US2597306A - Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ - Google Patents

Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ Download PDF

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US2597306A
US2597306A US11977449A US2597306A US 2597306 A US2597306 A US 2597306A US 11977449 A US11977449 A US 11977449A US 2597306 A US2597306 A US 2597306A
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diazo
acid
coupling
stencil
paper
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Eaton Samuel Edward
Robert W Fabian
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Arthur D Little Inc
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Arthur D Little Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00Inking and printing with a printer's forme
    • B41M1/12Stencil printing; Silk-screen printing
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00Printing
    • Y10S101/29Printing involving a color-forming phenomenon
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916Natural fiber dyeing
    • Y10S8/918Cellulose textile
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916Natural fiber dyeing
    • Y10S8/919Paper

Description

.USBS.

Patented May 20, 1952 UNITED STATES PATENT OFFICE Samuel Edward'Eaton, Lexington, and Robert W.

Fabian,

West Newton,

Mass, assignors to Arthur D. Little, Inc., Cambridge, Mass., a corporation of Massachusetts No Drawing. Application October 5, 1949,

, Serial No. 119,774

7 .Claims.

This invention relates to printing and more particularly to printing by means of dia zo compounds, and is a continuation-in-part of our U. S. application Ser. No. 633%, filed December 2, 1948, now abandoned.

The azo dyes are a well defined group containing the chromophor-N:N. The chromogen of azo dyestuffs with which we are concerned comprises at least one aryl radical with one or more chromophor groups attached to it. The mono azo dyes are generally prepared by joining two components of which the first is called the diazo component, and the second, usually a phenol, an amine, or an active methylene compound, is called the coupling component. The diazo component and the coupling component are caused to react to form a dye.

Use of the coupling action of diazo compounds to form dyes has been made in the printing art.

I In this process a light sensitive diazo compound, and a coupling agent, together with various stabilizing agents are coated on a support and dried; The paper is exposed through a printed pattern to light for several seconds and then to moist ammonia gas. The ammonia develops the dye by neutralizing the stabilizing acids present with the diazo and coupler components, i. e. it allows the diazo compound to couple to form a reproduction of the pattern. The pattern is faithfully reproduced since the light falling generally on the printed pattern passes only through those portions of the pattern not opaque to light and destroys the diazonium salt with liberation of nitrogen so that it is no longer capable of coupling.

The process of printing described above does, however, have several limitations for specialized It is, for instance, quite slow, taking several seconds to complete a reproduction. Other conventional printing processes such as those requiring the .use of ink associated with stencils have the difficulty that the stencils must be carefully cleaned before storage.

It is an object of the present invention to prepare mixtures of a diazo component and a coupling component that will serve to give a reproduction substantially instantly.

require little, if any, cleaning operations prior to, storage.

Still another object is to print sharp images.

These, and other objects, which will be apparent, may be preferably accomplished by first preparing an application of a diazo component and a dye-coupling component on a surface to be printed. Acid sufficient to stabilize a mixture of the diazo and coupler components on the base to be printed is included with the coating. The image is developed by an alkali which is placed on the treated surface in a predetermined pattern, and is fixed by destroying the unreacted diazo component. This may be done by the use of light, heat, or chemicals.

' placed through a stencil a sharp reproduction is produced almost instantly, while if a liquid is passed through a stencil there is a certain amount of spreading of the fluid due to capillary action of fibers in proximity to the liquid, and therefore some indistinctness about the edges develops.

Another advantage in the use of a gas is that the quantity need not be so critically controlled as in the case with a liquid. These factors are of more significance in some cases than in others.

In the practice of this invention the diazo component may be any diazo compound which, when coupled, will yield a colored dye. The dye formed may be fixed by the action of light, heat or chemicals. The fixing process serves to destroy the activity of any of the diazo component remaining uncoupled after the process is completed.

By so fixing, unwanted dye will not be subsequently formed in the background by any alkalinity which was present in the paper or which subsequently reached the paper or surface. The

' fixing is necessary since no amount of acid material will permanently prevent eventual coupling.

The diazo component may be any light sensitive diazo compound. The three preferred diazo compounds are:

l diazo-Z oXy naphthy1ene-4 sulfo-nate p-Diethyl amino benzene diazonium chloride ZnClz 4-benzoylamino-2-5-diethoxy benzene diazonium chloride.

Of the many diazo components the following are typical examples of useful compounds:

Para-chlorobenzenesulfonate of i-diazo-l-cyclohexylaniline Parachlorobenzene-sulfonate of 4-diazo-2-methoxy-l-cy clohexylamino benzene amino naphthalene-4 diazonium The preferred coupling components are:

Phloroglucinol Resorcinol Z-naphthol Other coupling agents include:

1-naphthol-4,7-disulfonic acid 1,8-dihydroxynaphthalene-3,6-disulfonic acid 2,3-dihydroxynaphthalene 2-naphthol-3,6-disulphonic acid Acetoacetanilide and its substitution products Phenylmethylpyrazazolone and its substitution products Anilides of 2-hydroxy-3-naphthoic acid, e. g. the

anilide, and 3-methyl-anilide.

The alkaline component is preferably a vapor such as ammonia gas, or methyl amine. Other alkaline agents which also may be used include aqueous solutions of ammonia, alkali metal hydroxides, alkali metal carbonates, and alkaline earth alkalies.

The acidic materials used are preferably nonvolatile or not readily volatile materials such as tartaric, boric, acetic, maleic, citric, ammonium sulfate, aluminum sulfate, and sodium acid sulfate.

The proportions of diazo component to coupler are well known and are not a part of this invention. It is customary to include an excess of the coupler component to insure the presence of sufficient coupler for any dye component that may be present.

The amount of a given acid present to insure stabilization in the preferred process is, to some extent, dependent upon the particular diazo compound stabilized. It is a fact that the reaction of diazo compound with a coupler may be retarded by preventing the hydrolysis of the diazo compound as by the addition of an acid. Normally, sufiicient acid is added to lower the pH to a point where the coupling action is prevented for long periods of time. For some purposes, we prefer to use only sufficient acidic material to prevent immediate coupling or to prevent coupling on the surface to be printed for a few hours. The speed of the neutralization process is thereby increased, but more importantly less alkali need be added thus requiring less time when reproduction is carried out by means of a stencil. The desired speed of contact for reproduction is usually between 0.001 and 1 second contact time, and these speeds are easily attainable by the process herein described.

The exact concentration of acid desirable is dependent partially upon the support being used. Many ordinary types of paper for instance appear to accelerate dye formation in the absence of sufficient acid, probably because of the alkalinity of the paper.

After the image is fixed, the print may not be color stable due to a difference in pH between the alkali developed image and the acid treated paper. That is, many of the diazo dyes, to some extent at least, change color with changing pH. Thus it is best to subject the acid surface to an alkali treatment after the fixing step to insure a permanent color, or adjust the pH of the original sensitizing solution so that it is harmless.

Example I The surface of a type-impressed stencil is placed in close contact with the outside surface of a perforated 10" diameter metal drum, to the inside surface of which is fastened a wad of cotton saturated with concentrated aqueous ammonia. A sensitizing solution of the composition presented below is applied to the paper which is to receive the image. While still moist, the paper is rolled against the stencil at the rate of about 250 linear feet per minute, pressure being exerted upon the paper over the area of contact, which should be about 1 linear inch of the sensitized paper at any given instant. A purple image of the openings of the stencil is immediately developed. The remaining uncoupled diazo component is destroyed by holding the developed paper under a No. 1 photoflood lamp for 5 seconds at a distance of four inches.

The composition of the sensitizing solution is as follows:

ZnClz double salt of 4-diethylamino diazo benzene gm 2.0 Phloroglucinol gm 0.25 Tartaric acid gm 0.4 Sodium acid sulfate gm 0.5 Water ml 100 Example II Example I is repeated except that the remaining uncoupled diazo component is destroyed by passing the image containing surface of the unfinished paper over a metal surface maintained at about 500 F. The time of contact between any one point of paper and the heated surface should be about 2 seconds.

Example III Example I is repeated except that the remaining uncoupled diazo component is destroyed by applying the following solution by kissroll:

Acetic acid (glacial) ml 5 Water ml Stannous chloride grams 5 Example IV p-Diazo-diphenyl amine sulfate gm 1 2-hydroxy-3-naphthoic acid-otoluidide gm 0.25 Tartaric acid gm 0.5 Water ml 50 Acetone ml 50 Destruction of the undeveloped diazo compound by exposure for two minutes to a Hanovia type 7420 ultraviolet light serves to fix the image by destruction of the unexposed diazo component. The final dry image is violet.

Water purple image.

7 Example V Paper is pretreated with a solution prepared as follows:

ZI1C12 double salt of 4-diethyl amino diazo benzene gm 2 Tartaric acid gm 0.5 ml 100 The paper is brought into contact with a cut stencil through which is passed an ink consisting of a thickened per cent solution of sodium carbonate to form the potential image. Subsequent treatment of the paper with a 0.25 per cent solution of phloroglucinol develops a deep The remaining uncoupled diazo component is destroyed by exposure to moderate- 'ly bright direct sunlight for 1 minute.

Example VI Example V is repeated with the exception that the paper is pretreated with the following. solu- After passing the sodium carbonate ink through the stencil, the paper is treated with a 2 per cent solution of ZnClz double salt of i-diethyl amino diazo benzene. Destruction of the uncoupled image is accomplished by simply leaving the paper exposed to ordinary daylight for 8 hours. The increased acid over that used in Example V prevents coupling of the undeveloped diazo compound for this extended period. In the practice of the invention it is advisable that the image accepting surface be distinctly moist, thereby considerably increasing the speed. Under such conditions the image is produced in only a fraction of a second, Whereas when ammonia gas is passed through a stencil onto a dry coating of the diazo component, the coupler component and acid, the time required is several times as long. It has been found, however, that when reproduction is made on paper the added moisture tends to curl the paper. The use of a non-swelling agent for cellulose fibers such as a Water-alcohol mixture helps to eliminate obj ectionable curl when printing a paper, and is therefore advised. On the other hand it may be necessary in the case of highly sized 0r wax coated papers to add a wetting agent in order to secure even distribution of the components over the surface to be printed. Such a procedure would not induce curl where spot sensitization is emp1oyed-a feature of this process. By spot sensi tization is meant coating over a limited area of the sheet on which printing is to take place. Further speed may be obtained where necessary when ammonia gas is passed through a stencil by applying pressure, although satisfactory speeds may be obtained without resort to this alternative.

In the practice of this invention either light sensitive and/or heat-sensitive diazo compounds may be employed. Many of the diazo compounds are quite light sensitive and relatively heat insensitive; these may be fixed by ultraviolet light or in fact ordinary daylight in a very short period. Other diazo compounds are quite heat sensitive and may be fixed rapidly by heat, as with an infra red lamp. Preferably both ultraviolet and infra-red radiations are to be used in conjunction since together they fix the reproduction more rapidly than either alone. Reducing chemicals, such as stannous chloride, may be employed, if

second to develop a deep purple image.

though this procedure is not recommended due to the incidental development of phenyl hydrazine.

In the preparation of the coating materials stabilizers and sensitizers well known in the art may be added if desired. These include such materials as thiourea to prevent the darkening of the background due to oxidation of thecouplers.

It is readily apparent that by the use of the above process rapid reproductions may be accomplished. In order to illustrate the process of the invention still further the following commercial use is described.

Magazines, house organs, papers, and so forth, are frequently mailed to an address Which may be applied by a stencil. Since these stencils become coated with a diflicultly removable ink during use, their storage and reuse is normally somewhat of a problem, In the preferred process, herewith described, no such cleaning and storing problem exists.

When a continuous strip of stenciled addresses is to be used to address envelopes, the. strip is placed in an automatic feed mechanism capable of advancing address areas singly and in rapid succession; the envelopes to be addressed are placed in another automatic feed mechanism. In operation, as each envelope is advanced, it is coated by kissroll in a given small area with the sensitizing solution noted in Example I above. Immediately after this spot-sensitization, the

stencil feed mechanism advances a stenciled address and places it in position over the slightly damp, sensitized area of the envelope. The stencil surface and paper are pressed into intimate contact and automatically advanced into and out of the ammonia chamber, stencil side toward the ammonia. Contact is maintained for about ,40 During each exposure, another envelope is being sensitized, ready for repetition of the above process.

After the image is developed upon the envelope, the remaining, undeveloped diazo material is destroyed by exposure to a No. 1 Photoflood lamp for live seconds at a distance of four inches, to prevent darkening of the background. The stencil strip, meanwhile, is taken u for subsequent filing and reuse.

In the above process, the sensitizing solution is applied by kissroll. Other methods of application such as spraying, sponging, etc may be employed as alternative if desired. It is also noted that the stencils are supplied in a continuous strip. Any alternative methods in which the addresses are singly framed or mounted in a Way which would permit the use of an automatic feed mechanism might be used.

In the above discussion reference has been made to passing an alkali, and particularly ammonia, through a stencil. It will be readily appreciated that the stencil need not be one which is permeable to light; there need be only a differential resistance to transfer through the stencil at predetermined points.

While the process of the invention is most advantageously practiced, for most purposes by passing ammonia gas through a stencil onto a moist, sensitized surface, other modifications of our process are possible.

The alkaline material may be applied to the sensitized support as by ofi-set, type, or by other printing means. In the case of ammonia it may be projected through the end of a tube onto a sensitized support.

The essential part of the application of alkali is that it be placed upon the support in a differential manner, to form a predetermined pattern. The diiferential quantity of alkali brings out variation in intensity of color and variation between color and no color.

A further modification or extension of our process includes the use of two or more dyes designed to complement one another to reproduce color. For example, by proper and known procedure a colored image may be broken down into the primary color images, and half tone stencils or printing plates made of these images. It is also known that suitable diazo-coupler systems yield the primary colors as Well as colors complementary to them. Multicolored printing then consists in developing the various colors separately with alkali and fixing after each operation. In any case the alkali is applied in a predetermined pattern upon the support thus producing, by the coupling of the dye components,

the predetermined image. The unreacted diazo component is then destroyed by light and/or other suitable means so that disturbing background color will not subsequently develop. Care must be taken that coupling previously employed does not interfere with subsequent dye systems.

The support commonly employed is of course paper. Other types of support include fabric such as cotton cloth, leather, wood, walls, etc.

Any support, in fact, on which the dye components may be placed and stabilized is subject to the operatio of the process herein described.

The above examples are given as illustrations only, and any modifications within the skill of the art are intended to be included within the appended claims.

In the practice of our invention it has been observed that after contact with alkali, the image, while appearing instantly, does not always reach its full intensity until perhaps several seconds after exposure to ammonia vapor. The time of development may be decreased considerably by insuring the amount of moisture, and by heat. It has been observed, for instance, that the rate of coupling increases rapidly with increasing temperature. Thus when it is desired to fix an image immediately after exposure to alkali, heat alone or heat as well as light could be employed to advantage.

We claim:

1. A process of printing which comprises applying to a support a diazo compound capable of yielding a dye when coupled, and a coupler for the diazo compound the reaction of said compounds being inhibited by acid, and an acid, said acid being present in an amount at least sufficient to prevent immediate coupling of the diazo compound, exposing the support through a stencil to sufiicient alkali to cause coupling of alkalized diazo component and said coupler, and fixing the uncoupled compound.

2. The process according to claim 1 wherein the alkalization takes place in the presence of moisture.

3. The process according to claim 2 wherein the alkali is ammonia gas.

4. The process according to claim 2 wherein the alkali is sodium carbonate.

5. A process of printing which comprises applying to a paper sheet with a light sensitive diazo compound capable of yielding a dye when coupled, a coupler for the diazo compound the reaction of said compounds bein inhibited by acid, and an acid, said acid being present in an amount surficient to prevent immediate coupling of the diazo compound, exposing the paper sheet through a stencil to sufiicient ammonia to cause coupling of exposed diazo compound, and fixing the uncoupled compound, said paper being moist at the time of contact with the ammonia.

6. A process of printing which comprises applying to a paper sheet a light sensitive diazo compound capable of yielding a dye when coupled, a coupler for the diazo compound the reaction of said compounds being inhibited by acid, and an acid, said acid being present in an amount sufllcient to prevent immediate coupling of the diazo compound, exposing the paper sheet through a stencil to sufficient alkali solution to cause coupling of exposed diazo compound, and fixing the uncoupled compound.

7. A process of printing which comprises applying to a paper sheet a heat sensitive diazo compound capable of yielding a dye when coupled, a coupler for the diazo compound the reaction of said compounds being inhibited by acid, and an acid, said acid being present in an amount sufficient to prevent immediate coupling of the diazo compound, exposing the paper sheet through a stencil to sufiicient alkali solution to cause coupling of exposed diazo compound, and fixing with heat the uncoupled compound.

SAMUEL EDWARD EATON. ROBERT W. FABIAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date R. 23,016 Rossander July 13, 1948 1,444,469 Kogel Feb. 6, 1923 1,572,715 Gunther Feb. 9, 1926 1,820,024 Keller Aug. 25, 1931 1,821,281 Grinten Sept. 1, 1931 FOREIGN PATENTS Number Country Date 17,694 Great Britain 1890 331,056 Great Britain June 26, 1930 452,177 Great Britain Aug. 18, 1936

Claims (1)

1. A PROCESS OF PRINTING WHICH COMPRISES APPLYING TO A SUPPORT A DIAZO COMPOUUD CAPABLE OF YIELDING A DYE WHEN COUPLED, AND A COUPLER FOR THE DIAZO COMPOUND THE REACTION OF SAID COMPOUNDS BEING INHIBITED BY ACID, AND AN ACID, SAID ACID BEING PRESENT IN AN AMOUNT AT LEAST SUFFICIENT TO PREVENT IMMEDIATE COUPLING OF THE DIAZO COMPOUND, EXPOSING THE SUPPORT THROUGH A STENCIL TO SUFFICIENT ALKALI TO CAUSE COUPLING OF ALKALIZED DIAZO COMPONENT AND SAID COUPLER, AND FIXING THE UNCOUPLED COMPOUND.
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2634677A (en) * 1952-05-13 1953-04-14 Dick Co Ab Azo dye duplicating process
US2743191A (en) * 1952-05-13 1956-04-24 Dick Co Ab Method for manufacturing transfer sheets for spirit duplication
US2795504A (en) * 1952-10-25 1957-06-11 Dick Co Ab Compositions for use in the manufacture of elements in reproduction
US2969015A (en) * 1953-07-14 1961-01-24 Dick Co Ab Method of producing a spirit master from a positive and a duplicating process with same
US3000298A (en) * 1956-01-03 1961-09-19 Sherman Printing by diazotization
US3063050A (en) * 1958-12-17 1962-11-06 Texas Instruments Inc Inkless recording method
US3096197A (en) * 1960-01-21 1963-07-02 Ralph W Buetow Marking method
US3153592A (en) * 1962-05-15 1964-10-20 Dietzgen Co Eugene Complex salt diazotype photoprinting materials
US3224354A (en) * 1960-07-07 1965-12-21 Dietzgen Co Eugene Apparatus for making copies on ray sensitive sheets upon exposure to ultraviolet and infrared radiation
US3261684A (en) * 1961-08-31 1966-07-19 Grinten Chem L V D Process and developer for developing exposed one-component diazotype materials
US3262386A (en) * 1959-11-23 1966-07-26 Little Inc A Duplicating method
US3418469A (en) * 1965-04-05 1968-12-24 Keuffel & Esser Co Diazo reproduction
US3435759A (en) * 1966-03-02 1969-04-01 Dymo Industries Inc Duplicating method involving color formation
US3510336A (en) * 1965-08-12 1970-05-05 Gaf Great Britain Ltd Reflex copying method
US3523866A (en) * 1968-11-19 1970-08-11 Wilbur W Krueger Authenticatable paper
US3622368A (en) * 1967-08-22 1971-11-23 Ricoh Kk Method for developing electrostatic latent images by utilizing coupling reaction
US4057389A (en) * 1975-12-20 1977-11-08 Hoechst Aktiengesellschaft Process for the printing with developing dyes
US4268600A (en) * 1977-12-09 1981-05-19 Issec and Tissages de Soieries Rennis Process for photochemically coloring textiles using photosensitive triazene and coupler therefor

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB331056A (en) *
US1444469A (en) * 1917-05-31 1923-02-06 Firm Of Kalle & Co Ag Manufacture of light copy paper
US1572715A (en) * 1926-02-09 Rhine
US1820024A (en) * 1925-01-19 1931-08-25 Gen Aniline Works Inc Diazosalt preparations for dyeing and printing
US1821281A (en) * 1926-12-11 1931-09-01 Frans Van Der Grinten Manufacture of diazo-types
GB452177A (en) * 1934-07-12 1936-08-18 Chem Ind Basel Process for producing fast printings on the fibre
USRE23016E (en) * 1948-07-13 Azo dye compositions stabilized with

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB331056A (en) *
US1572715A (en) * 1926-02-09 Rhine
USRE23016E (en) * 1948-07-13 Azo dye compositions stabilized with
US1444469A (en) * 1917-05-31 1923-02-06 Firm Of Kalle & Co Ag Manufacture of light copy paper
US1820024A (en) * 1925-01-19 1931-08-25 Gen Aniline Works Inc Diazosalt preparations for dyeing and printing
US1821281A (en) * 1926-12-11 1931-09-01 Frans Van Der Grinten Manufacture of diazo-types
GB452177A (en) * 1934-07-12 1936-08-18 Chem Ind Basel Process for producing fast printings on the fibre

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2634677A (en) * 1952-05-13 1953-04-14 Dick Co Ab Azo dye duplicating process
US2743191A (en) * 1952-05-13 1956-04-24 Dick Co Ab Method for manufacturing transfer sheets for spirit duplication
US2748024A (en) * 1952-05-13 1956-05-29 Dick Co Ab Transfer sheet for use in a hectograph duplicating process
US2798427A (en) * 1952-05-13 1957-07-09 Dick Co Ab Duplicating process
US2795504A (en) * 1952-10-25 1957-06-11 Dick Co Ab Compositions for use in the manufacture of elements in reproduction
US2969015A (en) * 1953-07-14 1961-01-24 Dick Co Ab Method of producing a spirit master from a positive and a duplicating process with same
US3000298A (en) * 1956-01-03 1961-09-19 Sherman Printing by diazotization
US3063050A (en) * 1958-12-17 1962-11-06 Texas Instruments Inc Inkless recording method
US3262386A (en) * 1959-11-23 1966-07-26 Little Inc A Duplicating method
US3096197A (en) * 1960-01-21 1963-07-02 Ralph W Buetow Marking method
US3224354A (en) * 1960-07-07 1965-12-21 Dietzgen Co Eugene Apparatus for making copies on ray sensitive sheets upon exposure to ultraviolet and infrared radiation
US3261684A (en) * 1961-08-31 1966-07-19 Grinten Chem L V D Process and developer for developing exposed one-component diazotype materials
US3153592A (en) * 1962-05-15 1964-10-20 Dietzgen Co Eugene Complex salt diazotype photoprinting materials
US3418469A (en) * 1965-04-05 1968-12-24 Keuffel & Esser Co Diazo reproduction
US3510336A (en) * 1965-08-12 1970-05-05 Gaf Great Britain Ltd Reflex copying method
US3435759A (en) * 1966-03-02 1969-04-01 Dymo Industries Inc Duplicating method involving color formation
US3622368A (en) * 1967-08-22 1971-11-23 Ricoh Kk Method for developing electrostatic latent images by utilizing coupling reaction
US3523866A (en) * 1968-11-19 1970-08-11 Wilbur W Krueger Authenticatable paper
US4057389A (en) * 1975-12-20 1977-11-08 Hoechst Aktiengesellschaft Process for the printing with developing dyes
US4268600A (en) * 1977-12-09 1981-05-19 Issec and Tissages de Soieries Rennis Process for photochemically coloring textiles using photosensitive triazene and coupler therefor

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