US3293060A - Writing and manifolding material - Google Patents

Writing and manifolding material Download PDF

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Publication number
US3293060A
US3293060A US483019A US48301965A US3293060A US 3293060 A US3293060 A US 3293060A US 483019 A US483019 A US 483019A US 48301965 A US48301965 A US 48301965A US 3293060 A US3293060 A US 3293060A
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acid
spiro
clay
paper
color
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Harbort Ludwig
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/15—Spiro-pyrans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders

Definitions

  • This invention relates generally to writing and manifolding materials rand-is more particularly directed to what is commonly known as carbonless or noacarbon papers.
  • the term paper is used in this context in a broad sense and includes typewriter ribbons.
  • Conventional carbon and other such transfer paper having a wax basis sufler from the disadvantage that they are not sufiiciently clean on handling. Dirtying of the hands and clothing of a user cannot be avoided even when extreme care is taken.
  • Great efforts have therefore been made to produce a carbonless transfer paper which would avoid this problem.
  • Numerous patents have thus issued to manifolding materials in which two substantially colorless layers are pressed into contact to cause a color reaction during writing, ty ping or other similar operations.
  • One basic form such materials have taken heretofore utilizes an adsorption color reaction wherein a color reactant material changes color when adsorbed on a suitable absorbent material, the reactant material being a dye intermediate such as crystal violet Lact-one or the like which is an electron donor, and the adsorbent material be-ng an inorganic sub-stance which is an acid relative to the dye intermediate so as to be an electron acceptor when in adsorption contact therewith.
  • the reactant material being a dye intermediate such as crystal violet Lact-one or the like which is an electron donor
  • the adsorbent material be-ng an inorganic sub-stance which is an acid relative to the dye intermediate so as to be an electron acceptor when in adsorption contact therewith.
  • carbonl-ess transfer or mam-folding materials have been an improvement over more conventional carbon papers, they still have numerous disadvantages 'from the standpoint of shelf life, sensitivity of copies to solvents, various chemical materials and light, disagreeable odor and inability to produce multiple clearly legible
  • a further object of this invention is the provision of a manifolding material of the type described which is insensitive to conditions encountered in ordinary use and storage while providing one or many excellent copies when brought into contact with a specific acid reactant on application of writing pressure.
  • a further object of this invention is the provision of such manifolding material which will produce copies which are substantially stable to solvents and various chemical compositions as well as sufficiently stable to light.
  • Yet another objective of this invention is the provision of a manifolding material utilizing as a color reactant a chemical composition which is not a dye and which therefore will be stable having no tendency to stain the hands or clothing of a user.
  • Another objective of the instant invention is to provide mam-folding materials wherein the color reacting components may be carried on separate sheets of paper, in separate layers on the same sheet of paper, or wherein one of the color reactants may be carried on a typewriter ribbon or the like.
  • a still further object of the invention is to provide cleanly handled manifolding material producing intensely colored, clearly legible transfers even on the last of numerous multiple copies.
  • FIG. 1 is a fragmentary plan view and a cross section of a writing paper carrying both color reacting layers directly thereon, a portion of the upper layer being broken away for illustrative clarity;
  • FIG. 2 is a fragmentary plan view and a cross section of two separate papers :forming a manifolding material in accordance with a modified embodiment of this inventiou.
  • acid activated clay or acid activable clay are recognized expressions in the art and generally refer to clay which has bee-n heat-treated, .such as boiled, with a strong mineral acid, "for example, hydrochloric acid or sulfuric acid, to increase the surface area of the clay and to remove certain mineral constituents, as will appear more fully from Example 8.
  • a strong mineral acid for example, hydrochloric acid or sulfuric acid
  • the clay which originally is slightly acidic is thus imparted with a considerable increase of acidity.
  • the surface area of the clay is significantly increased which makes it eminently suitable for the reception of the pyrylium color salts.
  • Acid activated clay products are known in the art and marketed under various trade names as will be set forth more fully hereinbelow.
  • the acid activated clay is subsequently enriched by the addition of a non-volatile inorganic or organic acid.
  • spiro-dipyrans in a non-volatile or a scarcely volatile solvent dispersed in the form of fine droplets in a suitable film mass coated on a paper with a layer containing the acid activated clay will jfllIlCfi'OIl upon exposure to appropriate local Writing pressures to provide the intensely colored product on contact of the reactants.
  • the paper coated with the acid activated clay is shown for example at 1 in FIG. 1 with the spiro-dipyran layer coated thereon as shown at 2.
  • Any suitable number of such sheets can be manifolded and impressed by any form of writing instrument including a typewriter, the application of pressure causing the spiro-dipyran to be transferred to, and to react with, the clay treated with the said acids in a color forming manner to produce a colored copy.
  • the two substantial-1y colorless materials can be individually supplied each on a separate sheet whereby a manifolding construction is produced to be used in an obvious manner.
  • a manifolding construction is produced to be used in an obvious manner.
  • a further use of the color reaction according to the invention for the production of a writing and manifolding material of the type desired consists in depositing the spiro-dipyrans in the form of a solution of the same in a non-volatile or scarcely volatile solvent in a porous synthetic substance coating of a neutral paper and transferring of the spiro dipyran to an underlying layer containing acid activated clay under suitable writing pressure.
  • the spiro-dipyran dissolved in a non-volatile or scarcely volatile liquid can also be used for saturating a typewriter or the like ribbon which when used in combination with paper coated with an acid activated clay will result in the desired product.
  • EXAMPLE 1 1 part by weight of a 0.3% solution of spiro-dibenzopyran in chlordip-henyl is dispersed in 5 parts by weight of a 20 percent gelatose solution in Water and a paper carrying a layer of acid activated clay is coated with this emulsion.
  • the spiro-di-benzopyra-n layer constitutes one component of the color reaction and the acid activated clay serves as the other.
  • On application of 1 part by weight of a 0.1 percent solution of spirodi-naphthopyran is dispersed in 5 parts by weight of a 20 percent gelatose solution in water and is coated on a neutral paper. Reaction of this material with an acid activated clay as th Example 1 produces blue colored copies.
  • the layer containing the acid activated clay can be produced as follows:
  • Clay activated with hydrochloric acid 70 Methylcellu-lose, 2 percent aqueous 120 Glycerine 10 Water 40 Methanol 20
  • the above composition can be modified by replacing the clay treated with hydrochloric acid, for instance with a clay treated with sulfuric acid to produce similar satisfactory results.
  • dibutyladipate Percent 3-methyl-spiro-dinaphthopyran 5 Dibutyladipate 50 Castor oil 45
  • the dibutyladipate may be replaced by another suitable dicarboxylic acid ester of aliphatic alcohols such as butylbcnzyladipate, benzyloctyladipate or the like.
  • Chlorodiphenyl 94 The concentration of the spiro-dipyran may vary between 2 10%; a preferred range is about 56%.
  • Suitable phthalic acid esters are, for example, phthalic acid -di(2-ethyl-hexyl) ester and butylbenzylphthalate.
  • Suitable softeners are generally phosphoric acid esters such as tricresylphosphate, trioctylphosphate and diphenyloctylphosphate.
  • the spiro-dipyrans of A-E are also soluble in other non-volatile or difficultly volatile solvents or softeners.
  • the solutions obtained according to A through E are colorless and ribbons are impregnated therewith in known manner.
  • the ribbons may consist of cotton, silk, nylon, Perlon or the like materials usually used for typewriter ribbons.
  • the ribbons are used in conjunction with an acid activated clay as described.
  • EXAMPLE 7 Coating of paper with a sponge-like plastic layer having incorporated therein spiro-dinaphthopyran Parts Butylstearate 20 Chlorodiphenyl 15 Color substance 5
  • Polymethacrylic acid resin for example, a resin
  • the color substance referred to under (A) and (B) above may be, for example,
  • the resins mentioned under (A) and (B) above may be replaced by other film forming compounds as, for example, polyvinyl chloride and/ or mixed polymers alone and/or in mixture with other resins to the extent that they are insoluble in the plasticizers employed.
  • the volatile solvents mentioned under (A) and (B) above may be partially replaced by higher boiling solvents as, for example, isopropyl alcohol, isobutyl alcohol, butyl alcohol, ethylglycol.
  • the mixtures thus obtained are coated onto a substrate in conventional manner.
  • the coating thus obtained reacts with acid activated clay upon application of inscribing pressure to form a colored pyrylium salt.
  • EXAMPLE 8 Preparation 0 acid activated clay and coating paper with acid activated clay layer
  • a spiro-dipyran containing layer is reacted with a layer of acid activated clay coated onto a substrate such as paper.
  • the reaction results in the formation of a colored pyrylium salt and is caused by exerting inscribing pressure, whereby the spiro-dipyran is brought into intimate contact with the pore structure of the clay exhibiting an acid reaction.
  • the acid activated clay layer may be provided on the same substrate as the spiro-dipyran layer or it may be anchored on a separate substrate.
  • the clay in slurry form, is boiled with a strong mineral acid, such as hydrochloric acid or sulfuric acid. Excess of acid is then washed out so that only trace amounts of acid remain which, however, impart the clay with an acid reaction.
  • the clay is then dried.
  • the acid treatment results in the removal by dissolution of the major amounts of calcium and magnesium originally contained in the clay. Minor amounts of iron and alumium are also removed.
  • the acid treatment of the clay considerably increases the surface area of the clay and the calcium clay is thus transformed into a hydrogen clay of large surface structure. Due to the surface enlargement caused by the acid treatment, a sponge-like structure is formed containing a multitude of pores.
  • This acid activated clay can be easily coated onto a paper base by conventional means. The acid which presumably is retained within the clay in an adsorbtive manner, immediately reacts with the spiro-dipyran without, however, having a destructive influence on the paper.
  • clays of the montmorillonite group are particularly suitable.
  • Clays embraced by this group are generally referred to as bentonites and include, for example, nontronite, beidellite and hectorite.
  • the residual acid content in the clay can be determined as follows:
  • Determination of pH value 5 grams of the acid activated clay are shaken for 25 minutes with grams of distilled water, whereby a slurry is obtained. The pH of the slurry is then determined.
  • the clay is suitable for the purposes of this invention if a pH in the range of 3.5-4.5 is obtained.
  • the residual acid content is very low. If the clay has been treated with hydrochloric acid, residual amounts of 0.02- 0.03% of HCl can usually be determined. In some commercial products, the residual acid quantity may be as high as 0.2%. Clays with acid contents of below.0.01% HCl are less suitable for the inventive purpose.
  • acid activated clays are, for example, the materials Frankonit and Filtrol, the latter being marketed by Filtrol Company of Los Angeles.
  • Tonsil manufactured by the German firm Siid-Chemie A. G. of Kunststoff is also available in the United States.
  • commercially available acid activated clay is further enriched by adding minor quantities of nonvolatile acid thereto.
  • additions of, for example, amidosulfonic acid, oxalic acid, maleic acid, sulfosalicylic acid, tetrachlorophthalic acid or aliphatic monoesters of the last mentioned acid have proved to yield superior results.
  • the addition of such acids or esters accelerates the formation of the color salt and increases the color intensity, sharpness and fastness. The resistance to organic solvents, alkalis and exposure of the color formed is thus significantly increased.
  • the paper or the like substrate is coated with a layer which contains a major amount of the acid activated clay and may contain a minor amount of the usual pigments and binders and the like paper-coating substances.
  • the coating mass will contain 50-90%, preferably 80-85%, calculated on the dry content, of acid activated clay. Calculated on the acid activated clay content, the mass may be admixed with between about 240% of a strong, non-volatile organic or inorganic acid of the nature hereinabove described. It has been established that the predominant portion of the acid which is added to the commercially available acid activated clay forms a stable addition product with the clay structure.
  • the coating mass should contain a hydrophilic binder compatible with the acid activated clay and is prepared in the usual manner by mixing and grinding, as is customary in the paper manufacturing industry.
  • Suitable hydrophilic binders are, for example, polyvinyl alcohol, methylcellulose, polyvinylacetate dispersions, starch and starch derivatives. Mixtures of such binders are also suitable.
  • the addition of the acid to the coating mass is advantageously effected as the last step after the mixing and grinding of the other ingredients.
  • the coating mass is applied to the paper substrate in customary manner as in known in the paper industry.
  • the paper should be coated with at least 6 g./ square meter of coating mass.
  • the amount of coating mass on the paper may exceed 15 g./ square meter.
  • the preferred range is 7-10 g./ square meter.
  • the acid activated clay had been obtained by boiling a montmorillonite clay with sulfuric acid or hydrochloric acid. Excess of acid was then washed out until residual acid content of 0.02% was observed.
  • the binders of (A) may be replaced by other binding agents compatible with the acid activated clay and the respective acids.
  • TEST B-SENSITIVITY TO CARBON DIOXIDE Materials of the same type as described in Test A above were subjected to carbonated water in the form of club soda thereby simulating the carbon dioxide which would be adsorbed by such materials from the air on storage. With the crystal violet carbinol materials, on shaking the mixture, a dark blue or purple dye resulted in 5 to 10 minutes. In contrast, with the spiro-dipyran, no color was formed even overnight.
  • Example 16 by heating a mixture of stearyl amine (a commercial mixture of hexadecyl and octadecyl amines) and isopropanol until a clear solution was obtained to which was added a sample of the product resulting from (a) above and an aqueous 36 percent solution of benzyl trimethyl ammonium hydroxide, the mix- TEST ESTAINING CHARACTERISTICS (1)
  • the materials of Test D2 were applied to the inside of a hand producing a strong blue-violet color reaction 9 from the (a) and (b) dyes and no color reaction of staining with the spiro-dipyrans.
  • Test D2 The substances of Test D2 were applied to various other materials to determine the staining of dyeing characteristics. Tests were made with filter paper, cotton fabric, cotton fabric washed with a washing powder at 60 C. having a pH of 9, silk fabric, silk fabric washed with a washing powder at 60 C. having a pH of 9, nylon fabric, and nylon fabric washed with a washing powder at 60 C. having a pH of 9. In each instance the (a) and (b) materials produced a strong blue-violet color reaction almost immediately whereas no reaction was realized with the spiro-dipyrans.
  • TEST LACID AND ALKALI SENSITIVITY Copies produced according to the prior art procedure of Test I were neither resistant to acid nor alkali, sprinkling of fresh writing wit-h dilute potassium hydroxide causing disappearance of the same, the writing being illegible even after drying. With such materials, hydrochloric acid cannot cause reappearance of writing made to disappear by potassium hydroxide. Writing several days old similarly disappears and does not reappear after drying. With spiro-dipyrans, the writing does not disappear on moistening with hydrochloric acid and, after drying, it is even more intensive in color than in the nontreated condition. Potassium hydroxide solutions of low concentration are without influence on the writing. Higher concentrations will cause disappearance of the writing gradually, but it can be brought baoh 'by subsequent treatment with hydrochloric acid with a resulting higher color than before. This operation can be repeated several times.
  • TEST MSENSITIVITY TO LIGHT The rear transfer surface of a sheet formed according to the prior art teachings as set forth in Test J discolors blue-green on exposure to sunlight for several hours. ThlS discoloration becomes noticeable even in diffuse daylight after a longer exposure. In contrast, the rear transfer surface of a spiro-dipyran manifolding paper does not discolor under the effect of such light.
  • Ethyl-mercapto-spiro-dinaphthopyran green n-butyl-mercapto-spiro-dinaphthopyran green. 3-methyl n-aphtho (3-methoxy-benzo)-spiro-pyran red. 3.3'-Dichloro-spiro-dinaphthopyran violet-black. 3-propyl-spiro-dibenzopyran red. 3:butyl-spiro-dibenzopyran red. 3-methyl-spiro-benzo-naphtho-pyran red-violet.
  • a substrate a first layer of acid activated clay anchored on said substrate, said acid activatedclay being enriched with a non-volatile acid and exhibiting strong acidic reaction, and a second layer superimposed on said first layer and containing as active ingredient an effective amount of a spiro-dipyran, said spiro-dipyran, upon application of inscribing pressure, forming a visible color salt on said first layer.
  • the acid activated clay is a montmorillonite clay which has been activated by a strong mineral acid, a water slurry of said clay exhibiting a pH of about between 3.54.5.
  • a recording and duplicating material with color reaction components which handles cleanly and is sensitive to writing presusre, comprising a paper coated with a layer containing a substantially colorless spirodipyran and a paper coated with a layer containing acid activated clay enriched with a non-volatile acid to exhibit strong acidic reaction, both said layers being brought into contact with each other on application of writing pressure without the interposition of an intermediate layer so that said spirodipyran in said first layer is transferred to said second layer and there reacts with said clay material in a color salt-forming manner to produce a colored copy.
  • a typewriter ribbon wherein a ribbon substrate is impregnated with a non-smearing loyer of an active color forming ingredient of a spirodipyran and a paper coated with acid activated clay of acid reaction and enriched with about between 240% of a non-volatile acid to produce colored writing on the paper when brought into contact with each other on application of writing pressure.
  • a recording and duplicating material comprising in combination: a first paper substrate having a coating which contains as active ingredient between about 2-10% of a spiro-dipyran, and a second paper substrate having a coating containing a major proportion of acid activated montmorillonite clay enriched with a minor proportion of a non-volatile acid to exhibit strong acidic reaction, said first and second paper substrates, when brought into contact with said coatings facing each other and upon application of inscribing pressure forming a visible color salt on said clay coating.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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US483019A 1956-02-06 1965-08-20 Writing and manifolding material Expired - Lifetime US3293060A (en)

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Application Number Priority Date Filing Date Title
DEW18372A DE1127920B (de) 1956-02-06 1956-02-06 Druckempfindliches Aufzeichnungsmaterial
AT50757 1957-01-24

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US (1) US3293060A (en, 2012)
BE (1) BE721713A (en, 2012)
DE (1) DE1127920B (en, 2012)
GB (1) GB810401A (en, 2012)
NL (2) NL102415C (en, 2012)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US3488207A (en) * 1965-10-22 1970-01-06 Us Plywood Champ Papers Inc Process of preparing a colored substance and transfer copy set
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
DE2303825A1 (de) * 1972-01-28 1973-08-02 Mizusawa Industrial Chem Einen farbbildner fuer druckempfindliches registrierpapier enthaltende waessrige zusammensetzung und verfahren zu ihrer herstellung
US3753761A (en) * 1968-11-12 1973-08-21 Mizusawa Industrial Chem Pressure sensitive recording paper
DE2230225A1 (de) * 1972-06-21 1974-01-10 Basf Ag Neue spiropyrane und farbbildner fuer kopierverfahren
US3900216A (en) * 1969-10-22 1975-08-19 Fuji Photo Film Co Ltd Method for producing clay coated paper for pressure sensitive copying paper
US3900218A (en) * 1972-08-30 1975-08-19 Fuji Photo Film Co Ltd Desensitizer composition
US3963852A (en) * 1973-08-04 1976-06-15 Moore Business Forms, Inc. Clay-coated record material of improved image durability
DE2612036A1 (de) * 1975-03-24 1976-10-14 Moore Business Forms Inc Kohlefreies mehrfach-kopierblattsystem
US4124227A (en) * 1976-05-31 1978-11-07 Moore Business Forms, Inc. Oxime ethers of Michler's hydrol, method of producing same and pressure-sensitive recording systems containing such compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL268635A (en, 2012) * 1960-08-26 1900-01-01

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1132537A (en) * 1913-08-23 1915-03-16 Crescent Clay Refining Company Process of treating clay and like materials.
US1251058A (en) * 1916-11-22 1917-12-25 Frank Langford Process for purifying aluminous ores, earths, clays, and sand.
US1840363A (en) * 1928-12-13 1932-01-12 Illner Rudolf Process for altering the physical properties of finely divided mineral substances
US2489332A (en) * 1946-04-30 1949-11-29 Houdry Process Corp Preparation of an iron-freed acid treated kaolin catalyst
US2550467A (en) * 1948-07-13 1951-04-24 Ncr Co Manifold record material and process for making it
US2755200A (en) * 1953-12-28 1956-07-17 Du Pont Stabilized coloring compositions and methods of making and using same
US2755201A (en) * 1954-01-08 1956-07-17 Du Pont Stabilized ink compositions, transfer sheets coated therewith and methods of making same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1132537A (en) * 1913-08-23 1915-03-16 Crescent Clay Refining Company Process of treating clay and like materials.
US1251058A (en) * 1916-11-22 1917-12-25 Frank Langford Process for purifying aluminous ores, earths, clays, and sand.
US1840363A (en) * 1928-12-13 1932-01-12 Illner Rudolf Process for altering the physical properties of finely divided mineral substances
US2489332A (en) * 1946-04-30 1949-11-29 Houdry Process Corp Preparation of an iron-freed acid treated kaolin catalyst
US2550467A (en) * 1948-07-13 1951-04-24 Ncr Co Manifold record material and process for making it
US2755200A (en) * 1953-12-28 1956-07-17 Du Pont Stabilized coloring compositions and methods of making and using same
US2755201A (en) * 1954-01-08 1956-07-17 Du Pont Stabilized ink compositions, transfer sheets coated therewith and methods of making same

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3488207A (en) * 1965-10-22 1970-01-06 Us Plywood Champ Papers Inc Process of preparing a colored substance and transfer copy set
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US3753761A (en) * 1968-11-12 1973-08-21 Mizusawa Industrial Chem Pressure sensitive recording paper
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US3900216A (en) * 1969-10-22 1975-08-19 Fuji Photo Film Co Ltd Method for producing clay coated paper for pressure sensitive copying paper
DE2303825A1 (de) * 1972-01-28 1973-08-02 Mizusawa Industrial Chem Einen farbbildner fuer druckempfindliches registrierpapier enthaltende waessrige zusammensetzung und verfahren zu ihrer herstellung
DE2230225A1 (de) * 1972-06-21 1974-01-10 Basf Ag Neue spiropyrane und farbbildner fuer kopierverfahren
US3900218A (en) * 1972-08-30 1975-08-19 Fuji Photo Film Co Ltd Desensitizer composition
US3963852A (en) * 1973-08-04 1976-06-15 Moore Business Forms, Inc. Clay-coated record material of improved image durability
DE2612036A1 (de) * 1975-03-24 1976-10-14 Moore Business Forms Inc Kohlefreies mehrfach-kopierblattsystem
US4124227A (en) * 1976-05-31 1978-11-07 Moore Business Forms, Inc. Oxime ethers of Michler's hydrol, method of producing same and pressure-sensitive recording systems containing such compounds

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GB810401A (en) 1959-03-18
NL214309A (en, 2012)
BE721713A (en, 2012) 1969-03-14
NL102415C (en, 2012)
DE1127920B (de) 1962-04-19

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