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Publication numberUS3907567 A
Publication typeGrant
Publication dateSep 23, 1975
Filing dateJan 17, 1974
Priority dateMay 1, 1970
Publication numberUS 3907567 A, US 3907567A, US-A-3907567, US3907567 A, US3907567A
InventorsAizawa Tatsuo, Kamezawa Yasutoki, Kouchi Toshihiro, Nihyakumen Kouzi, Ueda Yasuo, Yokoyama Taizo
Original AssigneeMita Industrial Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Waxy crayon or ink-like diazotype developer composition comprising heat transferrable azo coupler and transfer promotor
US 3907567 A
Abstract
A process for diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original area colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60 DEG - 80 DEG C.), and a color former to be used in such process, which comprises a thermosublimative coupler and a thermosublimative, organic, solid transfer promotor having no coupling property in itself.
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United States Patent Nihyakumen et al.

[ Sept. 23, 1975 Mita Industrial Company, Ltd., Osaka, Japan Filed: Jan. 17, 1974 Appl. No.: 434,139

Related U.S. Application Data Continuation of Ser. No. 139,442, May 3, 1971, abandoned.

Assignee:

Foreign Application Priority Data May 1, 1970 Japan 45-36851 U.S. Cl 96/49; 96/75; 96/91 R; 106/19; 117/368; 117/369; 250/317; 250/318 Int. Cl. G03C 5/34 Field of Search 96/49.75, 91 R; 117/368,

References Cited UNITED STATES PATENTS 4/1957 Kosar 96/49 3,162,763 12/1964 Huett et a1 250/318 3,169,067 2/1965 Benbrook et a1. 96/49 3,169,069 2/1965 Berman et al. 96/49 X 3,364,858 l/1968 Kojima et a1. 250/318 3,418,468 12/1968 Marx ct al. 250/318 3,454,764 7/1969 Collier 96/49 X 3,486,900 12/1969 Tsunoda et a1. 96/49 X 3,502,871 3/1970 Marx et al. 250/318 3,715,213 2/1973 Nihyakumen ct 96/49 3,725,066 4/1973 Nihyakumen et a1 96/49 FOREIGN PATENTS OR APPLICATIONS 895,249 5/1962 United Kingdom 96/91 R 1,000,151 8/1965 United Kingdom 96/91 R Primary Examiner--Charles L. Bowers, Jr. Attorney, Agent, or FirmSherman & Shalloway [57] ABSTRACT A process for diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original area colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at60 80C.), and a color former to be used in such process, which comprises a thermosublimative coupler and a thermosub- -1imative, organic, solid transfer promotor having no coupling property in itself.

19 Claims, 2 Drawing Figures US Patent Sept. 23,1975 3,907,567

F/ g. F g. 2

ORIGINAL I 2 3 I 2 3 i loRIeImAwigI PREPARATION OF ORIGINAL FOR MULTICOLOR DEVELOPMENT SHEETFOR :1

COUPLER ESG gEE E 2' 3 LIGHT SOURCE LIGHT HEAT.

LIGHT EXPOSURE I I 2' HEAT H PI-IO'I'gSENSITIV II I2 l3 WAXY CRAYON OR INK-LIKE DIAZOTYPE DEVELOPER COMPOSITION COMPRISING HEAT TRANSFERRABLE AZO COUPLER AND TRANSFER PROMOTOR This is a continuation of application Ser. No. 139,442, filed May 3, 1971, now abandoned.

This invention relates to a process for diazo-type multi-color reproduction and to a color former to be used in such process. More particularly, this invention relates to a process for the diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60 80C.), and to a color former to be used in such process.

A process for the diazo-type multi-color reproduction has been previously proposed based on the discovery that predetermined portions of an original can be reproduced into different hues regardless of difference or similarlity of the light transmission in the original, by conducting the steps of (A) exposing to light a diazotype photosensitive material containing at least one diazonium salt (which will be referred to as diazonium salt and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (which will be referred to as coupler (11)") disposed in face-toface contact with such diazo-type photosensitive material at a portion corresponding to a predetermined portion of the original to be colored in a different hue, the steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then developing the lightexposed photosensitive material in the presence of a coupler having a lower coupling rate under developing conditions (which will be referred as coupler (17)) than the thermovolatile or thermosublimative coupler (a). In this diazo-type multicolor reproduction process, a thermovolatile or thermosublimative coupler is combined with the back face of an original at one or more portions predetermined to be colored in a different hue. The thermovolatile coupler in the form of, for instance, an ink-like or waxy coloring composition is combined with the back face of the original by coating or transferring. Most of thermovolatile and thermosublimative couplers have relatively high volatilizing or sublimating temperatures, and therefore, the heat transfer must be conducted at temperatures exceeding 100C. The high heat transfer temperature results in l the following disadvantages. Namely, the life of a copy ing machine is extremely shortened and its structure is inevitably complicated. Further, the high heat transfer temperature causes various operational difficulties. Still further, when'multi-eolored copies are obtained by employing two or more thermovolatile or thermosublimative couplers differing in their volatilizing or sublimating temperature, it is difficult to determine the heat transfer temperature. More specifically, when the heat transfer temperature is determined depending on a coupler having a lower volatilizing or sublimating temperature, the amount of the coupler having a higher volatilizing or sublimating temperature transferred is very low and copies of a high color contrast cannot be obtained, whereas if the heat transfer temperature is determined depending on the coupler ofa higher vola tilizing or sublimating temperature, great excess of the coupler of a lower volatilizing or sublimating temperature is transferred by one transfer treatment. with the result that the transfer layer is consumed by conducting the heat transfer only several times and the number of copies is extremely lowered.

Further research on the above-mentioned diazo-type multicolor reproduction process has been conducted with a view to overcoming these defects, and it has now been found that when a certain solid substance having no coupling property in itself is incorporated into the thermovolatile or thermosublimative coupler (a). the transfer of the coupler (a) to a diazo-type photosensitive material can be effected at a relatively low temperature very easily and even if two or more couplers (a) are used, heat transfer temperatures and the amounts of the couplers transferred can be almost approximated. Based on this finding, the present invention has been developed.

Accordingly, the primary object of this invention is to provide a diazo-type multicolor reproduction process according to which the heat transfer of one or more couplers to a diazo-type photosensitive material can be effected ata relatively low temperature, and to provide a color former for use in conducting such process.

Another object of this invention is to provide a diazotype multicolor reproduction process according to which two or more couplers to be combined with a diazotype photosensitive material can be heattransferred with almost equal amounts at approximating temperatures, whereby many copies can be obtained from one original with the heat transfer layer formed thereon, while conducting the heat transfer at relatively low temperatures, and to provide a color former to be used in such process.

In accordance with this invention. a color former for use in the diazo-type multicolor reproduction is provided, which comprises a thermovolatile or thermosublimative coupler, and a thermosublimative, organic, solid transfer promotor having no coupling property in itself. The above objects of this invention can be attained by the useof such color former.

In accordance with this invention, an improvement of the above-mentioned diazo-type multicolor reproduction process previously proposed, is provided wherein a color former comprising a thermovolatile or thermosublimative coupler, and a thermosublimative, organic. solid transfer promotor having no coupling property in itself is usedas the coupler (a).

In this invention it is essential that the thermosublimative, organic, solid, transfer promoter should not possess any coupling property in itself. As such transfer promotor any organic compound that exhibits a high sublimating property at temperatures exceeding room temperature, especially at temperatures exceeding 60C. and has a melting point above 60C., preferably above C. can be used The transfer promoter may be chosen from naphthalene, naphthalene derivatives. terpene compounds, halogenated benzenes and other organic solid sublimative compounds. Typical examples of such transfer promotor are as follows:

Naphthalene d-Camphor Menthol Camphene Benzoie acid Maleic anhydride Phthalic anhydride Oxalic acid Fomic acid Anthranilic acid Ethylboric acid Phenylhydrazine hydrochloride p-Hydroxyphenyl acetic acid Atropine Z-Aminoquinoline a-Chloroacrylic acid o-Chlorobenzoic acid p-Dichloroben ze ne Chlorofumaric acid Diacetone-D-glucose 1,4 Cycl'ohexadione 2.6-Dichlorobenzoic acid Di-a-naphthyl ketone N,N-diphenyl acetamide I 2,4-Dimethyl-3-furan-carboxylic acid Dimethylphosphinic acid Cinnamylideneacetic acid Tartronie acid Thiourethane 2,3,4.5-Tetramethylpyrrol Triiodobenzene a-Naphthyl ketone 1,8-Naphthylene diamine Nitrobenzonitrile Hydrochelidonic acid I Pyridine carboxylic acid Pyrene Phenanthrene Phenylpropiolic acid 3-Furancarboxylic acid o-Benzylbenzoie acid Bornane Meconine Mesitylenic acid 5-Methyl2-furancarboxylic acid Lapachol It 'is essential that among the thermovolatile or thermosublimative coupler (a) to be used in the color former of this invention.a coupler (h) anda diazonium salt (0) the following relations should be established in conducting the multicolor reproduction according to this invention: 7

l. Thermovolatile or .thermosublimative coupler (a) has a higher coupling rate under developing conditions than coupler (h). 7

ll. Dyestuff (h)-(c), dyestuff(a)-(c), dycstuff(a')-(( formed at the development have hues different from one another.

Any coupler that can be volatilized or sublimated I under heating conditions may be used as the ther-" movolatile or thermosublimative coupler (a) in this invention. As such coupler (a) phenol derivatives, hydroxynaphthalene derivatives. aniline derivatives and active methylene group-containing compounds may be mentioned. In view of facilitation of the heat transfer operation it is preferred that these derivatives do not contain soluble groups such as a sulfonic acid group.

Examples of these derivatives usable as coupler (a) are as follows:

Phenol Derivatives Phenol Pyrocatechol Resorcin Phloroglucin o-Hydroxybenzalcohol Resorcin monoglycol ether Resorcin diglycol ether Hydrotoluquinone Pyrogallol S-Hydroxy-isophthalic acid Pyrogallol-4-carboxylic acid Vanillin Isovanillic acid Vanillic acid 2-l-lyclroxy-terephthalic acid Z-Hydroxy-p-toluylic acid 3-Hydroxy-p-toluylic acid 5-Hydroxy-o-toluylic acid 6-Hydroxy-m-toluylic acid Para-Hydroxyphenylacetic acid Para-hydroxybenzaldehyde Ortho-hydroxybenzoic acid Ortho-hydroxybenzyl alcohol 4,4-Dihydroxybiphenol 3,5-Dichloro-salicylic acid 5-Chloro-2-r1itrophenol 2,5-Dihydroxyacetophenone 2,5-Dinitrophenol 2,4-dinitrophenol 2,4-Dinitroresorcin 4,6-Dibromo-2-nitrophenol 2.5-Dimethyl hydroquinone Aniline Derivatives Meta-aminobenzoic acid Dimethyl-meta-amirio-phenol I Z-Amino-p-cresol Ortho-aminophenol Meta-aminophenol Para-aminophenol Para-chloroaniline 3.4-Diaminotoluene Active Methylene Group-Containing Compounds I -Phenyl- 3-methylpyrazolone (5) l-Phenyl-3-carboxypyrazolone Acetoacctic acid anilide Acetoacetic-o-chloroanilide Hydroxynaphthalene Derivatives 2,3-Dihydroxynaphthalene B-Naphthol q-Naphthol l,6 -Dihydroxynaphthalene 8-Amirio-2'naphthol 2,6-Dihydroxynaphthalene 2,7 Dihydroxynaphthalene S-Hydroxy-l-naphthonic acid 2,2-dihydroxy-l,1"-binaphthyl 4,4'-dihydroxy-l .l '-binaphthyl 3-Carboxy2naphthol As coupler (b) to be used in combination with the thermovolatile or thermosublimative couple (a) for conducting the multicolor reproduction with use of the color former of this invention. any coupler that has a lower coupling rate with the diazonium salt (0) under the developing conditions than the rate of coupling of the thermovolatile -or the'rmosublimative coupler (a) contained in the color former with the diazonium salt can be used. When a plurality of thermovolatile or thermosublimative couplers (a) are used. the coupling rate of the coupler (h) should be lower than that of any of couplers (a). Selection of couplers (a) and (h) meeting the above requirement may be easily performed by those skilled in the art based on simple experiments.

Couplers having a relatively lower coupling rate may be selected among couplers recited above with respect to the thermovolatile or thermosublimative couplers (a) and be used as the coupler (b). In addition. the following may be used as coupler b) in this invention.

Phenol Derivatives 2.5.6-Trimethylphenol Z-Hydroxymethylphenol B4 2-hydroxyphenyl)-propionic acid Z-(e-Phenylaminomethyl)-phenol B44-Methyl-2-hydroxyphenyl)-glutaric acid 2,5-Dimethyl-6-(N-dimethylaminomethyl)-phenol l.3-Dimethyl ether of pyrogallol a-Resorcylic acid ethanolamine B-Resorcylic acid N-Lauryl-p-aminophenol N-Acyl-m-aminophenol Meta-hydroxy-acetoanilide Ortho-N-hydroxyphenyl-monoguanidine Para-N-hydroxyphenyl-biguanidine 2,5-Dimethyl-4-morpholinomethyl phenol 2-Methyl-5-isopropyl-m0rpholinomethyl phenol 4-Morpholinomethylresorcinol monomethyl ether 3,3',5 Trihydroxydiphenyl 3,3',5,5'-Tetrahydroxydiphenyl 2,2',4,4'-Tetrahydroxydiphenyl 2,4,4-Trihydroxydiphenyl-2-sulfonic acid 2,4 6,3,5'-Pentahydroxydiphenyl 2,2,4,4-Tetrahydroxydiphenyl sulfide Naphthols 23-Dihydroxynaphthalene-o-sulfonic acid 2-Naphthol-3,6-disulfonic acid 2,7-Dihydroxynaphthalene-3-sulfonic acid 2 8-Dihydroxynaphthalene-o-sulfonic acid l,8-Dihydroxynaphthalene-8-sulfonic acid l,8-Aminonaphthol-5-sulfonic acid 2.7-Dihydroxynaphthalene-3,6-disulfonic acid l.8-Benzoylaminonaphthol-Z-sulfonic acid l.8-Dihydroxynaphthalene-o-sulfonic acid 2Hydroxy-3-naphthionic-N-B-hydroxyethyl amide B-Hydroxynaphthionic acid aminoethylamine Z-Hydroxy-3-naphthionic-N,N-bis-,B-hydroxy ether amide S-Hydroxy-Z-naphthionic-hydroxyethyl amide l-( N-Carboethoxymethylamino) 8-naphthol-4- sulfonic acid v 5-( Para-nitro )-benzamidol-naphthol l-Hydroxynaphthyl-7-phenyl-guanidine Z-Hydroxynaphthyl-8-biguanidine l-Naphthol-3-(N-B-hydroxyethyl)-sulfonie amide l-Naphthol-3-(N-o-methoxyphenyl)-sulfonic amide Bis-t 5-hydroxy-7-sulfo-naphthyl( 2 ]-amine N.N-Bis[ l-hydroxy-3-sulfo-naphthyl(6)]-thiourea Active Methylene Group-Containing Compounds Acetoacetic acid cyclohexylamide Acetoacetic acid benzylamide Cyanoacetoanilide l-( 3 '-Sulfoamide )phenyl-3-methylpyrazolene-S l-(4-CarboXy-ethylphenyl )-3-dodecyl-pyra2olone-5 S-Hydroxyl .2-naphthylimidazole 2-Methyl-4-hydroxybenzimidazole 7-Methyl-4-hydroxybenzothiazole l ,7-Dimethyl-4-hydroxy-benzotriazole 3-Hydroxythiophene-5-carboxylic acid l-3-4-Cyelopentatrione In conducting the diazo-type multicolor reproduction with use of the color former comprising the abovementioned thermovolatile or thermosublimative coupler (a) and thermosublimative. organic. solid transfer promotor in accordance with this invention, at first an original for multicolor development is formed by apply ing at least one transparent or semi-transparent layer of a mixture of a thermovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promotor onto the back surface of a transparent or semi-transparent original to be copied, in one or more predetermined portions thereof.

The so formed original for multicolor development is over-lapped on the diazo-type photosensitive material containing at least one diazonium salt in a manner such that the layer of coupler (u) will confront the photosensitive surface of the photosensitive material. and the light-exposure and heating are effected coincidentally or successively in this order or the reverse order. Thus, the thermovolatilc or thermosublimative coupler (a) is heat-transferred to the predetermined portion of the surface of the photosensitive material together with the transfer promotor at a relatively low temperature C. and the light resolution of the diazonium salt (0) in the photosensitive material occurs depending on the light transmission of the original. When the so exposed photosensitive material is developed by a method known per so, at the predetermined portion to which the coupler (a) has been heat-transferred, the diazonium salt (c) at the non-exposed area reacts selectively and preferentially with the coupler (a) to form a dyestuff (c) (a) and at other portions the diazonium salt (c) in the non-exposed area reacts with coupler (b) to form a dyestuff (c) (b). As a result a multicolored reproductive copy in which the predetermined portion is colored in a hue different from that of the other portion is obtained.

The above-mentioned original for multicolor development may be prepared, for instance, by a method comprising applying a coating composition containing the above-mentioned color former comprising the thermovolatile or thermosublimative coupler (a) and the transfer promotor onto the back surface of a portion predetermined to have a different hue, of a transparent or semi-transparent original to be copied, or by a method comprising coating or impregnating a transparent or semi-transparent substrate with a coating composition comprising the color former of this invention and combining the resulting sheet for heat-transferring thecoupler, with the back surface of the specific portion of the original predetermined to have a different hue in a manner such that the layer for heattransferring the coupler will confront the photosensitive'material. l

The color former of this invention for use in the diazo-type multicolor reproduetion can be easily prepared by dispersing a thermovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promotor in a liquid. semi-solid or solid dispersion medium.

Such color former composition will now be described by referring to some embodiments.

l. Ink-like color former composition:

'Coupler (a) 5.0 40.0 "/1 Thermosublimativc transfer promotor 5.0 30.0 "/1 Coloring material 3.0 "/1 Binder 0 5.0 "/1 Dispersion assistant 0 "/1 Dispersion medium balance As the dispersion medium aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, isobutyl alcohol and dimethyl formamide; aromatic solvents such as benzene, toluene, xylene; esters; and neutral liquids having OH groups and boiling points of 100 250C. such as water, high boiling point alcohols, e.g., n-hexyl alcohol, n-heptyl alcohol, 3-heptanol, 4-heptanol, and octanol, and glycols, e.g., glycerine, ethylene glycol, propylene glycol. polyethylene glycol, 1,3-butanediol, l,4-butancdiol and 2,3-butanediol may be used. These liquid substances may be used singly or in combination.

It is possible to incorporate a coloring material so as to confirm the formation of a film of the color former composition, or to use a binder for the purpose of obtaining a good fixation of the coupler (a).

The composition of the above recipe is applied to the back surface of an original in a portion predetermined to have a different hue by means ofa brush, an installed felt pen, a ball pen, a coating roller, a sprayer or a printing machine.

2. Waxy color former composition:

Coupler (a) 0.5 40.0 "/1 Thcrmosuhlimative transfer promotor 0.5 Z Wax 80 5 '7( Oil 10 "/1 Coloring material 0 10 '71 The composition of the above recipe is shaped to have a crayon stick-like form or a chalk-like form, and

the back surface of a portion of an original predetermined to have a different hue is painted therewith. It is also possible to form a pressure-sensitive transfer sheet by melting the above composition or dissolving it in a suitable solvent and coating the melt or solution on a substrate such as paper and plastic film. The so formed pressure-sensitive transfer sheet is overlapped on the back surface of an original sheet. and then pressing is effected thereon by means of a typewriter or other writing means to form a heat-transferable layer comprising the coupler (a) and transfer promotor on the back surface of an image predetermined to have a different hue.

3. Coupler-transferring sheet for treating the back surface of an original:

The ink-like color former composition for treating the back surface of an original, which was described in l or a composition obtained by incorporating a binder or an extender into such ink-like composition is coated on a transparent or semi-transparent sheet such as paper. plastic film or non-woven fabric. The so formed sheet for heat-transferring the coupler is cut into a desired size, if necessary, and then applied to the back surface of a portion of an original predetermined to have a different hue. It is possible to form a pressuresensitive adhesive layer on the back surface of the coupler-transferring layer for preventing it from exfoliating from the original.

The so prepared original for multicolor development may be generally used 5 to times repeatedly for the multicolor development. though the applicable frequency of the repeated use varies depending on the amount of coupler (a) coated. the coating method, the heating method and the developing method. Of course. when the heat-transferability of coupler (a) in the layer for heat-transferring the coupler is lowered, it is sufficient to newly supply an additional layer for heattransferring the coupler.

The above-mentioned color former composition in use for the multicolor reproduction is applied to the back surface of a predetermined portion of an original to be copied, and is overlapped on a photosensitive material in a manner such that the heat transfer layer containing the coupler (a) and thermosublimative transfer promotor will be in facc-to-face contact with the photosensitive surface of the photosensitive material. Then, the assembly is exposed to light and heated.

The photosensitive material containing a diazonium compound (c) may be prepared by coating a sensitizing composition comprising the diazonium compound (c) and optionally the coupler (12) according to need depending on the developing method, on a substrate such as paper. plastic film. non-woven fabric and metal foil. The preparation of such photosensitive material will now be described by referring to same examples.

A. Sensitizing composition for dry development:

Azo coupling component (b) 0.2 5.0 "/1 Diazonium compound (c) 0.2 5.0 "/1 Organic acid 0.] 5.0 "/1 Coloring matter 0.00] 0.025 Development promotor l.0 l0.() "/1 Extender 0- 2.5 "/1 Solvent balance The sensitizing composition of the above recipe is coated on a substrate such as paper and plastic film and dried to form a photosensitive sheet.

I B. Two-component-type sensitizing composition for wet development:

Azo coupling component (b) 0.2 5. Diazonium compound (c) 0.2 5. Organic acid 0.] 5. Extender 0- 2 Stabilizer 0- 5. Coloring matter Solvent balance The sensitizing composition of the above recipe is coated on a substrate such as paper and plastic film to form a photosensitive sheet.

C. One-component-type sensitizing composition for wet development:

Diazonium compound (c) 0.2 5.0 /1 Organic acid 0.] 5.0 "/1 Extender 9 2.5 "/1 Coloring matter 0,00l 0.025 Solvent balance The sensitizing composition of the above recipe is coated on a substrate such as paper, and dried to form a photosensitive sheet.

As the diazonium compound any diazonium com pound that can couple withthe above-mentioned couplers (u) and (1;) under ordinary developing conditions.

CO in- OOX wherein X stands for an anion. R and R each are aliphatic groups. and Z and Y denote groups which can be introduced into the benzene nucleus. Specific examples of the compounds of this type are as follows:

4-Diazo-N.N-dimethyl aniline (referred to simply as MA salt) 4-Diazo-N,N-diethyl aniline (referred to simply as EA salt") 1 4-Diazo-N-ethyl-N-B-hydroxyethyl aniline (referred to simply as EH salt") 4-Diazo-N,N-bis,8-hydroxyethyl aniline 4-Diazo-N-methyl-N-Bhydroxyethyl aniline 4-Diazo'N-ethyl-N-Bhydroxypropyl aniline Other diazonium salts of p-phenylene diamines N.N- substituted with alkyl or hydroxy-alkyl groups:

4-Diazo-N-ethyl-N-(B-diethylamino)-ethyl aniline 4-Diazo-2-chloro-N,N-diethyl aniline 4-Diazo-2'methylN.N-diethyl aniline 4*Diazo-2-iodo-N,N-diethyl aniline 4'Diazo-2-trifluoromethyl-N.N-diethyl aniline 4-Diazo-N-ethyl-N-benzyl aniline 4-Diazo-N-methyl-N-benzyl aniline (referred to simply as methyl benzyl) Aminohydroquinone ether-type compounds of the following general formula:

xoeN.

wherein R. R and R" are alkyl or aryl groups and X stands for an anion. Specific examples of the compounds of the above type are as follows:

4-Diazo-2,5-dibutoxy-N.N-diethyl aniline 4-Diazo-2.S-diethoxy-N-benzoyl aniline (referred to simply as BB salt") 4-Diazo-2.5-diethoxy-N-ethyl-N-benzoyl aniline 4-DiaZo-2.5-dibenzyloxy-N-benzoyl aniline 4-Diazo-2-chloro-5-methoxy-N-benzoyl aniline 4-Diazo-2,5-diethoxy-N-benzoyl-methyl aniline 4-Diazo-Z.S-diethoxy-N benzoyloxy-methyl aniline Other 4-diazo-2.5-dioxyalkyl (or dioxyaryl)-N-alkyl (or aryl) compounds and derivatives thereof Aminodiphenyl compounds. aminodiphenyl amine compounds and their analogues of the following general formulas:

LII

wherein A is an anion. R is a divalent aryl group. R is a monovalent or divalent aryl or alkyl group. A is a divalent group or a direct bond and examples of the RA-R' are diarylamine (A; NH di phenyl A; direct bond). diphenyl oxide (A: O-

diaryl methane (A; -CH stilbene (A; -CH=CH-) and diaryl or dialkyl sulfide (A; S).

Specific examples of the compounds of the above type are as follows:

Para-diazophenyl amine 4-diazo-2.5.4'-triethoxydiphenyl amine 4Diazo-2.5.4-triethoxydiphenyl 4.4'-Bis-diazo2.2',5.5-tetrahydroxydiphen yl methane Bis-diazo-8.8'-dichloro-5.5'-dimethoxy benzidine 4-Diazo-2.S-dimethoxyphenylethyl sulfide 4-Diazo2.5-diethoxy-4'-methyl-diphenyl sulfide Heterocyclic amine derivatives of the following general formula:

wherein X stands for an anion. Y and Z are groups which can be introduced into the benzene nucleus. and A is a direct bond (phenyl pyrrolidine) or a divalent group such as -O (morpholine). S (thiomorpholine) and methylene (phenylpiperidine).

Specific examples of the compounds of this type are as follows:

4-Diazo-2.5-dibutoxy;N-phenyl morpholine 4-Diazo-2.S-diethoxy-N-phenyl morpholine 4-Diazo-2-methoxy-N-thio morpholine 4-Diazo-N-phenyl piperidine 4-Diazo-N-phenyl pyfrrolidine 4-Diazo-2,5-di-n-butoxy-N-phenyl piperidine Other derivatives-of 4-Diazo-N-phenyl heterocyclic amines.

N,N-Substituted ortho-phenylene diamine derivatives and orthoamino-phenol derivatives.

Specific examples of the compounds of this type are as follows:

2-Diazo-4-methylmercapto-N,N-dimethyl aniline 2Diazo5-benzoylaniino-N.N-dimethyl aniline 2Diazo-l-naphthol-5-sulfonic acid The above-mentioned diazonium compounds may be used in the form of a relatively stable salt with sulfuric acid or hydrochloric acid. They may be also used in the form of a double salt with zinc chloride. tin chloride. aluminum sulfate or the like. Further, they may be used in a state stabilized by an aryl sulfonate (in the form of a diazonium salt of an aromatic sulfonic acid). a diazosulfonate or the like.

The light exposure ofthe photosensitive material and the transfer of the color former of this invention to the photosensitive surface of the photosensitive material may be effected coincidentally. For instance, when a mercury lamp is used as the light source for exposure, the heat transfer of the coupler (a) may be effected coincidentally with the exposure by the heat conveyed through a cylinder glass of the light sourcemaintained at a relatively high temperature. Of course. the heat transfer of the coupler (a) may be also effected by'the radiation heating of an image of the original. The heat transfer of the coupler (a) may be effectively performed at a temperature above 50C.. preferably 60 1009C. though a preferable heating temperature varies to some extent depending on the type of the coupler (a) and heating time. 7 i

It is also possible to adopt a method comprising piling the above-mentioned-original for multicolor development and the photosensitive material, passing, the assembly through a heated roller or an infrared radiation zone to heat the coupler layer of the originalat the above-mentioned temperature and to effect the heat transfer of the coupler (a). and then passing. the same through an exposure zone to effect the exposure of the photosensitive material. 3

It is also possible to adopt a methodin which the exposure and heat transfer are conducted in an order reverse to that of the above method, namely a method comprising forming an assembly of the original formul: ticolor development and the photosensitive material. passing the assembly through an exposure zone to effect the exposure of the photosensitive material and then passing the same through a heating zone to effect the heat transfer of the coupler (a).

Since the color former of this invention contains a thermosublimative, organic. solid transfer promoter as well as the coupler (a). in the heat transfer of the coupler (a) the heat transfer temperature can be considerably lowered by the interaction of the coupler (a) and the transfer promoter, as compared with the case where thecoupler (a) is used singly. Further, when a plurality of couplers (a), (a'). (a) forming colors differing in hues are coated on predetermined portions of an original to be copied and the heat transfer is conducted, the heat transfer temperatures of couplers (a). (a'). (a") can be approximated because of the presence of the thermosublimative, organic. solid transfer promotor.

The photosensitive material which has been thus exposed to light and on a predetermined portion of which the coupler (u) has been heat-transferred, is developed by customary known developing methods. The coupler (b) may be either contained in the photosensitive material in advance or made present in the developer. The development may be conducted by either a dry method or a wet method. When a photosensitive material containing coupler (h) as well as diazonium salt is used. it is preferred that prior to the development the photosensitive material on which the coupler (a) has been heat-transferred is subjected to an affinity-increasing pre-trcatment with a treating liquor comprising. singly or in combination. an aliphatic alcohol. an aromatic solvent. an ester. a glycol or a liquid having OH groups and boiling at 100 200C. such as water or high boiling point alcohols, to thereby attain a uniform contact between the heat-transferred coupler (a) and the diazonium salt remaining unexposed. In conducting the above pre-treatment it is desired to allow the above treating liquor to contact the photosensitive material while keeping the liquor in the liquid or vapor state. In the case of the dry development. the development may be accomplished sufficiently only by exposing the lightexposed photosensitive material to a mixture of'ammonia and steam. Whena one-component-type photosen- .12 sitive sheet for wet development is used. the development can be accomplished by dipping. roller coating or spraying methods with useofa liquid developer having. for instance. the following recipe:

Coupler (h) 0.2 5' Alkali 0.5 10C: Reducing agent 0 20 2 Surfactant 0 0.5 '2 Water balance When a two-component-type photosensitive sheet for wet development is used. the development may be accomplished by contacting the light-exposed photosensitive sheet with a liquid developer containing an alkali.

Thus multi-colored reproductive copies in which the portion corresponding to the predetermined portion of the original is colored with a dyestuff (a )(c) and other portions are colored with a dyestuff (b)(() can be obtained.

The diazo-type multicolor reproduction process with use of the color former of this invention will now be explained by referring to the accompanying drawings.

FIGS. ,1 and 2 are diagrams illustrating the process for obtaining multi colored copies with use of the color former of this invention.

In the embodiment of this invention illustrated in FIG. 1, different thermovolatile or thermosublimative couplers 2 and 3 are coated on the back surfaces of images 2 and 3, respectively, of an original having images I, 2 and 3. When the so formed original for multicolor development is overlapped on a photosensitive paper, and exposed to light emitted from a suitable light source. latent images 1, 2" and 3 corresponding to images 1, 2 and 3 are formed on the photosensitive layer and couplers 2 and 3' are transferred on the upper surface of the photosensitive layer by the heat from the light source. When this photosensitive sheet is developed. the diazonium salt in latent images 2" and 3 of the photosensitive layer reacts selectively with transferred couplers 2' and 3. while the diazonium salt in latent image 1" reacts with a coupler contained in the photosensitive layer. As a result a reproductive copy which has images ll, 12 and 13 colored in different hues is obtained.

FIG. 2 is a view illustrating an embodiment similar to the above embodiment shown in FIG. 1, except that a heat-transferable sheet containing coupler 2 and another heat-transferable sheet containing coupler 3 are applied to the back surfaces of images 2 and 3, respectively.

When the color former of this invention is used for the multicolor reproduction, it is possible to heat transfer the coupler (a) from the predetermined portion of the original to be copied in a different hue to the photosensitive material at a relatively low temperature, i.e., a temperature only l0 20C. higher than the temperature adopted in the ordinary diazo-type reproduction process. and therefore. it is possible to obtain a copy in which the portion corresponding to the predetermined portion of the original is colored selectively in a different hue very distinctly without substantial mingling of colors. Further. formation of a plurality of different colors may be accomplished by one development treatment. Once an original is treated with the color former of this invention. at leastSimulti-colored copies, usually 20 I00 multi-col'ored copies. can be obtained from the original. and it is unnecessary to treat the original repeatedly every time one copy is formed. Further. the treated original used for the multicolor reproduction can be returned to the original state only by peeling off the layer or sheet of the color former applied thereto or by heating the color former-colored original at about 100C.

The multicolor reproduction process with use of the color former of this invention is effectively and conveniently applied when copies in which special portions are colored in different hues are desired, and further. ordinary multi-colored copies can be obtained with ease in accordance with this invention.

This invention will now be explained by referring to examples.

Examples of Preparation of lnklike Color Former Composition for Use in Multicolor Reproduction:

EXAMPLE 1 An ink-like composition of the following recipe is prepared as a yellow color-forming agent for treating the back surface of an original:

Acetoacetic anilide 20 i Alkyd resin 3 g Camphor l5 g Diethylcne glycol 5 g Tolyol balance Total 100 ml The above composition is directly used as a material to be coated on the back surface of a portion of the original desired to be reproduced in yellow by means of a brush. a coating roller or a sprayer. or after it has been charged in a felt pen or a ball pen. it is used as a material for treating the back surface of a portion of the original desired to be reproduced in yellow.

EXAMPLE 2 An ink-like composition for forming a yellowish orange color is prepared by using acetoacetic-ochloroanilide instead of the acetoacetic anilide of Example 1.

EXAMPLE 3 An ink-like composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:

l-Phenyl-3-mcthylpyrazolone (5) 25 i g l-lydrochloric acid (36 a l 5 ml Naphthalene l5 g (ilyeerinc g Ethanol balance Total 100 ml The above composition is directly used as a material to be coated on the back surface of a portion of the original to be reproduced in red by means of a brush, a coating roller or a sprayer. or after it has been charged in a felt pen or a ball pen. it is used as a material for treating the back surface of a portion of the original to be reproduced in red.

EXAMPLE 4 An ink-like composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:

Resorcin 20 g \inyl acetate resin 3 g ()xalic acid' l5 g Methanol 0 ml Water balance Total ltltl ml The above composition is directly used as a material to be coated on the back surface of a portion of the original desired to be reproduced in brown by means of a brush. a coating roller or a sprayer. or after it has been charged in a felt pen or a ball pen. it is used as a material for treating the back surface of a portion of the original desired to be reproduced in brown.

EXAMPLE 5 An ink-like composition of the following recipe is prepared as a blue color forming agent for treating the back surface of an original:

2.3-Dihydroxynaphthalenc g Alkyd resin 3 g Bornane l5 g Ethylene glycol l() g l-Ithanol balance Total ltltl ml The above composition is directly used as a material to be coated on the back surface of a portion of the original desired to be reproduced in blue by means of a brush. a coating roller or a sprayer. or after it has been charged in a felt pen or a ball pen. it is used as a color former for treating the back surface of a portion of the original to be reproduced in blue.

EXAMPLE 6 An ink-like composition of the following recipe is prepared a reddish brown color-forming agent for treating the back surface of the original:

Dimcthyl-m-aminophcnol 20 g Naphthalene l5 g Glycerine It) g Ethanol balance Total I00 ml EXAMPLE 7 A waxy composition to be used as a yellow colorforming agent for treating the back surface of an original .is prepared by heat melting Acetoacetic acid anilide g Camphor 15 g Stearic acid l()() g Paraffin g Terraabla and solidifying the melt.

The above composition is molded into a crayon sticklike or chalk-like form and is used as a color former to be coated on the back surface of a portion of the original desired to be reproduced in yellow.

EXAMPLE 8 A waxy composition to be used as a yellowish brown color-forming agent is prepared by heat melting Pyrogallol 20 g Menthol 15 g Paraffin 50 g Terra abla 70 g HLIZC was 20 g Stearic acid 100 g Magnesium carbonate 20 g and solidifying the melt.

The so formed composition is molded into a crayon stick-like or chalk-like form and is used as a material for coating the back surface of a portion of an original desired to be reproduced in a different hue.

EXAMPLE 9 To the composition of Example 8 100 g of mineral oil and 30 g of oleic acid are added, and the mixture is kneaded in a ball mill. Then, the kneaded mixture is coated on a substrate such as paper to obtain a pressure-sensitive copy sheet. The so formed copy sheet is overlapped on the back surface of an original and the pressing is effected thereon by means ofa typewriter or other writing tool. Thus. the sheet is used as a material for forming a layer of the waxy color former agent on the back surface of a portion of the original desired to be reproduced in a different hue.

EXAMPLE 10 A waxy composition for forming a red color is prepared by heat melting l-Phenyl-3-methylpyrazolonc 25 g p-Diehlorohcnzenc l5 g Paraffin 50 g Stearic acid 100 g Diatomeceous earth 3() g Haze wax 20 g and solidifying the melt.

The above composition is molded into a crayon sticklike or chalk-like form and is used as a material for coating the back surface of a portion of the original desired to be reproduced in a different hue.

EXAMPLE ll To the composition of Example 100 g of mineral oil. 50 g oleic acid and g of Permanent Red are added. and the mixture is kneaded in a ball mill to dispcrse additional components uniformly. Then. the kneaded mixture is coated on a substrate as paper to obtain a pressure-sensitive copy sheet. The so formed pressure-sensitive copy sheet is used as a material for forming a layer of the waxy color former composition 6 on the back surface of a portion of the original to be copied in a different hue. in the same manner as described in Example 9.

EXAMPLE l2 7 A waxy color former composition for forming a blue color is prepared by heat melting 2.3-Dihydroxynaphthalenc 30 g Naphthalene 15 g Stearic acid g Paraffin 50 g Diatomaeeous earth 30 g Haze wax 20 g and solidifying the melt.

The above composition is molded into a crayon sticklike form and is used as a material to be coated on the back surface of a portion of the original desired to be reproduced into a different hue.

EXAMPLE 13 To the composition of Example 12 lOO g of mineral oil, 30 g of oleic acid, 20 g ofOil Blue and 50 ml of ethanol are added. The mixture is well kneaded in a ball mill and coated on a substrate such as paper to form a pressure-sensitive copy sheet. The sheet is used as a material for forming a layer of the waxy color former composition on the back surface of the original to be reproduced in a different hue. in the same manner as described in Example 9.

Examples of Preparation of Coupler-Transferring Sheets Comprising Color Former:

EXAMPLE 14 A composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:

l-Phenyl-3-methylpyrazolone (5) 25 g Camphor l5 g Triacetatc resin l0 g Methanol 50 ml Acetone 50 ml .The above composition is coated on a transparent or semi-transparent sheet such as polyester film by means 'of a rod coater and dried at a relatively low temperature (40 50C.) to form a sheet for heat-transferring the coupler. After being cut into a desired size according to need. the sheet is used as a material to be applied to the back surface ofa portion of an original desired to be reproduced in a different hue.

EXAMPLE 15 A composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:

m-Aminophenol 25 g Anthranic acid l5 g Triaeetate resin 10 g Methanol 50 ml Acetone 50 ml The above composition is coated on a transparent or semi-transparent sheet such as polyester film by means of a rod coater and dried at a relatively low temperature (40 50C.) to form a sheet for heat-transferring the coupler. After being cut into a desired size according to need, the sheet is used as a material to be applied to the back surface of a portion of the original desired to be reproduced in a different hue.

EXAMPLE 16 A composition to be used as a brown color-forming agent for treating the back surface of an original is prepared by using pyrogallol instead of l-phenyl-3- methylpyrazolone (5) in Example l4. From this composition a sheet is formed for heat-transferring the coupler capable of forming a brown color.

EXAMPLE 17 A composition to be used as a blue color-forming agent for treating the back surface of an original is prepared by using 1,6-dihydroxynaphthalene instead of l-phenyl-3-methylpyrazolone in Example 14. From this composition a sheet is prepared for heat transferring the coupler capable of forming a blue color.

Application of Color-Forming Agents to Diazo-type Multicolor Reproduction:

EXAMPLE 18 Multicolor-forming diazo-type photosensitive paper in use for wet development First, l g of 4-diazo-2,5-diethoxy-benzoylaniline chloride l/2ZnCl 8 g of citric acid, 0.1 g of Patent Blue and 10 g of dextrin are dissolved successively in water, and the amount of the solution is adjusted to 1 liter by controlling the amount of water added. The so formed solution is coated on a base paper of a photosensitive sheet by a customary coating method employing an air knife coater, and dried to form a photosensitive sheet.

The sheet is overlapped on an original in which the back surface of a portion is treated with the ink-like color former composition prepared in Example 1 and the back surface of another portion is treated with the color former composition prepared in Example 3. Then the assembly is heated and light exposed by means of a mercury lamp and developed with a liquid developer of the following recipe:

NW acid Potassium carbonate Sodium bicarbonate Sodium thiosull'ate Activator Water b Aurora Total 1 EXAMPLE l9 Multicolor-Forming Diazotype Photosensitive Sheet for Dry Development A solution of the following recipe is prepared:

4-DiazoN-ethyl-N-/3-hydroxycth)laniline -Continued chloride l/ZZnCl g Diethylene glycol 50 g Citric acid 20 g Bisl 5-hydrosy-7-sull'onaphthyll 2 llaminc 15 g Zinc chloride 40 g Thiourea g Patent Blue (Ll g Water balance 'lotal l liter The solution is coated on a base paper by a customary coating procedure such as using an air knife coater and dried to form a photosensitive sheet.

The sheet is piled on an original in which one portion of the back surface is treated with the color former composition prepared in Example 2, another portion of the back surface is treated with the color former composition prepared in Example 3 and still another portion of the back surface is treated with the color former composition of Example 5. Then, the assembly is heated and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt.

Next, the so treated sheet is subjected to development with gasified ammonia and steam. Thus. there is obtained as a result a clear multicolor copy in which a portion corresponding to the portion treated with the material of Example 2 is colored in yellowish orange, a portion corresponding to the portion treated with the material of Example 3 is colored in reddish brown, a portion corresponding to the material of Example 5 is colored in bluish violet, and a portion corresponding to the untreated portion of the original is colored in dark blue is obtained.

EXAMPLE 20 Multicolor-forming diazo'type photosensitive paper in use for dry development A solution of the following recipe is prepared:

4-Diazo-N.N-dimethyl-aniline chloride.l/2Zn(.l 10 g Diethylene glycol 40 g Citric acid g 2.3-Dihydroxynaphthalene-f sull'onie acid 20 g Zinc chloride 50 g Thiourea 50 g Patent Blue 0.1 g Water balance Total 1 liter In the same manner as in Example, 18, a photosensitive paper is prepared from the above solution by coating and drying. The photosensitive paper is piled on an original, a portion of the back surface of which is treated with the coupler-heat-transferring sheet prepared in Example-l4. Then the assembly is heated and printed by means ofa mercury lamp, followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy in which a portion corresponding to the portion treated with the treating agent of Example l4 is colored in red and another portion corresponding to the untreated portion is colored in dark blue is obtained.

EXAMPLE 21 Multicolor-forming photosensitive paper in use for dry development A solution of the following recipe is prepared:

4-l)ialo-N.N-dimethylaniline chloride.l/27.nCl g Ethylene glycol 50 g Citric acid 'g 2.7-Dihydroxynaphthalene 3.(i-tlisulfonic acid sodium salt I 8 g Zinc chloride 20 g Thiourea H10 g l.3.o-Naphthalene-trisulfonic acid sodium salt 20 g Patent Blue 0.1 g Water balance Total 1 liter By a customary coating method such as using an air knife coater, a photosensitive paper is prepared from the above solution. The photosensitive paper is overlapped on an original in which a portion of the back surface is treated with the waxy composition prepared in Example 8 and another portion of the back surface is treated with the composition prepared in Example 10. The assembly is exposed to light and heated by means of a mercury lamp. Then, the so treated sheet is subjected to development with gasified ammonia and steam. As a result a clear three-color reproductive copy in which a portion corresponding to the portion of the original treated with the composition of Example 8 is colored in brown, a portion corresponding to the portiontreated with the composition of Example 10 is colored in red, and other portion corresponding to the untreated portion of the original is colored in bluish violet is obtained.

EXAMPLE 22 Multicolor-forming photosensitive paper for dry development A solution of the following recipe is prepared:

4-DiaxoN.N-dicthylaniline The above solution is applied to a photosensitive paper substrate by a customary coating method such as using an air knife coater, and the resulting photosensitive sheet is piled on an original in which the back surface of a part of an image is treated with the ink-like composition obtained 'in-Example 3. the back surface of another part of the image is treated with the composition of Example 4 and the back surface of still another part is treated with the composition of Example 5. Then, the assembly is heated and printed at 70 80C. by means ofa mercury lamp, and the so treated photosensitive sheet is developed with gaseous ammonia and steam. As a result a four-colored copy of a clear color contrast is obtained in which a portion corresponding to the portion treated with the composition of Example 3 is colored in red, a portion'corresponding to the portion treated with the composition of Example 4 is colored in yellowish brown, a portion corresponding to the Patent Blue portion treated with ithefeoinposition of Example 5 is colored in blue. and a portion corresponding to the untreated portion of the original is colored in black.

EXAMPLE 23 Multicolor-forming diazo-type photosensitive paper for dry development for forming second original A solution of the following recipe is prepared:

The above solution is coated on a semi-transparent paper for second original such as tracing paper and dried to form a photosensitive paper. The photosensitive paper is piled on an original, a portion of the back surface of which is treated with the waxy color former composition prepared in Example 12. Then the assembly is'heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy usable as the intermediate second original is obtained in which a portion corresponding to the portion of the original treated with the composition of Example 12 is colored in red and another portion corresponding to the untreated portion of the original is colored in yellowish brown.

EXAMPLE 24 MuIti-color-forming photosensitive paper for dry development A solution of the following recipe is prepared:

4-DizmrN-ethyl-N-hydroxyethylaniline ehloride.l/2ZnCl 15 g Diethylene glycol St) g Citric acid 30 g a-resorcylic acid ethanol amine 8 g Zinc chloride 50 g Thiourea 25 g Patent Blue 0.] g Water balance Total 1 liter By a customary coatingmethod such as using an air knife eoater, the above solution is applied to a substrate of a photosensitivepaper and dried. The so formed photosensitive paper is piled on an original, a portion of the back surface of which is treated with a couplerheat-transferring sheet prepared in Example 17. and the assembly is heated at 60 C. and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy without any substantial mingling of colors is obtained, in which a portion corresponding to the portion ofthe original treated with the sheet obtaine d in Example 17 is colored in blue and the remaining portion corresponding to the untreated portion of the original is colored inred.

EXAMPLE 2'5 Multicolor-forming sensitive paper in use for either dry or wet development A solution of the following recipe is prepared:

-lDiane-2.5-dibutoxy-N-phenylmorpholinellIZnCl l5 g Citric acid 30 g Diethtlene glycol 40 g [3 Hydroxynaphthonic acid aminoethyl amine lhydroehloridel 7 g 'l'hiourea 40 g Zinc chloride 30 g Patent Blue (Ll g Water balance Total 1 liter From the above solution. a photosensitive paper is prepared by conducting the coating and drying in the same manner as in Example 18. The so formed photo sensitive paper is piled on an original. a portion of the back surface of which is treated with the pressuresensitive sheet prepared in Example 9 and another portion of the back surface of which is treated with the pressure-sensitive sheet prepared in Example l 1. Then the assembly is heated and printed by means of a mercury lamp. followed by development with gaseous ammonia and steam or with an alkaline liquid developer of the following recipe:

Potassium carbonate 20 g Sodium thiosullate 40 g Sodium bicarbonate 30 g Potassium tctraborate 5 g Water balance Total 1 liter As a result a clear three-color reproductive copy without any substantial mingling of colors is obtained, in which a portion corresponding to the portion of the original treated with the pressure-sensitive sheet of Example is colored in brown, a portion corresponding to the portion of the original treated with the pressuresensitive sheet of Example 1 l is colored in'red and the remaining portion corresponding to the untreated portion of the original is colored in blue.

EXAMPLE 26 Multicolor-forming film A solution of the following recipe is prepared:

4-Diazo-2.5 dibutoxy-N-phenyl morpholinel/ZZnCh [5 g Citric acid g B'Hydroxynaphthoie acid ethanol amine 7 g Triaeetate resin g Oil Blue 02 g Acetone 400 ml Methanol 700 ml The solution is coated on a polyester film by a rod coater and dried at a relatively low temperature (40 50C.) by warm air to form a photosensitive film. The film is piled on an original in which a part of the back surface of an original imagcis treated with the colorforming agent prepared in Example 3 and another part ofthe back surface ofthe original image is treated with the color-forming agent prepared in Example 4. The

assembly is exposed to light by a mercury lamp and heated and printed. The photosensitive film containing a latent image of the diazonium salt is developed with gasified ammonium and steam. As a result a clear three-color reproductive copy without any substantial mingling of colors'is obtained. in which a portion corresponding to the part treated with the treating material of Example 3 is colored in red. a portion corresponding to the part treated with the treating material of Example 4 is colored in brown. and another portion corresponding to the untreated part ofthe original is colored in blue.

COMPARATIVE EXAMPLE 1 This example illustrates results of comparative experiments conducted to confirm effects attained by the in corporation of the thermosublimative. organic, solid transfer promotor in the color former of this invention.

EXPERIMENTAL PROCEDURES Four ink-like color-forming compositions of the following recipes are prepared.

Each of the above solutions is coated on the back surface of a semi-transparent original (tracing paper; Chemical No. 60) in an amount of about 0.2 g/m". The so coated original is dried to form a sample sheet original. Then, the sample sheet is piled on the photosensitive sheet prepared in Example 21 in a manner such that the treated surface of the sample is in face-toface contact with the photosensitive layer of the photosensitive sheet. Then, the assembly is allowed to pass through hot rolls maintained at 50C.. 60C.. C.. C. and C., respectively, to effect the heat transfer of the thermovolatile or thermosublimative coupler. Then, the so treated photosensitive sheet is subjected to the development with gaseous ammonia and steam. With respect to each sample original, the number of copies ofa distinct color contrast obtained at each heat transfer temperature is counted. Results are shown in Table 1 below.

Table 1 Recipe No. 50 60 70 80 90 Table l-Continued Number of Copies of Distinct Color Contrast Heat Transfer Temperature (C.) 1

Recipe No. 50 60 80 90 COMPARATIVE EXAMPLE 2 EXPERIMENT PROCEDURES As the thermovolatile or thermosublimative coupler sample 1-phenyl-3-methylpyrazolone (5) and resorcin are selectedEach of the sample chemicals is sufficiently ground in a mortar and is sufficiently dried in a silica gel desiccator. A precisely weighed amount (0.3 g) of each sample is charged in a vessel having a certain inner surface area and subjected to a heat treatment at 100C., 1 C. and 120C. The weight of the sample is determined at certain time intervals and the weight loss is calculated each time.

Then, each sample is blended with 1.5 g of camphor (special grade) and the blend is sufficiently mixed and ground in a mortar. Then, the blend is subjected to the same heat treatment as above to determine the weight loss of the blend. Then, the weight loss of the coupler alone is calculated by reducing the weight loss of camphor alone determined separately, from the above determined weight loss of the blend. Thus, the effect of camphor for promoting the volatilization or sublimation of the sample coupler is examined. Results are shown in Tables 2 and 3 below.

Table 2 Weight Loss (mg) of l-Phenyl-3-Methylpyraznlone (5) Treatment Time Treatment Temperature In Tables 2 and 3. the values are values 1n parenthesis obtained when d-camphor is incorporated in the sample coupler.

From the results of Comparative Examples 1 and 2. the following can be concluded.

As is seen from the results shown in Table l, the use of the color former of this invention increases the number of copies by 7 sheets at C.. by 12 sheets at C. and by 18 sheets at C. in the case of l-phenyl-3- methylpyrazolone (5). as compared with the use of the coupler alone. Accordingly. it is construed that the heat transfer temperature may be lowered by about 10 15C. with the use of the color former of this invention comprising the thermovolatile or thermosublimative coupler and the thermosublimative. organic. solid transfer promotor. 1n the case of resorcin. the use of the color former of this invention increases the number of copies by 7 sheets at 60C. and by 22 sheets at 70C. Accordingly. it is construed that also in this case the heat transfer temperature may be lowered by about 10 15C. with the use of the color former of this invention.

As is seen from the results of Comparative Example 2 shown in Tables 2 and 3, when comparison is made at the same treatment temperature. in the case of the color former of this invention the weight loss of l-phenyl-3-methylpyrazolone (5) is about 2.5 times as large as in the case of the color former free of camphor, and the weight loss of resorcin in the case of the color former of this invention is about 2 times as large as in the case of the color former comprising resorcin alone. Accordingly, it is construed that the heat transfer temperature may be lowered by about 10 15C. with the use of the color former of this invention.

In view of the foregoing, it can be readily understood that when the thermosublimative. organic, solid transfer promotor is used in combination with a thermovolatile or thermosublimative coupler. the efficiency of transfer of the coupler can be greatly improved.

What we claim is:

l. A waxy color former composition of crayon sticklike form or a chalk-like form for treating the back surface of an original in diazo-type multicolor reproduction, which consists essentially of a. a thermovolatile or thermosublimable azo coupler;

and

b. a solid organic thermosublimable compound selected from the group consisting of camphor. naphthalene. bornane. menthol. and p-dichlorobenzene.

said components (a) and (b) dispersed in a wax.

2. The waxy color former composition of claim 1, in which said composition consists essentially of a. 0.540.0% by weight of a thermovolatile or thermosublimable azo coupler;

1). 05-25% by weight of a solid organic thermosublimable compound selected from the group consisting of camphor. naphthalene. bornane. menthol. and p-dichlorobenzene c. 80-571 by weight of a wax; and

d. ()10% by weight of color material.

3. The waxy color former composition of claim 1 in which said thermovolatile or thermosublimable azo coupler is at least one member selected from the group consisting of phenol compounds. hydroxynaphthalene compounds. aniline compounds and active methylene group-containing compoundsv 4. The waxy color former composition of claim 1 in which said composition consists essentially of;

Acetoacetic acid aniline 15 parts by weight. ('amphor l parts by weight. Slearie acid H parts by weight. Paral'l'in 50 parts by weight.

and Terra abla 50 parts by weight.

5. The waxy color former composition of claim 1 in which said composition consists essentially of:

Pyrogallol 21) parts by weight. Menthol parts by weight. Paraffin 50 parts by weight. Terra abla 7!) parts by weight. Haze wax parts by weight. Stearic acid [00 parts by weight.

and Magnesium carbonate 20 parts by weight.

6. The waxy color former composition of claim 1 in which said composition consists essentially of:

l-Phenyl-B-methyl pyrazolone parts by weight.

p-Dichlorobenzene 12 parts by weight.

Paraffin 50 parts by weight.

Stearic acid 100 parts by weight.

Diatomaceous earth parts by weight.

and

Have wax 20 parts by weight.

7. The waxy color former composition of'claim l in which said composition consists essentially of:

2.3-dihydroxynaphthalene 30 parts by weight.

Naphthalene 15 parts hyweight.

Stearic acid IOU parts by weight.

Paraffin parts by weight.

Diatomaccous earth 3() parts by weight.

and

Have wax 20 parts by weight.

pound (h) is bornane.

11. The waxy color former composition of claim 1 wherein said solid organic thermosublimable compound (b) is menthol.

12. The waxy color former composition of claim 1 wherein said solid organic thermosublimable compound (h) is p-dichlorobenzene.

13. An ink-like color former composition for treating the back surface of an original in the diazo-type multicolor reproduction. which consists essentially of a. 5.040.()'/( by weight of a thermovolatile or thermosublimable azo coupler;

b. 5.040.071 by weight ofa solid organic thermosublimable compound selected from the group consisting of camphor. naphthalene. bornane. menthol. and p-dichlorobenzene;

c. ()-().3'/( by weight of a color material: and

d. 0-5.07: by weight of a resinous binder. said components (a). (b). (c) and (d) dispersed in a dispersion medium selected from aliphatic alcohols. aromatic solvents and neutral liquids containing OH groups. said dispersion medium boiling at l ()()-250C 14. The ink-like color former composition of claim 13 wherein said solid organic thermosublimable compound (b) is camphor.

15. The ink-like color former composition of claim 13 wherein said solid organic thermosublimable compound (b) is naphthalene.

16. The ink-like color former composition of claim 13 wherein said solid organic thermosublimable compound (b) is bornane.

17. The ink-like color former composition of claim 13 wherein said solid organic thermosublimable compound (h) is menthol.

18. The ink-like color former composition of claim 13 wherein said solid organic thermosublimahle compound (b) is p-dichlorobenzene.

19. The ink-like color former composition of claim 13 in which said thermovolatile or thermosublimable azo coupler is at least one member selected from the group consisting ofphcnol compounds. hydroxynaphthalene compounds. aniline compounds. and active methylene group-containing compounds.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3981730 *Apr 16, 1974Sep 21, 1976Mita Industrial Company, Ltd.Diazo-type multicolor reproduction process
US4042545 *Jun 11, 1975Aug 16, 1977Ciba-Geigy AgNovel printing inks for sublimation transfer printing
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US20130180430 *Sep 13, 2011Jul 18, 2013Yamamoto Chemicals, Inc.Heat-sensitive color-developing composition and heat-sensitive recording material comprising the composition
Classifications
U.S. Classification430/154, 430/142, 430/146, 106/31.18, 106/31.2, 106/31.8, 250/318, 430/151
International ClassificationB41M5/10, G03C1/52, G03C1/60
Cooperative ClassificationB41M5/10, G03C1/60
European ClassificationG03C1/60, B41M5/10