US3486923A - Water treated shadowmarks - Google Patents

Water treated shadowmarks Download PDF

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US3486923A
US3486923A US707151A US3486923DA US3486923A US 3486923 A US3486923 A US 3486923A US 707151 A US707151 A US 707151A US 3486923D A US3486923D A US 3486923DA US 3486923 A US3486923 A US 3486923A
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paper
resin
water
opacity
water treatment
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Bruce D Skofronick
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Customark Corp
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Customark Corp
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    • 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

Definitions

  • a paper article is made opaque relative to the original light transmission properties of the paper.
  • the opaque area may extend throughout the entire sheet or may be a limited area of a selected design to obtain a shadowmark.
  • the opaque area is obtained by applying a resin to a paper area and then contacting the area with water. The opaque area is raised relative to the original thickness of the paper.
  • the paper articles are made by applying a liquid composition to the surface of a sheet of paper.
  • the liquid composition includes a resin which can be laid down as a wet lm and which will impregnate paper fibers or the paper web.
  • the resin is applied to the surface of paper to opacify the entire paper or a limited area to provide a shadowmark. While one water treatment step may be sufficient for some embodiments, it is provided that other embodiments may require a plurality of successive Water treatment and intervening drying steps to develop or enhance the development of the opaque area.
  • This invention relates to a paper article having 'areas more opaque than the original paper, and it also relates to a method for opacifying areas.
  • the liquid resin compositions are applied to the surface of the paper, and the resin is then hardened r dried, limited only to a portion of the surface area, and when a whereupon a translucent area is obtained.
  • the translucent area may be considered as being a watermark.
  • Such a watermark may appear to be of the same quality as conventional watermarks, and they may also be referred to as simulated watermarks or chemical watermarks. This is a recognized advance in the paper art because high quality watermarks are obtained which have economic advantages as a result of the substantially lower costs incurred in producing the marks.
  • Such marks may be applied or printed on paper in smaller runs after the paper is formed. This is in contradistinction to the conventional watermarks which are made by a dandy roll during the paper forming stage.
  • Shadowmarks are formed in paper sheets for the same 3,486,923 Patented Dec. 30, 1969 Mice general purposes as are watermarks, that is, for reasons of quality, identification, esthetics and the like.
  • the conventional shadowmarks are opaque relative to the balance of the paper as distinguished from watermarks which are translucent relative thereto.
  • shadowmarks Up to the ⁇ time of the present invention, shadowmarks have been formed by a dandy roll during a paper making stage. Watermarks have been formed by a raised die on the dandy roll spreading paper fibers, whereas shadowmarks have been formed by a recess or well in the dandy roll in which the paper fibers collect.
  • a feature of this object is the attainment of opaque areas on paper which are serviceable in the sense of substantial permanency, receptivity to writing or printing, freedom froml discoloration, and other properties which are desirable for paper as such.
  • Another important object of this invention is a paper sheet on which shadowmarks of Varying design may be formed by the simple step of applying a liquid composi- ⁇ tion to the surface of the paper in a selected design, and then treating the applied liquid composition by one or more following steps which are simple and economical.
  • Yet another important object of this invention is a method by which paper sheets may be entirely opacified by applying a liquid composition to the sheet to impregnate the paper fibers with a resin and then inducing the formation of a plurality of interfaces in the deposited resin -to render such resin-deposited areas opaque relative to the original light transmission of the paper.
  • a similar and important object of this invention is to make shadowmarks on sheets of paper by the same general procedure as suggested in the preceding object.
  • Yet another important object of this invention is a new paper article, with opaque areas, yand methods for preparing such an article which allows the use of a wide variety of available resin materials which can be laid down as a wet lm and which can impregnate the paper fibers or paper web.
  • a desired feature of this lobject are process steps which allow Various means to be successfully used in the method.
  • FIGURES 1-6 illustrate how capacity of paper is increased in accordance with the teachings of ⁇ the invention.
  • This invention provides that opaque areas are made on paperl by applying a liquid composition containing one or more resins to the surface of the paper so that the resin islaid down as a wet film and irnpregnates the paper fibers or the paper web.
  • the composition is in a 'liquid form to facilitate application, and has a viscosity which is sufficiently low to allow the desired impregnation.
  • the viscosity is sufficiently high to retain the design which has been applied to the surface of the paper. In other words, 'the'vi'scosity' is low enough to impregnate, but not low enough to distort the preselected design which has been applied to the surface.
  • the liquid resin film or layers which have been ap- -plied to the surface of the paper are then rendered more opaque than the original paper by contacting such resin with water. This step leads to attaining an opaque area which is further raised relative to the original surface of the paper.
  • a single water treatment step will lead to forming an opaque area but, in many instances, this will not lead to a desirably formed opacity. It has likewise been discovered that a plurality of successive water treatment and intervening drying steps can lead to the development of an opaque area, or to the forma'- tion of better defined opacity.
  • Some sort of incompatability may result between the resin and water following one or more steps of contacting the resin with the water.
  • the presence of the water is believed to directly participate in the development of opacity to measurable or recognizable levels following a plurality of successive water treatment and drying steps.
  • the water may be functioning in conjunction with a subsequent heating step.
  • liquid composition will refer to the entire liquid body which is handled and applied to the surface of a sheet of paper. Such a composition need only be liquid so that it may be conveniently applied either to the entire sheet or to a limited area to form Ia shadowmark.
  • the liquid composition may consist of a resin alone which is in fluid form, or it may include a mixture of resins-'to effect greater fluidity, for example, it may include'a plasticizer which acts as a diluent.
  • the liquid composition may also contain an organic solvent in many of the preferred forms to provide good workable fluidity and to further effect a neat impregnation and hardening of the resin following a drying step or a curing step.
  • the resin in the liquid composition may contain a chemical curing agent for the resin in many preferred forms, but
  • the water treatment step is performed before the resin substantially cures, dries or hardens.
  • the water treatment step is preferably made while the composition remains wet on the paper, that is, before all the solvent has been removed.
  • the amount of solvent which may be removed may be a major amount of more than 50% of the original amount and, say, less than about Opaque marks may be formed on a sheet of paper by a printing step where a liquid composition is printed as a wet film on the surface. This may be conventionally done by a hand stamp, an elastomeric die on a roller or by similar letter press techniques. While a printing step is a preferred form, the film of liquid composition may be applied otherwise as by brushing or spraying the liquid compositions through a stencil. Other methods of application will occur to practitioners in this art.
  • This paper may be made entirely opaque by dipping ⁇ the sheet in the liquid composition or by depositing a charge of the liquid composition on the surface of the 'paper and then pulling a roller or the like through the deposited charge until the entire surface is covered with a wet film of the liquid composition. Whatever the identity of the resin material which is deposited, it is preferred that the wet film undergo some drying before the water treatment step.
  • a sheet of paper with the wet film may be passed, for example, over a hot felted drum dryer, for 60 seconds, said drum being held at 79 C.
  • the water treatment step may be performed in a variety ofv ways such as spraying, fogging, dipping, providing a high humidity environment, or by other means.
  • a successful step provides for dipping the sheet of paper in a body of water, then nipping the paper between rollers to remove excess water, and then air drying or drying at moderate temperature levels.
  • the sheet may be dipped in water and nipped between rollers, dried in an oven at temperatures of about C. or over a hot felted dryer held at 78-80 C., dipped again, nipped, dried again, and so on.
  • the dipping technique provides that the paper is immersed in the water, and then withdrawn without prolonged immersion. It is not known for certain to what degree the thermosetting resin film has dried or hardened during the plural execution of such successive steps. Clearly, it is preferred no t to encounter any undue delays between the successive steps butto repeat them as quickly as possible until the opaque area is desirably developed. In general, it is preferred that the first water treatment be applied after ⁇ about a minute or two following application of the liquid composition so that adequate impregnation occurs.
  • the successive wetting step is preferably executed immediately following drying or substantial drying of. the. paper. Further wetting steps are likewise preferably executed immediately. following substantial drying.
  • the resins may include the natural resins which may be substituted or modified, such as rosin; hydrogenated methyl ester rosin; partially decarboxylated rosin; triethylene glycol ester of hydrogenated rosin, hydrogenated abietate esters with various mono, diand trialkyl glycols or mixtures thereof; and others. Natural resins may be combined with solvents or plasticizers to desirably attain an operable viscosity.
  • the liquid composition may even be a softened solid such as Aquapel, an alkyl ketene dimer supplied by the Hercules Powder Co.
  • esters of polyols Iwith saturated diacids and unsaturated diacids may be polyesters of glycols 1with dicarboxylic acids which are saturated such as adipic, pimclic, and azelaic. They may also be glycols esterilied with unsaturated dicarboxylic acids such as succinic.
  • Some representative esters are polypropylene adipate, triethylene glycol hydroabietate and the like.
  • Other esters are dialkyl sulfosuccinates; sucrose acetate isobutyrate, and sucrose acetate butyrate as disclosed in U.S. 3,085,898 issued to the present assignee.
  • the resins may be used alone or in a mixture in the liquid composition.
  • Thermosetting resins are successfully used, and representative resins of this type are disclosed in U.S. Letters Patent No. 3,140,050 issued to the present assignee.
  • Such resins include the urea melamine formaldehydes, polyester, phenolic resins and epoxy resins,
  • Other thermosetting resins are the alkoxy substituted melamine resins such as hexamethoxymethylmelamine.
  • Such resins may be combined with a variety of organic solvents or plasticizers to effect the desired viscosity.
  • Said solvents include ketones such as methyl isobutyl ketone; esters such as dibutyl phthalate; various alkylene glycol alkyl ethers such as ethyleneglycol monomethyl ether; and a large number of other solvents. Representa- ⁇ tive solvents and plasticizers are also listed in the foregoing U.S. Patent No. 3,140,959.
  • thermosetting resins are preferably used for the foregoing thermosetting resins, and such agents are well Iknown in the art. While a preferred liquid composition vvould include a thermosetting resin, a solvent, and a curing agent, it should be noted that the solvent and curing agent may be omitted. Selected thermosetting resins or combinations of resins may be sufficiently liquid to be applied to the sheet of paper in the form of a design, and then be water contacted. Certain epoxy resins have been used successfully Without a curing agent. Certain epoxies have also been used successfully without a sol- .vent. Reference is likewise made to the foregoing U.S.
  • the resin esters may also be polymeric plasticizers such as the plasticizer provided under the name of Eastman N.P. supplied by the Eastman Chemical Products Company.
  • the Eastman plasticizer is derived from neopentyl glycol.
  • the ester may be a monomeric plasticizer used in conjunction Wtih some higher molecular Weight polyester to provide dilution or solvation.
  • These plasticizers may include diesters of phthalic esters and lower monohydric alcohols, such as the dimethyl, di-
  • plasticizers or solvent esters may include cyclohexanone.
  • monomeric plasticizers are preferred as diluents for polyesters or other resins to effect the desired fluidity.
  • a monomeric ester may, however, be useful for developing an opaque mark ⁇ by itself and one such ester is the monomeric epoxide supplied under the trademark Monoplex MS-73 by the Rohm and Haas Company.
  • Still other resins may be used such as aryl sulfonamides diluted with a plasticizer such as dioctyl phthalate.
  • Thermoplastic resins also iind useful application in this invention, such as acrylonitrile butadiene styrene or ABS.
  • thermoplastics may be of the allyl type, of the acrylic type, of the amide type, of the iluoro type, of the vinylchloride type, and still other types.
  • Still other resins include the cellulosic such as acetate, propionate, or ethyl cellulose resins.
  • film formers and paper impregnators such as triacetin, -diethyleneglycol monomethyl ether, and N methyl Z-pyrrolidone.
  • the opaque area may be formed on various paper, say from 9 pounds to 44 pounds. Such weights conventionally refer to a ream of 500 paper sheets, each having a dimension of 17 x 22". Greater paper weights may become eliminating factors by themselves because they transmit little light.
  • the opacity of the treated area increases in general about at least 1% relative to the original condition of light transmission.
  • the opacity may increase to higher levels depending on the particular resins used in the liquid compositions. In any event, an increase of at least 1% results in a sufficiently observable opacity.
  • ⁇ opaque area also results in a measurable and definite rise Irelative to the original surface of the paper, and this rise may be determined by caliper measurements.
  • the caliper rises by at least about 5% relative to the original thickness of the paper, but this may vary and include substantially higher levels. This again may be determined by the nature of the resin and the liquid composition.
  • EXAMPLE 1 A liquid composition is prepared by mixing the following impregnating materials in the listed amounts:
  • Epoxy resin Parts by weight Epoxy resin (Dow DER-332) 5 -Epoxy Hardener (Dow Experimental Hardener X-2654.4) a Methyl Carbitol (diethylene glycol monomethyl ether) 4.5
  • a small metered amount of liquid composition is deposited on the surface of a foot square piece of 1/2 thick plate glass.
  • the composition is spread uniformly over the surface with a hand roll, consisting of an engraved roll bearing 75 depressions per inch and tted With a handle.
  • a die or hand stamp of rubberlike material having inscribed on the face thereof a typical watermark design is rst pressed against the Wet lm of the composition on the glass and then stamped on a paper sheet.
  • the sheet is dried in a hot air stream at about C. for about 30 seconds.
  • the sheet of paper is then totally immersed in a bath of water maintained at room temperature.
  • the sheet of paper is removed, the excess water is removed as by a nipping operation between a brass roller and a rubber covered roller, and the paper is then subjected to heating by hot air at about 105 C. for about 1 minute.
  • the paper is reWetted in water and again dried as described. The procedure is repeated until a desirable opacity is obtained.
  • Epoxy resin Dow DER-332
  • Pyromellitic dianhydride l Methyl Carbitol 41/2
  • the above liquid composition, with epoxy resin impregnating compound, is manipulated in the same Way described for Example 1 to obtain a shadow chemical watermark of desirable properties.
  • the pyromellitic dianhydride which is supplied by the Du Pont Company, is a good curing agent or hardener for the epoxy resin'since likelihood of possible discoloration is even further reduced. The same property makes it a desirable curing agent also for translucent chemical watermarks.
  • water in the water treatment step may be present in mixtures, solutions, suspensions or the like.
  • the use of the term water may be used interchangeably or in an equivalent manner with aqueous liquids.
  • Such aqueous liquids may particularly include sizing solutions.
  • sizing solutions are commonly used in the paper art, and the most popular are starch solutions, such as the chlorinated and ethylated starches.
  • Other sizing agents in water solutions may be used as aqueous liquids in the wetting step.
  • the sizing solution may include a chlorinated starch and water solution which has been cooked for a sufficient time and at a suicient temperature to swell the starch granules to form the desired solution.
  • the various starch concentrations in water may be maintained at moderate temperatures ranging from about room temperatures to about 150 F.
  • Such a sizing solution may be in a conventional size tub, and the paper web may be moved to such tub to complete the contact of the paper and the starch solution.
  • Various equivalent means are known for sizing paper. In addition to the size tub, there are horizontal and vertical size presses of puddles, kiss coating and the like. The use of the term sizing is intended to refer to surface sizing rather than internal sizing. After the paper web has left the size tub, it may be nipped between rollers to remove the excess starch. The entire web of paper is therefore coated with a starch solution so that the paper is simultaneously sized and the impregnating resin is wetted with the starch sizing solution.
  • the following example presents an embodiment to teach the formation of opaque areas with a sizing solution.
  • EXAMPLE 3 A liquid composition is prepared from the ingredients of Example 1 and treated ⁇ by similar process steps. However, the sheet of paper is totally immersed in a bath containing 8% chlorinated starch in water, said bath maintained at 80 F.1to 150 F. The sheet of paper is removed' and subjected to heating by hot air until the paper is dry. The paper is then rewetted and again dried as described in Example l.
  • the strips are dipped in the water, npped between the described rollers and then dried by being passed twice over the felted drum for a total drying time of 120 seconds. This series of dipping, nipping and drying is followed for each additional Water treatment. Opacity measurements were made on control strips and on the water treated strips.
  • the following table lists the opacity measurements obtained with liquid impregnating compositions A and B.
  • the opacity measurements represent the average of three readings on spaced portions of each strip, and they are collected with a Bausch & Lomb opacimeter, B & L Optical Co., Rochester, N.Y.
  • Composition A A:
  • the liquid compositions may be used with paper which is either surface sized previously or not surface sized.
  • An important advantage of the process is that non-surface sized paper may be simultaneously surface sized and rendered opaque.
  • the opaque area may be limited as for a shadowmark, or may extend throughout theV entire surface of the ⁇ iinished paper sheet.
  • Apreyiously sized paper will receive an additional sizing treatment which may be cumulative or complementary to an original sizing to obtain desired sizing properties.
  • composition A The data of the foregoing table (composition A) lis utilized to graphically represent the difference in opacity following a plurality of water treatments.
  • FIGURES 1 to 6 The increase in opacity is represented as being directly proportional to the number of water treatments.
  • EXAMPLE 5 A liquid composition is prepared from the following The epoxy resin and the curing agents are supplied by the Shell Chemical Company. The above liquid composition is applied t0 9 lb. and 20 lb. paper strips by following the process steps generally as disclosed in Example 4. Replicate runs of each paper weight is wetted, dried and rewetted in a series of twelve separate water treatment steps. The opacity of a blank paper is measured, and the treated areas are meausred after selected successive water treatments. The data of following Table II shows that the opacity of the treated area is increased with successive- 25 sive water treatments, and that the opacity of the 9 1b.
  • the 12th Percent (7)/(5) X100 paper is increased up to the 9th water treatment, whereupon it remains substantially unchanged up to water treatment.
  • a liquid impregnating composition is prepared from the following ingredients and amounts:
  • the epoxy resin is Obtained from the DOW Chemical io tt tl t:1113111113331121111.- 3?:5 Company and the curing agent from the U.S. Borax Ref lgltihwatr tiieatilnentE gl search Corporation.
  • the above liquid composition is mh tfgtgt:j 7513 applied to 20 lb. and 9 lb.
  • Each gure is an average of nine separate values, three measurements manner indicated in Example 4. Following Table lII shOWS 15 prfallllleh f ft t l th that the opacity is continuously increased with successive mentsacper allefs an average o een separa e Va ues ree measme' water treatments up to and including the 12th water treatment.
  • a liquid impregnating composition is prepared from befQfe al1d after treatment 1S measllled th1'0ugh-a SUC the following ingredients and amounts Stated; cessive series of water treatment steps by following the P t b .oh procedure of previous Example 4. Following Table VI Ingredlentsl 1 300 1500 ar s y Welnu; shows that the opacity measurement is continuously in- Polyesler resul; KOP ac D 2 35 creased to the 12th water treatment step on one 9 lb. enzy perold, 10 paper sample, and through the 4th water treatment step Met y1 Car o on the other 9 lb. sample.
  • the polyester resin is obtained from Koppers Company, taken.
  • the measured opacity is also continuously n- Inc.
  • the liquid composition is applied to 9 and 20 lb. creased for the 20 lb. paper sample. paper strips which opacity is measured through a successive- 40 sive series of water treatment steps as described in preceding Example 4.
  • Table IV shows that the opacity TABLE VI is continuously increased with successive water treatments as veried by selected opacity measurements.
  • EXAMPLE 10 A liquid impregnating composition is prepared from the EXAMPLE 12 uollngt mgredlents and amounts Statesart by ight Eight impregnating liquid compositions, designated A gre le s: s We throu h H res ectivel are re ared-as follows' Hexarnethoxymethylmelamine, Cymel 301 l() g p y P P Curing agent, Epi-Cure 8771 3 Methyl Carbitol 2 Ll The hexmethorrymethylmelamine ls obtained frorifi the gosmon Ingredients American yanimid Company, and t e curing agent rom A Monomer X 970 (Rohm & Haas 0o.).
  • EXAMPLE 13 30 corded opacity measurements are presented in following A liquid impregnating composition is prepared from Table X' the following ingredients in the amounts listed.
  • Paper strips of varying weight are given 906 Gigef E510 (General the same treatments, and the opacity and caliper readings 911 Methyl oe'rbirei (Union ar are reported as average of three readings on spaced por 907 N Methy1 2 1,yrrohdoue (Gem tions of each strip. Such averages are listed in following Anii'me).
  • the Dresinol material is a partially decarboxylated opacity is not, for the most part, substantially changed pale rosin; Morester X-973 is a saturated polyester; and with water treatments in excess of one.
  • the increase in the 'Silicone L-53l0 is an organo-silicone copolymer.
  • EXAMPLE l5 A liquid impregnating composition is prepared from an alkyl ketene dimer supplied by the Hercules Chemical Co. under the trademark, Aquapel. The resin is heated until it liquifys at about 120 F. The process steps of Example 4 are then followed by using two water treatment steps to obtain an opaque area. The opacity of the heated area increases upon standing.
  • EXAMPLE 16 A liquid impregnating composition of Silicone L-5310 is used to impregnate entire strips by the procedure described in Example 4, Another liquid composition of Surfynol 485 is used to impregnate other strips of the same paper. Some of the strips are given a plurality of water treatments by following the method of dipping, nipping and drying as described in Example 4, and other strips are given a plurality of prolonged water treatments of three minutes per treatment. Still others are given a plurality of prolonged water treatments of varying immersion times. The results are shown in the following Table XI.
  • EXAMPLE 17 Paper strips of the type described in Example 4 are dipped in a liquid impregnating composition of N methyl- Z-pyrrolidone. The strips are nipped and then passed twice over a hot felted drum dryer at 60 seconds a pass. Opacity developed during the drying treatment, that is, even before the iirst water treatment. Following water treatments enhance the development of the opaque area.
  • Paper articles of this invention have opaque areas which may have some variance relative to their permanence and serviceability and color.
  • the art may very well accept certain paper articles with opaque areas which have a permanency and serviceability less than that of the paper itself. But, in general, many paper articles are obtained in which the opaque area is serviceable towards receiving writing and printing and is substantially permanent as the paper itself.
  • the attribute of permanency would include substantial resistance of the opaque area to mechanical abrasion encountered by means such as erasing.
  • the attribute of serviceability would include a resistance to discoloration for at least desirable periods of time.
  • the useful life of the paper may be variously measured, and the substantial majority of stationery bond, for example, has a relatively short, useful life. Nonetheless, the shadow-marks and opacity on such bond papel would retain the desirable properties, in most instances, even after the stationery bond has been stored or vetted for substantial periods.
  • Methods for making the paper articles of this invention can include the batch or continuous processing.
  • the continuous process will be preferred for a large scale production wherein a run of paper web will move through appropriate stations.
  • a marking station would contain the liquid composition and the paper web would receive the conguration of the marking formulation or be entirely covered at such a station.
  • the running web would then pass through an aqueous station where contact would be made with the aqueous liquid before the resin in the liquid composition hardens or dries.
  • the paper web leaving the iirst water station would then be passed through succeeding stations for drying and wetting the papers to effect a successive number of drying and wetting steps, if desired.
  • the paper web could then be severed at a cutting station into selected dimensions or be otherwise handled.
  • a method for opacifying areas on paper which comprises,
  • a non-aqueous liquid composition to the surface of said paper, said composition including a resin, said resin capable of being laid down as a wet iilm and impregnatin-g the paper,
  • the opaque area on the paper is developed by repeating a suicient number of successive water contacting and drying steps until the opaque area is desirably formed.
  • a method for opacifying areas on paper which comprises,
  • a non-aqueous liquid composition to the surface of said paper, said composition including a resin, said resin capable of being laid down as a wet lrn and impregnating the paper,
  • liquid composition has a viscosity sufficiently high to retain the applied design configuration, but suiciently low to permit impregnation of the paper.
  • a method as in claim 2 in which said selected design is printed on a limited surface area of the sheet of paper so that a film of the liquid composition is laid down in the selected design, and said film being sufficient to impregnate the paper while still retaining the configuration of the selected design.
  • liquid composition includes an organic solvent in which the resin is soluble.
  • liquid composition includes a chemical curing agent for said resin.
  • the resin material is of the class of tripropionin, N methyl 2-pyrrolidone and diethylene glycol monomethyl ether.
  • a method as in claim 2 wherein the resin is a polypropylene glycol having a molecular weight of about 400.
  • the resin is of the class of a natural resin, a substituted resin and a modiiied resin.
  • thermosetting resin 23.
  • thermosetting resin 24.
  • the liquid composition includes a chemical curing agent for said thermosetting resin.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904791A (en) * 1971-09-10 1975-09-09 Elizabeth M Iverson Ornamental coating method and articles
US3985927A (en) * 1975-02-24 1976-10-12 Nekoosa Edwards Paper Company, Inc. Compositions and method for producing a chemical watermark on finished paper products
US6334678B1 (en) 1999-09-01 2002-01-01 International Paper Company Method for applying chemical watermarks on substrate
US20030056673A1 (en) * 2001-09-21 2003-03-27 Klumpp John J. Method for producing unobtrusive ornamental visual effects for design configurations and point of reference patterns which enhance the aesthetics and functional criteria of paper and printable substrates
US20040249754A1 (en) * 2001-09-17 2004-12-09 Wittich Kaule Papermaking mould for producing two-stage watermarks and method for producing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933416A (en) * 1960-04-19 Process for fixing figments on
US3140959A (en) * 1960-12-27 1964-07-14 Customark Corp Paper product with chemical watermark and means for making same
US3288628A (en) * 1962-10-01 1966-11-29 Olin Mathieson Process for chemically watermarking paper and product thereof
US3293062A (en) * 1963-04-05 1966-12-20 Customark Corp Chemical watermark applied on finished paper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933416A (en) * 1960-04-19 Process for fixing figments on
US3140959A (en) * 1960-12-27 1964-07-14 Customark Corp Paper product with chemical watermark and means for making same
US3288628A (en) * 1962-10-01 1966-11-29 Olin Mathieson Process for chemically watermarking paper and product thereof
US3293062A (en) * 1963-04-05 1966-12-20 Customark Corp Chemical watermark applied on finished paper

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904791A (en) * 1971-09-10 1975-09-09 Elizabeth M Iverson Ornamental coating method and articles
US3985927A (en) * 1975-02-24 1976-10-12 Nekoosa Edwards Paper Company, Inc. Compositions and method for producing a chemical watermark on finished paper products
US6334678B1 (en) 1999-09-01 2002-01-01 International Paper Company Method for applying chemical watermarks on substrate
EP1208010A1 (en) * 1999-09-01 2002-05-29 International Paper Company Method and apparatus for applying chemical watermarks on substrate
EP1208010A4 (en) * 1999-09-01 2002-10-29 Int Paper Co METHOD AND APPARATUS FOR APPLYING CHEMICAL WATERMARK ON A SUBSTRATE
US20040249754A1 (en) * 2001-09-17 2004-12-09 Wittich Kaule Papermaking mould for producing two-stage watermarks and method for producing the same
US8524039B2 (en) * 2001-09-17 2013-09-03 Giesecke & Devrient Gmbh Papermaking mould for producing two-stage watermarks and method for producing the same
US20030056673A1 (en) * 2001-09-21 2003-03-27 Klumpp John J. Method for producing unobtrusive ornamental visual effects for design configurations and point of reference patterns which enhance the aesthetics and functional criteria of paper and printable substrates

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ES353714A1 (es) 1970-02-16
FR1577563A (es) 1969-08-08

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