watermark.
- inert organic solvents having boiling points at atmospheric pressure in the range of 100 C. to 250 C. possessed vapor pressures at room temperatures suitable for this invention.
- inert in the present discussion is intended to mean that the solvent enters no chemical reaction under the conditions of this invention.
- the composition employed for forming a watermark in paper according to this invention is a liquid solution consisting of about 30% to 70% by weight of at least one organic salt selected from the group consisting of sucrose acetate butyrate, sucrose acetate isobutyrate and alkali metal salts of an alkyl sulfosuccinate, and the balance of 70% to 30% by weight being an organic solvent therefor having a boiling point in the range of C. to 250 C. Concentrations of the compounds in solvents above about 70% by weight were found to produce indistinct watermarks due to lIlSUffiClGllt penetra' tion of the paper while concentrations below about 30% by weight produced watermarks of insufficient visibility in reflected or transmitted light.
- solvents successfully employed in composi' tions according to this invention included diethylene glycol monoethyl ether (Carbitol), ethylene glycol monomethyl ether, ethylene glycol diethyl ether, benzyl alcohol, Z-(Z-methoxyethoxy) ethanol, ethylene glycol monophenyl ether and ethylene glycol monoethyl ether.
- Carbitol diethylene glycol monoethyl ether
- ethylene glycol monomethyl ether ethylene glycol diethyl ether
- benzyl alcohol Z-(Z-methoxyethoxy) ethanol
- ethylene glycol monophenyl ether ethylene glycol monoethyl ether
- Example 1 Percent Sodium dioctyl sulfosuccinate 50 2-methoxy ethanol 50
- Example II Sodium dioctyl sulfosuccinate 50 2-methoxy ethanol 25 Diethylene glycol monoethyl ether 25
- Example III Sodium dioctyl sulfosuccinate 50 Diethylene glycol monoethyl ether 50
- Example IV Sucrose acetate isobutyrate 50 Ethylene glycol monomethyl ether 50
- Example V Sucrose acetate isobutyrate 50 Diethylene glycol monoethyl ether 50
- Example VI Sucrose acetate isobutyrate 35 Diethylene glycol monoethyl ether 65
- Example VII Sucrose acetate isobutyrate 50 Ethylene glycol monoethyl ether 50
- Example VIII Sodium dioctyl sulfosuccinate 50 Diethylene glycol monoethyl ether 50
- Example IX Sodium
- Example X VI Sodium dioctyl sulfosuccinate .25 Sucrose acetate isobutyrate 49.75 Diethylene glycol monoethyl ether 50.00
- Example XVII Sodium dioctyl sulfosuccinate .5 Sucrose acetate isobutyrate 49.5 Diethylene glycol monoethyl ether 50.0
- Example XVIII Sodium dioctyl sulfosuccinate 1.0 Sucrose acetate isobutyrate 49.0 Diethylene glycol monoethyl ether 50.0
- the blank paper product employed was of the bond grade consisting of 25% cotton and 75% chemical Woodpulp.
- the apparent density of the blank paper stock was about 5.0 and its thickness about 4.0 mils.
- the resulting watermarks possessed a high degree of transparency.
- opaque and semiopaque can refer to varying levels of opacity, depending on the specific type of paper under discussion. For purposes herein, more definite meanings can be given these terms by the following explanation.
- semi-opaque is generally accepted by the trade as a standard weight sheet of bond paper having a TAP PI opacity somewhere between 87% and 65%.
- TAPPI opacity less than 65% are often referred to as transparent. It will suifice to say that the lower the TAPPI opacity, the more often the trade refers to transparency, and the closer the opacity is to 65%, the more often the trade uses the term translucent. Translucent papers usually retain the more common characteristics of bond papers, such as formation and brightness, whereas transparent sheets most often have. a more uniformly translucent fibre mass with considerably less brightness.
- the term translucent usually implies that a ray of light passing through a material is difiiused while the term transparent implies that a ray of light passing through is not diffused.
- a translucent object may vary from opaque to true transparent according to the magnitude of difi'usion of light passing therethrough.
- transparent is used to denote that the magnitude of diffusion of light passing through the paper is not greater than that found in commercial tracing paper.
- TAPPI opacity less than 65 it is termed herein as transparent and conversely if 65% or greater it is termed herein as translucent.
- Tr-ansparentized paper has many commercial uses such as tracing paper and the like. Also there is a commercial demand for translucent paper having only a portion of the sheet transparentized such as the window type mailing envelopes wherein the address is printed on the contents of the envelope and positioned beneath the transparent window.
- Example XX Composition A Percent Sucrose acetate isobutyrate 50 Diethyl glycol monoethyl ether 50 Paper: Bond grade, 25 cotton-75% chemical wood pulp, having a thickness of 4.0 mils and an apparent density of 5.0.
- Example XXI Paper Same as in Example XX.
- the watermark was first applied on one side employing composition B and then, in register, the other side employing composition A.
- the rate of application on each side was the same as that of Example XX. watermark was clear and distinct.
- Example XXII Same as Example XXI except the following composition C was substituted for Composition B.
- Example XXI The resulting Same as for Example XXI except that the paper employed had additiona1 sizing. The resulting watermark was clear and distinct.
- Example XXIV Same as Example XXIII except that the rate of application was increased to 100 feet per minute. The resulting watermark was distinct.
- Example XXV Same as Example XXII except that onionskin paper was employed. The resulting watermark was clear and distinct.
- Example XXVI Same as Example XXII except that onionskin paper was employed and treated only on one side using composition C. The resulting watermark was clear and distinct.
- Example XX VII Same as Example XXII except that onionskin paper was employed and treated only on one side using Composition A. The resulting watermark was clear and distinct.
- the amount of imregnating composition in terms of percent by Weight may vary due to the type and density of the paper used. Therefore a sufiicient amount effective to reduce the TAPPI opacity to below 65% is necessary to transparentize translucent paper.
- an impregnation in the amount of 15% by weight of the impregnating composition based on the weight of the paper gave satisfactory results.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a composition consisting of about 30 percent by weight to about 70 percent by weight of at least one organic compound selected from the group consisting of sucrose acetate butyrate sucrose acetate isobutyrate and an alkali metal salt of a dialkyl sulfosuccinate dissolved in an inert organic solvent, said solvent having a boiling point in the range of about C. to about 250 C. in an amount of about 70 percent by weight to about 30 percent by weight.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium dioctyl sulfosuccinate dissolved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said organic solvent having a boiling point in the range of about 100 C. to about 250 C.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium diamyl sulfosuccinate dissolved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium dihexyl sulfosuccinate dis- 9 solved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
- the method of imparting a substantial-1y permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of from 0.3 percent by weight to 40 percent by weight of sodium dioctyl sulfosuccinate, from percent by weight to 69 percent by Weight of sucrose acetate isobutyrate, and at least 30 percent by Weight and not more than 70 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of from 0.3 percent by weight to 40 percent by Weight of sodium dihexyl sulfosuccinate, from 10 percent by weight to 69 percent by weight of sucrose acetate isobuty-rate, and at least 30 percent by weight and not more than 70 percent by weight of an inert organic sol- 1O vent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
- the method of imparting a substantially permanent Watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design With a liquid composition consisting of about 12.5% by Weight of sodium dioctyl sulfosuccinate, about 37.5% by weight of sucrose acetate isobutyrate and about by weight of diethylene glycol monoethyl ether.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of forming a liquid composition consisting of from 0.3 percent by weight to 40 percent by Weight of sodium dioctyl sulfosuccinate, from 10 percent by weight to 69 percent by Weight of sucrose acetate isobutyrate and from 30 percent by weight to 70 percent by weight of an inert inorganic solvent, and thereafter displacing entrapped air in a portion of said paper with said composition in an area conforming to the said design of said watermark.
- the method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of forming a liquid composition consisting of from 0.3 percent by Weight to 40 percent by weight of sodium dihexyl sulfosuccinate, from 10 percent by weight to 69 percent 'by weight of sucrose acetate isobutyrate and from 30 percent by Weight to 70 percent by 7 weight of an inert inorganic solvent, and thereafter displacing entrapped air in a portion of said paper with said composition in an area conforming to the said design of said watermark.
Landscapes
- Paper (AREA)
Description
i tr
ice
This invention relates to a paper product having a watermark therein and means for making same. More in particular this invention relates to means for forming a watermark in otherwise finished paper products.
A simplified flow diagram of the method is as follows:
Dissolve impregnating compound in an organic solvent of boiling point about C. to about 250 C.
Apply impregnating composition to impregnating tool having design on face Impregnate in composition to transparcntize Contact impregnating tool p p r with paper Impregnate design in paper Dry paper Particularly in ofiice operations of commercial enterprises it is often desirable to have writing stationery and other forms of business and professional papers watermarked. Oftentimes business trademarks are watermarked for identity and protective purposes and such watermarking serves as an additional means of distinctivity associated with a particular business enterprise.
The present practice of watermarking is usually performed during the paper-making process by providing embossed rolls interposed usually at a point before the wet paper Web enters the dryers. The fibres in the web are displaced in horizontal position and the paper is thus rendered thinner and consequently more transparent at the area of the watermark. Thus the embossed rolls form the mark in the damp or wet paper which upon drying remains permanent. After the paper making and watermarking process is complete the finished paper is cut into sheets of various sizes, such as those established for stationery and the like.
Another known method of forming a watermark involves the employment of a band fitted about a roll and carrying the design of the Watermark in relief. The design is brought into contact with the wet paper web at the wet presses beyond the Fourdrinier or wet end. At that point the paper is still plastic and compresses readily. The resulting compression of fibres, reducing entrapped air and light refraction, increases the transparency of the area of the watermark.
Watermarked paper made as above described has several disadvantages. First, the commercial paper making machines are very large and produce paper at a high volume rate. Thus for economical reasons a customer desiring stationery bearing a private watermark such as a trademark must purchase a large amount of each kind of paper needed. This of course limits such privately watermarked papers to a few but relatively large industrial users or governmental departments as it is obvious that smaller enterprises could not economically purchase and stock a supply sufiicient for several years. Second, the cost of the embossed or banded rolls for the paper making machine is obviously extremely high and could therefore not be aiforded by smaller industrial users. Third, the cost of setting up the embossed or banded rolls involves both labor as Well as loss of production on the paper making machinery which must be taken into account in the net cost to the purchaser. Furthermore, among other disadvantages, the purchaser finds that his private watermark is not positioned uniformly in the finished cut stationery unless he assumes the additional labor cost and paper waste involved in constantly positioning relatively the rolled paper and cut-01f knife. While private watermarks may be formed by presently known methods, it is thus clear that orders for paper products so marked must be large if the cost thereof is to be economically justified and orders in small quantities are of such cost as to he rarely justilied.
The present invention contemplates the elimination of the above mentioned disadvantages. It is therefore one object of this invention to convert blank paper into a paper product having a uniformly positioned watermark therein.
Another object of this invention is to form in a blank cut sheet paper product a visible watermark.
A further object of this invention is to form by impregnation of blank paper an effective watermark.
A still further object of this invention is to provide blank paper intended for use as paper sheet products with a satisfactory watermark, according to the preceding objects, wherein the watermark may be positioned uniformly on all sheets.
A yet further object of this invention is to provide such paper products, according to the preceding objects, in small qu-antieties at low cost.
Another important object of this invention is to provide a particular means for converting opaque or translucent paper into a substantially more transparent paper.
Another object is to provide a method of forming a watermark in paper involving the adequate displacement of entrained air.
Another purpose is to provide a method of forming a watermark by replacing air in a paper product with a material having an index of refraction similar to that of cellulose.
Another purpose is to provide a method of forming a watermarked paper product by impregnation thereof to replace entrapped air in a localized area.
These and other desirable objects inherent in and encompassed by the invention will be more readily understood from the ensuing description and the appended claims.
According to this invention blank paper (i.e. having no watermark) is impregnated with a watermark by employing a novel chemical composition whereby after drying transparent areas are created in the paper sheet conforming to the desired configuration of the watermark. The resulting watermark possesses for all practical purposes the same general characteristics in use as that of a watermark formed by the earlier, known processes above described.
A chemical composition suitable for forming a watermark as above mentioned must have the ability to mark the paper in a manner to render it more translucent or substantially transparent in the impregnated area. Further the chemical composition should not alter the surface of the paper adversely. For example, it must not render the surface glossy in the impregnated area and must not alter the erasability characteristic of the paper. In addition the chemical composition must withstand aging without discoloration and must not become indistinct through migration of the chemicals or otherwise. And of course, aside from low cost, the watermarked area must accept typing, penciling, printing and writing inks without adverse effects such as feathering or skipping. Certain chemical compositions of this invention have been successfully employed in the formation of watermarks which conform to the above mentioned requirements as hereinafter described.
A Watermark, from a fundamental viewpoint, possesses a translucency of higher degree of transparency in the marked area than that possessed by the paper in the unmarked areas. The most common type of watermark appears more transparent than the surrounding unmarked paper.
After considerable experimental work four organic compounds were discovered which, when properly applied to or impregnated into the paper, imparted to the paper sheet a watermark which was more translucent than the surrounding paper. These four organic compounds are defined as follows:
(1) Sodium dioctyl sulfosuccinate (2) Sucrose acetate isobutyrate (3) Sodium dihexyl sulfosuccinate (4) Sodium diamyl sulfosuccinate Although sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate and sodium diamyl sulfosuccinate were found to be excellent for the purpose of this invention it appears that corresponding salts of other alkai metals are equally applicable for the same purpose. Likewise in the case of sucrose acetate isobutyrate, the isobutyrate radicals may well be substituted with normal butyrate radicals, the chemical and physical analogy between these two radicals being substantially the same. Sucrose acetate isobutyrate may be prepared by the procedure set out in US. 2,931,802. Furthermore it appears that none of these organic chemicals enter into chemical reaction with the constituents of the paper. Rather it appears to be a matter of obtaining proper displacement of entrained air with these organic compounds to create a satisfactory mark in the paper.
In order to obtain the necessary degree of impregnation or coating with the above described organic compounds certain fundamental characteristics of the paper sheet must be considered. For example, the thickness, composition and weight (density) of the paper sheet are variables and must be considered. Surprisingly, however, it was found that such variables were largely overcome by adjusting the concentration of the above described chemicals in selected organic solvents. The selection of the organic solvent as a carrier is important for if the solvent evaporates at an excessive rate the penetration of the paper is insufficient to result in proper impregnation by the organic solutes employed. On the other hand if the solvent evaporates too slowly, the organic solutes tend to migrate in the paper resulting in an indistinct watermark. In this respect it was found that inert organic solvents having boiling points at atmospheric pressure in the range of 100 C. to 250 C. possessed vapor pressures at room temperatures suitable for this invention. The term inert in the present discussion is intended to mean that the solvent enters no chemical reaction under the conditions of this invention.
Broadly speaking, the composition employed for forming a watermark in paper according to this invention is a liquid solution consisting of about 30% to 70% by weight of at least one organic salt selected from the group consisting of sucrose acetate butyrate, sucrose acetate isobutyrate and alkali metal salts of an alkyl sulfosuccinate, and the balance of 70% to 30% by weight being an organic solvent therefor having a boiling point in the range of C. to 250 C. Concentrations of the compounds in solvents above about 70% by weight were found to produce indistinct watermarks due to lIlSUffiClGllt penetra' tion of the paper while concentrations below about 30% by weight produced watermarks of insufficient visibility in reflected or transmitted light.
Some of the solvents successfully employed in composi' tions according to this invention included diethylene glycol monoethyl ether (Carbitol), ethylene glycol monomethyl ether, ethylene glycol diethyl ether, benzyl alcohol, Z-(Z-methoxyethoxy) ethanol, ethylene glycol monophenyl ether and ethylene glycol monoethyl ether.
In order to evaluate the various compositions of this invention, Watermarks of excellent quality were obtained in the laboratory by hand impregnation. The hand impregnation was accomplished by depositing a small metered amount of the composition on the surface of a footsquare piece of one-quarter inch thick plate glass. The composition was spread uniformly over the glass surface with a handproofer consisting of an engraved roll bearing 75 depressions per inch and fitted with a handle. A die or hand stamp of rubber-like material having inscribed on the face thereof a typical watermark design was first pressed against the wet film of the composition on the glass and then stamped on the paper sheet. The watermarked paper sheet was allowed to dry and then examined.
By way of illustration of the invention, excellent watermarks were obtained by laboratory hand impregnation, as above described, employing novel compositions of this invention in each of the following examples, the stated proportions being in terms of weight:
Example 1 Percent Sodium dioctyl sulfosuccinate 50 2-methoxy ethanol 50 Example II Sodium dioctyl sulfosuccinate 50 2-methoxy ethanol 25 Diethylene glycol monoethyl ether 25 Example III Sodium dioctyl sulfosuccinate 50 Diethylene glycol monoethyl ether 50 Example IV Sucrose acetate isobutyrate 50 Ethylene glycol monomethyl ether 50 Example V Sucrose acetate isobutyrate 50 Diethylene glycol monoethyl ether 50 Example VI Sucrose acetate isobutyrate 35 Diethylene glycol monoethyl ether 65 Example VII Sucrose acetate isobutyrate 50 Ethylene glycol monoethyl ether 50 Example VIII Sodium dioctyl sulfosuccinate 50 Diethylene glycol monoethyl ether 50 Example IX Sodium dioctyl sulfosuccinate 40 Sucrose acetate isobutyrate l0 Diethylene glycol monoethyl ether 50 Example X Sodium dioctyl sulfosuccinate 25 Sucrose acetate isobutyrate 25 Diethylene glycol monoethyl ether 50 lam Example XI Percent Sodium dioctyl sulfosuccinate Sucrose acetate isobutyrate 40 Diethylene glycol monoethyl ether 50 Example XII Sodium dihexyl sulfosuccinate 50 Diethylene glycol monoethyl ether 50 Example XIII Sodium diamyl sulfosuccinate 50 Benzyl alcohol 50 Example XIV Sodium diamyl sulfosuccinate 50 2-(2-methoxyethoxy) ethanol 50 Example XV Sodium dioctyl sulfosuccinate 0.05 Sucrose acetate isobutyrate 49.95 Diethylene glycol monoethyl ether 50.00
Example X VI Sodium dioctyl sulfosuccinate .25 Sucrose acetate isobutyrate 49.75 Diethylene glycol monoethyl ether 50.00
Example XVII Sodium dioctyl sulfosuccinate .5 Sucrose acetate isobutyrate 49.5 Diethylene glycol monoethyl ether 50.0
Example XVIII Sodium dioctyl sulfosuccinate 1.0 Sucrose acetate isobutyrate 49.0 Diethylene glycol monoethyl ether 50.0
Example XIX Sodium dihexyl sulfosuccinate 2.5 Sucrose acetate isobutyrate 47.5 Diethylene glycol monoethyl ether 50.0
Accelerated aging of the watermarks in the above examples at 150 F. for 72 hours showed no discoloration.
In the above examples the blank paper product employed was of the bond grade consisting of 25% cotton and 75% chemical Woodpulp. The apparent density of the blank paper stock Was about 5.0 and its thickness about 4.0 mils. The resulting watermarks possessed a high degree of transparency.
In the paper industry the terms opaque and semiopaque can refer to varying levels of opacity, depending on the specific type of paper under discussion. For purposes herein, more definite meanings can be given these terms by the following explanation.
In the writing paper field, trade practice classifies an opaque sheet of bond paper as one of a standard weight (500 sheets, cut 17 inches by 22 inches, weighing between 19.5 lbs. and 20.5 lbs.) having a TAPPI opacity in excess of 87%. This percent is the reciprocal of the transmission of monochromatic light passing through the paper and photometrically measured.
The less commonly used term, semi-opaque, is generally accepted by the trade as a standard weight sheet of bond paper having a TAP PI opacity somewhere between 87% and 65%.
Writing papers having a TAPPI opacity less than 65% are often referred to as transparent. It will suifice to say that the lower the TAPPI opacity, the more often the trade refers to transparency, and the closer the opacity is to 65%, the more often the trade uses the term translucent. Translucent papers usually retain the more common characteristics of bond papers, such as formation and brightness, whereas transparent sheets most often have. a more uniformly translucent fibre mass with considerably less brightness.
This explaantion holds true whether the paper under discussion is made entirely of'chemical wood pulp, a blend of chemical wood pulp and cotton or linen fibres, or entirely of cotton and/ or linen fibres.
Technically the term translucent usually implies that a ray of light passing through a material is difiiused while the term transparent implies that a ray of light passing through is not diffused. Thus a translucent object may vary from opaque to true transparent according to the magnitude of difi'usion of light passing therethrough. However, for purpose of this discussion the term transparent is used to denote that the magnitude of diffusion of light passing through the paper is not greater than that found in commercial tracing paper. Thus if a sheet of paper possesses a TAPPI opacity less than 65 it is termed herein as transparent and conversely if 65% or greater it is termed herein as translucent.
In the foregoing examples the areas covered by the Watermark on paper known commercially as opaque and semi-opaque were distinct and transparent. In the same manner, as described in the examples, it is obvious that the entire translucent blank paper known commercially as opaque and semi-opaque may be transparentized, that is to say, converted from a translucent paper to a transparent paper. Several successful tests were made in the transparentizing of entire sheets of translucent paper of the type used in the above examples employing the same compositions. The transparency of the products obtained was greater than that of some commercial tracing papers.
At this point it should be mentioned that in the transparentizing of a sheet of paper, the matter of migration of the chemical impregnant over a period of time becomes unimportant as distinguished from the process of forming watermarks. Migration of the chemical impregnant in the case of Watermarks must necessarily not occur as such migration would tend to obliterate the mark over a period of time.
Tr-ansparentized paper has many commercial uses such as tracing paper and the like. Also there is a commercial demand for translucent paper having only a portion of the sheet transparentized such as the window type mailing envelopes wherein the address is printed on the contents of the envelope and positioned beneath the transparent window.
In order to confirm the laboratory hand impregnating technique employed in the above examples, the novel compositions of this invention were employed in forming watermarks on blank paper by means of a commercially usable process. The results of the commercial type application of the invention are illustrated in the following additional examples, the proportions all shown in the terms of Weight.
Example XX Composition A: Percent Sucrose acetate isobutyrate 50 Diethyl glycol monoethyl ether 50 Paper: Bond grade, 25 cotton-75% chemical wood pulp, having a thickness of 4.0 mils and an apparent density of 5.0.
'Therate of travel or production was 40 feet per minute. The resulting watermark was clear and distinct.
Example XXI Paper: Same as in Example XX.
The watermark was first applied on one side employing composition B and then, in register, the other side employing composition A. The rate of application on each side was the same as that of Example XX. watermark was clear and distinct.
Example XXII Same as Example XXI except the following composition C was substituted for Composition B.
The resulting Same as for Example XXI except that the paper employed had additiona1 sizing. The resulting watermark was clear and distinct.
Example XXIV Same as Example XXIII except that the rate of application was increased to 100 feet per minute. The resulting watermark was distinct.
Example XXV Same as Example XXII except that onionskin paper was employed. The resulting watermark was clear and distinct.
Example XXVI Same as Example XXII except that onionskin paper was employed and treated only on one side using composition C. The resulting watermark was clear and distinct.
Example XX VII Same as Example XXII except that onionskin paper was employed and treated only on one side using Composition A. The resulting watermark was clear and distinct.
Satisfactory results were also achieved in the commercial type application of the invention in the following examples in which a clear and distinct Watermark was achieved:
Example XX VIII Percent Sodium dioctyl sulfosuccinate 1.6
Sucrose acetate isobutyrate 48.4
Diethylene glycol monoethyl ether 50.0 Example XXIX Sodium dioctyl sulfosuccinate Sucrose acetate isobutyrate 3O Diethylene glycol monoethyl ether 50 Example XXX Sodium dioctyl sulfosuccinate 3O Sucrose acetate isobutyrate 20 Diethylene glycol monoethyl ether 50 Example XXXI Sodium dioctyl sulfosuccinate 38.8
filcrose acetate isobutyrate 12.2
Diethylene glycol monoethyl ether 50.0
Generally, it was found unnecessary to apply the watermark on both sides, but in some instances application of the watermark on both sides, in register, was advantageous, particularly on thick and dense papers. Forced drying, such as by radiant heat, generally was found to be unnecessary. However, where the design of the Watermark is characterized by large areas it may be advantageous to force-dry the sheets to prevent migration of the chemical which may occur if drying is too slow.
It has thus been shown that ordinary grades of writing stationery can be provided with a watermark by chemical impregnation according to this invention by means of hand impregnating or commercially acceptable application methods. From this it can be readily appreciated that small quantities of paper may be provided with such marking at costs which meet the requirements of smaller volume customers and thereby making available, economically, a long sought paper product. Further, there has been shown a convenient means for transparentizing a translucent paper product, such as that commercially known as opaque and semi-opaque, economically for manufacturing tracing papers and the like.
Based on the weight of the paper the amount of imregnating composition in terms of percent by Weight may vary due to the type and density of the paper used. Therefore a sufiicient amount effective to reduce the TAPPI opacity to below 65% is necessary to transparentize translucent paper. In the case of the bond paper used in the examples, an impregnation in the amount of 15% by weight of the impregnating composition based on the weight of the paper gave satisfactory results.
Having thus described several embodiments of the invention it can now be seen that the objects of the invention have been fully achieved and it must be understood that changes and modifications may be made which do not depart from the spirit of the invention nor from the scope thereof as defined in the appended claims.
What is claimed is:
l. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a composition consisting of about 30 percent by weight to about 70 percent by weight of at least one organic compound selected from the group consisting of sucrose acetate butyrate sucrose acetate isobutyrate and an alkali metal salt of a dialkyl sulfosuccinate dissolved in an inert organic solvent, said solvent having a boiling point in the range of about C. to about 250 C. in an amount of about 70 percent by weight to about 30 percent by weight.
2. The paper product having a substantially permanent watermark of selected geometrical design imparted thereto obtained in accordance with the method of claim 1.
3. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium dioctyl sulfosuccinate dissolved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said organic solvent having a boiling point in the range of about 100 C. to about 250 C.
4. The paper product obtained in accordance with claim 3.
5. The method of imparting a substantially permanent watermark of selected geometrical design to paper according to claim 3 wherein the solvent is selected from the group consisting of diethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, 2-(2-methoxy ethoxy) ethanol ethylene glycol monoethyl ether.
6. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium diamyl sulfosuccinate dissolved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
7. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sodium dihexyl sulfosuccinate dis- 9 solved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
8. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of about 30 percent by weight to about 70 percent by weight of sucrose acetate isobutyrate dissolved in about 70 percent by weight to about 30 percent by weight of an inert organic solvent, said organic solvent having a boiling point in the range of about 100 C. to about 250 C.
9. The method of imparting a substantially permanent watermark of selected geometrical design to a paper sheet according to claim 8, wherein the solvent is selected from the group consisting of diethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, Z-(Z-methoxy ethoxy) ethanol ethylene glycol monoethyl ether.
10. The method of imparting a substantial-1y permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of from 0.3 percent by weight to 40 percent by weight of sodium dioctyl sulfosuccinate, from percent by weight to 69 percent by Weight of sucrose acetate isobutyrate, and at least 30 percent by Weight and not more than 70 percent by weight of an inert organic solvent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
11. The method of imparting a substantially permanent watermark of selected geometrical design to paper according to claim 10 wherein the solvent is selected from the group consisting of diethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, 2-(2-methoxyethoxy) ethanol and ethylene glycol monoethyl ether.
12. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design with a liquid composition consisting of from 0.3 percent by weight to 40 percent by Weight of sodium dihexyl sulfosuccinate, from 10 percent by weight to 69 percent by weight of sucrose acetate isobuty-rate, and at least 30 percent by weight and not more than 70 percent by weight of an inert organic sol- 1O vent, said solvent having a boiling point in the range of about 100 C. to about 250 C.
13. The method of imparting a substantially permanent watermark of selected geometrical design to paper according to claim 12 wherein the solvent is selected from the group consisting of diethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, 2-(2-methoxyethoxy) ethanol and ethylene glycol monoethyl ether.
14. The method of imparting a substantially permanent Watermark of selected geometrical design to paper comprising the steps of impregnating a portion of said paper in the configuration of said design With a liquid composition consisting of about 12.5% by Weight of sodium dioctyl sulfosuccinate, about 37.5% by weight of sucrose acetate isobutyrate and about by weight of diethylene glycol monoethyl ether.
15. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of forming a liquid composition consisting of from 0.3 percent by weight to 40 percent by Weight of sodium dioctyl sulfosuccinate, from 10 percent by weight to 69 percent by Weight of sucrose acetate isobutyrate and from 30 percent by weight to 70 percent by weight of an inert inorganic solvent, and thereafter displacing entrapped air in a portion of said paper with said composition in an area conforming to the said design of said watermark.
16. The method of imparting a substantially permanent watermark of selected geometrical design to paper comprising the steps of forming a liquid composition consisting of from 0.3 percent by Weight to 40 percent by weight of sodium dihexyl sulfosuccinate, from 10 percent by weight to 69 percent 'by weight of sucrose acetate isobutyrate and from 30 percent by Weight to 70 percent by 7 weight of an inert inorganic solvent, and thereafter displacing entrapped air in a portion of said paper with said composition in an area conforming to the said design of said watermark.
References Cited in the file of this patent UNITED STATES PATENTS 1,996,858 Davidson Apr. 9, 1935 2,028,091 J aeger Jan. 14, 1936 2,108,808 Finzel et a1. Feb. 22, 1938 2,176,423 Jaeger Oct. 17, 1939 2,702,818 Jaquay Feb. 22, 1955 2,931,802 Touey et al. Apr. 5, 1960 2,955,958 Brown Oct. 11, 1960
Claims (1)
1. THE METHOD OF IMPARTING A SUBSTANTIALLY PERMANENT WATERMARK OF SELECTED GEOMETRICAL DESIGN TO PAPER COMPRISING THE STEPS OF IMPREGNATING A PORTION OF SAID PAPER IN THE CONFIGURATION OF SAID DESIGN WITH A COMPOSITION CONSISTING OF ABOUT 30 PERCENT BY WEIGHT TO ABOUT 70 PERCENT BY WEIGHT OF AT LEAST ONE ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF SUCROSE ACETATE BUTYRATE SUCROSE ACETATE ISOBUTYRATE AND AN ALKAI METAL SALT OF A DIALKYL SUFLOSUCCINATE DISSOLVED IN AN INERT ORGANIC SOLVENT, SAID SOLVENTHAVING A BOILING POINT IN THE RANGE OF ABOUT 100*C. TO ABOUT 250*C. IN AN AMOUNT OF ABOUT 70 PERCENT BY WEIGHT OT ABOUT 30 PERCENT BY WEIGHT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US832148A US3085898A (en) | 1959-08-07 | 1959-08-07 | Paper product with watermark and process therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US832148A US3085898A (en) | 1959-08-07 | 1959-08-07 | Paper product with watermark and process therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3085898A true US3085898A (en) | 1963-04-16 |
Family
ID=25260825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US832148A Expired - Lifetime US3085898A (en) | 1959-08-07 | 1959-08-07 | Paper product with watermark and process therefor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3085898A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404029A (en) * | 1965-01-27 | 1968-10-01 | Interchem Corp | Transparentized drafting paper |
| US4073982A (en) * | 1975-07-18 | 1978-02-14 | Weck Friedrich J | Newsprint coupon separator |
| US4112154A (en) * | 1977-09-02 | 1978-09-05 | Olin Corporation | Method for obtaining uniform porosity in printed inherently porous cigarette tipping papers |
| US4162339A (en) * | 1975-07-18 | 1979-07-24 | James Hunkins | Newsprint coupon separator |
| US4600629A (en) * | 1985-09-16 | 1986-07-15 | Westvaco Corporation | Selectively absorbent mask printing process |
| US5085936A (en) * | 1988-01-18 | 1992-02-04 | The Wiggins Teape Group Limited | Watermarked paper sheet for use in xerographic imaging processes |
| US6334678B1 (en) | 1999-09-01 | 2002-01-01 | International Paper Company | Method for applying chemical watermarks on substrate |
| WO2010046534A1 (en) * | 2008-10-20 | 2010-04-29 | Valtion Teknillinen Tutkimuskeskus | Modified fibrous product and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1996858A (en) * | 1933-11-02 | 1935-04-09 | Davidson Paul Ballinger | Translucent paper |
| US2028091A (en) * | 1933-07-28 | 1936-01-14 | American Cyanamid & Chem Corp | Esters of sulphodicarboxylic acids |
| US2108808A (en) * | 1934-06-26 | 1938-02-22 | Du Pont | Transparent materials and method of making same |
| US2176423A (en) * | 1936-01-13 | 1939-10-17 | American Cyanamid & Chem Corp | Esters of sulphodicarboxylic acids |
| US2702818A (en) * | 1953-10-14 | 1955-02-22 | American Cyanamid Co | Free-flowing surface active agent in discrete-particle form |
| US2931802A (en) * | 1958-04-30 | 1960-04-05 | Eastman Kodak Co | Mixed esters of glucose and sucrose |
| US2955958A (en) * | 1956-03-05 | 1960-10-11 | Nathan J Brown | Process of treating woven textile fabric with a vinyl chloride polymer |
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1959
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2028091A (en) * | 1933-07-28 | 1936-01-14 | American Cyanamid & Chem Corp | Esters of sulphodicarboxylic acids |
| US1996858A (en) * | 1933-11-02 | 1935-04-09 | Davidson Paul Ballinger | Translucent paper |
| US2108808A (en) * | 1934-06-26 | 1938-02-22 | Du Pont | Transparent materials and method of making same |
| US2176423A (en) * | 1936-01-13 | 1939-10-17 | American Cyanamid & Chem Corp | Esters of sulphodicarboxylic acids |
| US2702818A (en) * | 1953-10-14 | 1955-02-22 | American Cyanamid Co | Free-flowing surface active agent in discrete-particle form |
| US2955958A (en) * | 1956-03-05 | 1960-10-11 | Nathan J Brown | Process of treating woven textile fabric with a vinyl chloride polymer |
| US2931802A (en) * | 1958-04-30 | 1960-04-05 | Eastman Kodak Co | Mixed esters of glucose and sucrose |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404029A (en) * | 1965-01-27 | 1968-10-01 | Interchem Corp | Transparentized drafting paper |
| US4073982A (en) * | 1975-07-18 | 1978-02-14 | Weck Friedrich J | Newsprint coupon separator |
| US4162339A (en) * | 1975-07-18 | 1979-07-24 | James Hunkins | Newsprint coupon separator |
| US4112154A (en) * | 1977-09-02 | 1978-09-05 | Olin Corporation | Method for obtaining uniform porosity in printed inherently porous cigarette tipping papers |
| US4600629A (en) * | 1985-09-16 | 1986-07-15 | Westvaco Corporation | Selectively absorbent mask printing process |
| US5085936A (en) * | 1988-01-18 | 1992-02-04 | The Wiggins Teape Group Limited | Watermarked paper sheet for use in xerographic imaging processes |
| US6334678B1 (en) | 1999-09-01 | 2002-01-01 | International Paper Company | Method for applying chemical watermarks on substrate |
| WO2010046534A1 (en) * | 2008-10-20 | 2010-04-29 | Valtion Teknillinen Tutkimuskeskus | Modified fibrous product and method of producing the same |
| US20110256362A1 (en) * | 2008-10-20 | 2011-10-20 | Teknologian Tutkimuskeskus Vtt | Modified fibrous product and method of producing the same |
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