US3695885A

US3695885A - Heat developable diazotype copying material

Info

Publication number: US3695885A
Application number: US43968A
Authority: US
Inventors: Shoji Maryama; Tadashi Saito; Tomiaki Asami
Original assignee: Individual
Current assignee: Individual
Priority date: 1969-06-07
Filing date: 1970-06-05
Publication date: 1972-10-03
Anticipated expiration: 1989-10-03
Also published as: GB1307314A; FR2056231A5; DE2018908B2; NL7006018A; DE2018908A1; DE2018908C3

Abstract

A HEAT DEVELOPABLE DIAZOTYPE COPYING MATERIAL COMPRISING A SUPPORT AND A LIGHT-SENSITIVE LAYER FORMED ONTO ONE SURFACE OF SAID SUPPORT. SAID LAYER CONTAINING A COUPLER WHICH ACTIVATED DURING THE HEAT DEVELOPMENT OF THE COPYING MATERIAL AND AT LEAST TWO KINDS OF DIAZONIUM COMPOUNDS FORMING A BLACK AZO DYE AS A RESSULTOF A REACTION BETWEEN SAID COUPLER AND SAID DIAZONIUM COMPOUNDS.

Description

United States Patent M US. Cl. 96-91 R 27 Claims ABSTRACT OF THE DISCLOSURE A heat developable diazotype copying material comprising a support and a light-sensitive layer formed onto one surface of said support, said layer containing a coupler which activated during the heat development of the copying material and at least two kinds of diazonium compounds forming a black azo dye as a result of a reaction between said coupler and said idazonium compounds.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a diazotype copying material capable of forming a desired black copied-image through heat development.

(2) Description of the prior art The conventional heat developable diazotype copying materials may be divided broadly into three categories as follows by the components of the light-sensitive layer thereof and the pattern of the heat development process applicable thereto.

(a) Copying materials whose light-sensitive layer contains diazonium compounds, a coupler and an alkali-producing agent capable of producing ammonia gas when heated, such as urea, so that the coupling is effected by virtue of alkali produced by heating the copying material at the time of development thereof.

(b) Copying materials whose light-sensitive layer contains an alkali salt of an acid such as trichloroacetic acid which may be decomposed by heating to form an alkali producing agent, so that the coupling is effected by means of alkalizing the light-sensitive layer by heating the copying material at the time of development thereof.

(c) Copying materials whose light-sensitive layer does not contain any alkaline component, but contains a coupler together with diazonium compound, said coupler being activated and combined with said diazonium compounds when heated, so that the coupling is eflected by heating the copying material at the time of development thereof.

SUMMARY OF THE INVENTION The object of the present invention is to provide a heat developable diazotype copying material of the foregoing category (c), and particularly materials which are capable of effecting the coupling of a copied image in black color tone.

The coupler constituting one component of the lightsensitive layer applicable in the present invention, it includes such compounds as expressed by the following general formula:

$OOH

HO OH 3,695,885 Patented Oct. 3, 1972 wherein:

R and R each is a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 6 carbon atoms, benzyl, bromine, chlorine, iodine, acetyl, and w-carboxyalkyl radicals having 1 to 4 carbon atoms; and R is a radical selected from the group consisting of hydrogen, hydroxyl radical alkyl radical having 1 to 2 carbon atoms, alkyl-sulfonyloxy (--0--SO -alkyl) radicals in which the alkyl group has 1 to 4 carbon atoms, carboalkoxyoxy radicals in which the alkyl group has 1 to 4 carbon atoms, acylacyoxy o (-OO-acyl)t radicals having 7 to 9 carbon atoms, alkylacyloxy radicals having 2 to 12 carbon atoms, w-hydroxyalkyl radicals having 1 to 3 carbon atoms, w-hydroxyalkyloxy radicals having 1 to 3 carbon atoms and alkoxy radicals having 1 to 4 carbon atoms; and

R is a radical selected from the group consisting of hydrogen, hydroxyl radical, alkyl radicals having 1 to 2 carbon atoms, alkoxyl radicals having 1 to 4 carbon atoms, sulfonyloxy (-O-SO radical, alky1-sulfonyloxy (OSO -alky1) radical in which the alkyl group has 1 to 4 carbon atoms, carbamoyl radical, carbamoyloxy radical, carboalkoxyloxy radicals in which the alkoxyl group has 1 to 4 carbon atoms, acyloxyl radicals in which the acyl group has 2 to 9 carbon atoms, alkyl-acyloxyl radicals having 2 to 12 carbon atoms, w-hydroxyalkyl radicals having 1 to 3 carbon atoms and w-hydroxyalkyloxy radicals having 1 to 3 carbon atoms.

C O O H Y is a member selected from the group consisting of wherein:

(wherein R represents a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 4 carbon atoms, hydroxyethyl radical, hydroxypropyl radical and acetyl radical); and X is a member selected from the group consisting of Cl-' /2ZnCl wherein:

R" is a radical selected from the group consisting of hydrogen, cyclohexyl radical, alkyl radicals having 1 to 4 carbon atoms, hydroxyalkyl radicals having 2 to 4 carbon atoms, cyano radical and aralkyl radicals hav- 5 ing 7 to 11 carbon atoms, such as R' is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, aralkyl radicals having 7 to 11 carbon atoms, such as cyclohexyl radical, hydroxyalkyl radicals having 2 to 4 carbon atoms and benzoyl radical; and X is the radical identical with that of said X expressed in the general Formula I.

00011 COOH Specific examples of diazonium compounds within the scope of general Formula I, are such compounds:

00 COOH Gen, noonrcni Diazonium compounds of dialkylaniline group expressed by the following general Formula II:

wherein:

R" and R""' each is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, hydroxylalkyl radical having 2 to 3 carbon atoms and benzyl radical; and

X" is the radical identical with that of X expressed in the general Formula I.

Diazonium compounds expressed by the following general Formula III:

l rv wherein:

X" and Y are the radicals identical with that of X and Y, respectively, expressed in the general Formula I; and

R and R each is a radical selected from the group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen.

Diazonium compounds of benzoyl amide group expressed by the following general Formula 1V:

wherein R and R each is a radical selected from the group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen;

R is a radical selected from the group consisting of hydrogen and alkyl radicals having 1 to 3 carbon atoms; and X" is the radical identical with that of X expressed in the general Formula I.

A coupler expressed by the above-mentioned general formula usually forms a purple azo dye or a blue azo dye as a result of a coupling reaction between said coupler and a diazonium compound generally employed for conventional diazotype copying materials, but in case where a coupling reaction is effected between said coupler and a member selected from the group consisting of diazonium compounds expressed by the foregoing general Formulas I and I along with a member selected from the group consisting of diazonium compounds expressed by the foregoing general Formulas II, III or IV, there is formed a black azo dye. And, in case where a coupling reaction is effected between said coupler and a single member selected from the group consisting of diazonium compounds expressed by said general Formula I or general Formula I, there is formed a yellow azo dye.

In other words, the present invention stems from the knowedge obtained through observation and study of the coupling reaction effected by means of varieties of combinations of diazonium compounds and coupler. At least one member as illustrated by Formulas I and I must be contained in the light-sensitive layer of the copying material. Diazonium compounds expressed by the general Formulas II through IV represent the optimum examples,

but any other diazonium compound generally employed in this field of art and capable of forming a blue azo dye or a purple azo dye as a result of coupling reaction between a coupler expressed by the foregoing general formula and said diazonium compound is also applicable in the present invention.

In addition to the diazonium compounds and the coupler as mentioned above, an organic acid such as citric acid, tartaric acid, etc. as the acid component contributing to the preservability of the copying material, thiourea contributing to the prevention of fading as well as the preservability of the copying material, and so-called coupling assistant such as guanidine sulfate, pentaerythritol, O- methyl-isothiourea, guanylurea, etc. contributing to accelerating the coupling can be also employed as a component of the light-sensitive layer in the same way as in the case of conventional heat developable diazotype copying materials. Further, though it has no direct bearing on the component of the light-sensitive layer, a small amount of alkali metal or alkaline earth metal salt of an organic acid such as sodium citrate, calcium citrate, magnesium citrate, sodium tartrate, calcium tartarate, calcium gluconate, etc. may be employed as a assistant dissolving agent to accelerate dissolution of the foregoing coupler in preparing a solution for use in forming the light-sensitive layer.

By applying an aqueous solution comprising the above mentioned components dissolved therein onto one surface of a support such as paper, an acetate film, a polyester film, a synthetic paper, etc. and drying thereafter, the intended copying material can be obtained. The thus obtained heat developable diazotype copying material of the present invention is characterized not only by the production of a distinct black-color image when employed for actual copying but also by the fact that the light-sensitive layer has a satisfactory heat-resisting property. In other words, the decomposition temperatures of diazonium compounds expressed by the general Formula I or I' are comparatively higher than those of conventional diazonium compounds and are in the range of from 150 to 200 C. Accordingly, in case of a copying material employing the compounds of this invention, the decomposition loss of the diazonium compound at the time of heat development is relatively small and a highly concentrated color development can be obtained. That is, since the copying material of the present invention employs a specifically selected diazonium compound as set forth above, even if the coupling is effected at a temperature in the range of from 150 to 200 (3., there will occur no loss of the diazonium compound due to heating, and a highly concentrated color development can be expected. Moreover, the copied image formed by the copying material of the present invention, that is, the dye produced thereby has excellent interceptive property for ultarviolet rays. Therefore, it has the advantage of being also applicable as the copying material for a second original for use in a diazotype copying material. Further, since the present copying material contains no alkaliproducing agent in the light-sensitive layer, the preservability of the copying material per se is superb, and at the same time, it has the advantage of minimizing the discoloration of the copied image formed thereon.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The etfect of the present invention will be further eluciated in the following comparative examples of copying materials provided with a light-sensitive layer containing just one kind of diazonium compound together with coupler expressed by the foregoing general formula and examples embodying the present invention wherein the copying material is provided with a light-sensitive layer containing at least two kinds of diazonium compounds together with said coupler.

COMPARATIVE EXAMPLE 1 Water ml Phloroglucinol-carboxylic acid g 3 Sodium citrate g- 2 Citric acid g 1 Thiourea g 3 Caffeine g 5 (1) ..-g- 0.5 Saponin g 0.1

Formula:

n N -morgmon An aqueous solution comprising the foregoing components was applied onto the surface of a support consisting of paper precoated with silica, starch, polyvinyl acetate emulsion, etc. and dried at. a temperature in the range of from 100 to C. After superposing the original thereon, the thus treated support was exposed by means of a mercury lamp or a fluorescent lamp in conventional method and subsequently developed by heating at 170 Crfor 5 seconds. As a result, there was obtained a distince yellow-color image formed on a white background.

COMPARATIVE EXAMPLE 2 Water -ml..- 100 'y-resorcinol-carboxylic acid g 2 Sodium tartrate g 1 Tartaric acid g 1 Caffeine g- 5 Thiourea g 3 (1) g 0.5 Saponin .g 0.1

Formula:

COOH

An aqueous solution comprising the foregoing components was treated in the same manner as in Comparative Example 1, and by treating the resultant copying material in the same way as in Comparative Example 1, coupling was effected. As a result, there was obtained a yellowcolor image formed on a white background.

COMPARATIVE EXAMPLE 3 The below-mentioned aqueous solution (A) and aqueous solution (B) were respectively treated in the same manner as in Comparative Example 1, and subsequently by treating the resultant two kinds of copying materials in the same way as in Comparative Example 1, heat development was effected. As a result, there was obtained a yellow-color image formed on a White background in both cases.

Aqueous solution (A) Aqueous solution (8) Components:

Water l 100 3-bromo-resorcinol-carboxylic acid ..g 2 Sodium acetate 2 1 Citric acid g 1 Caffeine 2 2 0.5 Saponin g-.. 0.1

Formula:

coon HOCHlGE:

N -N1Cl'ZnCla CHaCs EXAMPLE 1 Water ml 100 'y-resorcinol-carboxylic acid g 3 Calcium citrate g 2 Citric acid g 1 Thiourea g 1 Caffeine g 5 Guanidine sulfate g 2 (1) g 0.3 (2) g 0.5 Saponin a 0.1

Formuls:

H-N H N Nio1- zno1,

Formula:

NNz0l-Z11Ch Home,

An aqueous solution comprising the foregoing components was treated in the same manner as in Comparative Example 1, whereby a heat developable diazotype copying material was prepared. Subsequently, the thus prepared copying material was exposed and developed in the same way as in Comparative Example 1, and, as a result, there was obtained a distinct black-color image formed on a white background. In those cases where resorcinol-carboxylic acid employed for the foregoing aqueous solution was replaced by a member selected from the Group-A consisting of couplers expressed by the below-mentioned structural formulas, the effect was the same as in the present example.

8 EXAMPLE 2-Continued Guanidine sulfate g 3 (1) g 0.3 (2) g 0.7 Saponin g..- 0.1

1 Formula COOH 011.011,

N N;Cl-Sn0l4 (31 .50

9 Formula N-N:Cl-Zn0h An aqueous solution comprising the foregoing components was treated in the same manner as in Example 1, whereby a heat developable diazotype copying material was prepared. As a result of employing this copying material for actual copying, there was obtained a distinct black-color image formed on a white background. In those cases where 3-chloro-resorcinol-carboxylic acid employed for foregoing aqueous solution was replaced by a member selected from the Group-A consisting of couplers as described in Example 1, the effect was the same as in the present example.

EXAMPLE 3 Aqueous solution (a) 1 Formula C O O H 9 Formula Subsequent to applying the foregoing aqueous solution (a) onto a support consisting of paper pre-coated in the same manner as in Comparative Example 1, and drying, the coated surface was further coated with the foregoing aqueous solution (b) and dried again, whereby a heat developable diazotype copying material was prepared. The image-forming property and the color of image of this copying material proved equal to that of Example 1. In those cases where the coupler employed for the foregoing aqueous solution (a) was replaced by a member selected from the below-mentioned Group-B of couplers, the effect was the same as in the present example.

Group B coon OOOH HO- OH 110- -oH B1 B1' CHzCHzCOOH 30 OH 0 OH HO- -01: HO OH B1 CH2| OOOH coon no -on no-Qon on, n,

coon coon no-on no-Qon OCzHa OCOCH;

coon 00011 HO OH HO on on; C2H5 ('30 on o 0 on HO--- OH HO -OH (CH2)3CHs -OHa- EXAMPLE 4 Aqueous solution (a) Components:

Water ml 100 3,5-dichloro-y-resorcinol-carboxylic acid .45.. 3 Calcium citrate g 1.5 Saponin g 0.1

Aqueous solution (b) Components:

Water ml 100 g 0,5 (2) g 0.7 Citric acid g 1.0 Calcium gluconate g 2.0- Thiourea g 5.0 Pentaerythritol g 5.0 Saponin g 0.1 Formula:

coon CN\ N -NO1-Zn0l G) 2 Formula Gib /N-N2C1'ZI1CI7 02136 The above-mentioned aqueous solution (a) and aqueous solution (b) were respectively treated in the same manner as in Example 3, whereby a heat developable diazotype copying material was prepared. As a result of employing the thus prepared copying material for actual copying, there was obtained a distinct black-color image formed on a white background. In those cases Where 3,5-dich1oro-'y-resorcinol-carboxylic acid employed for the foregoing aqueous solution (a) was replaced by a member belonging to the Group-B of couplers described in Example 3, the elfect was the same as in the present example.

EXAMPLE 5 Aqueous solution (a) Components:

Water ml (1) g 3.0 Magnesium citrate g-.. 1.0 Saponin g 0.1 liormnla:

COOEI HO- on CH3 Aqueous solution (b) Components:

Water ml-.. 100 (1) g-.. 0.5 (2) g 0.5 Citric acid g 1.0 Thiourea g 3.0 Guanidine sulfate 5 1.0 Saponin g 0.1

Formula:

COOHI OHgCO-N H N NzCl-LZnCl;

Formula:

Cifi

N-N2c1-5znoh C|H1 The above-mentioned aqueous solution (a) and aqueous solution (b) were respectively treated in the same manner as in Example 3, whereby a heat developable diazotype copying material was prepared. And, as a result of exposing and developing the thus prepared copying material in the same manner as in Example 1, there was obtained a black-color image formed on a white background.

Meanwhile, in case where the coupler employed for the foregoing aqueous solution (a) was replaced by a member of the below-mentioned Group-C of couplers, the effect was the same as in the present example.

Group C coon coon noon nono s oicna c o-Qonr coon coon coon nono noon noon n,on CHzCHzOH bn coon coon coon no on noon no I on Br can, coon; c1 Br bn on n 11 EXAMPLE 6 Aqueous solution (a) Components:

Water ml 100 4-methoxy-y-resorcinol-carboxylic acid g 3.0 Magnesium citrate g 1.0 Saponin g 0.1

Aqueous solution (b) Components:

Water ml 100 (1) g 0.5 (2) g 0.5 Citric acid g 1.0 Thiourea g 3.0 Guanidine sulfate g 1.0 Saponin g 0.1

Formula:

COOH N omen-Z1101: CH3 N Formula: 0%

/N NaCHZnCl, C3H7 The above-mentioned aqueous solution (a) and aqueous solution (b) were respectively treated in the same manner as in Example 3, whereby a heat developable diazotype copying material was prepared. And, as a result of employing the thus prepared copying material for actual copying, there was obtained a distinct black-color image formed on a white background.

In those cases where 4-methoxyl-'y-resorcinol-carboxylic acid employed for the foregoing aqueous solution (a) was replaced by a member of the Group-C of couplers described in Example 5, the effect was the same as in the present example.

EXAMPLE 7 Aqueous solution (a) Components:

Water ml 100 (1) g 5.0 Sodium citrate g 1.0 Saponin 0.1

Formula:

HO- OH Bl CHQCH Aqueous solution (b) Components:

Water ml 100 g 1 5 (2) g 0 5 FDartarie acid g 1.0 Thiourea g 3.0 Pentaerythritol g 5.0 Ethylene glycol g 5.0 Saponin g 0.1 Formula:

00011 at H N-Nlo1-gznoh llimrmula:

6 n N-mo1-z,znoh

By means of applying the above-mentioned aqueous solution (a) and aqueous solution (b) onto the tracing paper through the same operation as in Example 3 and drying, a heat developable diazotype copying material was prepared. The image-forming property of the thus prepared copying material proved equal to those copying materials in the above Examples 3 through 6. Moreover, the copied image produced by this copying material proved suitable for use as a second original. In those cases where the coupler employed for the foregoing aqueous solution (a) was replaced by a member of the belowmentioned Group-D of couplers, the eflect was the same as in the present example.

Group D 0 OH 0 0 0H 0 0 OH HO -OH HO- OH HO- 0H Br Br Br Cl 01 CH3 CH3 6H3 o 0 OH 0 0 OH 0 OH HO OH HO- OH HO- OH Br Br O1 CH3 (1H (3H o 0 o 0 EH;

0 0 0H 0 0 0H 0 0 OH HO- OH HO-- OH HO OH Br- Br Br- Br I -I CHQOH H a EXAMPLE 8 Aqueous solution (a) Components:

Water ml 3 ethyl 5 bromo phloroglucinol carboxylic acid g 5.0 Sodium tartrate g 1.0 Saponin g 0.1

Aqueous solution (b) Components:

Water ml 100 (1) g 1.5 (2) g 0.5 Tartaric acid g 1.0 Thiourea g 3.0 Pentaerythritol g 5 .0 Propylene glycol g 5.0 Saponin g 0.1

1 Formula COOH OIHI I /N-N;Cl-Zn0h C3H7 I Formula.

6 H N-G-N 101-}211011 The above-mentioned aqueous solution (a) and aqueous solution (b) were respectively treated in the same manner as in Example 3 by using tracing paper as a support, whereby a heat developable diazotype copying material was prepared. And, as a result of employing the thus prepared copying material for actual copying, there was obtained a distinct black-color image formed on a white ground. In those caseswhere 3,5-dichlOrO-7-1e80fcinol-carboxylic acid employed for the foregoing aqueous solution (a) was replaced by a member of the Group-D of couplers discribed in Example 7, the effect was the same as in the present example. It was recognized that the copies obtained from the copying materials of the present examples are effectively applicable for the second originals.

The total molar quantity of diazonium compounds in the compositions of this invention is normally from about 0.2 to 1, based on the molar quantity of coupling compound, and the ratio of blue or purple color-producing diazonium compound to yellow color-producing diazonium compound is in the range of from about 0.2 to 2.0 mols per 1 mol of yellow color-producing diazonium compound.

What we claim is:

1. A black line heat developable diazotype copying material comprising a support and a light-sensitive layer formed onto one surface of said support wherein said layer contains:

(A) As the only coupler present a coupler selected from the group consisting of compounds having the general formula radicals in which the alkyl group has 1 to 4 carbon atoms, arylacyoxy radicals having 7 to 9 carbon atoms, lalkylacyloxy radicals having 2 to 12 carbon atoms, w-hydroxylalkyl radicals having 1 to 3 carbon atoms,

w-hydroxyalkyloxy radicals having 1 to 3 carbon atoms and alkoxy radicals having 1 to 4 carbon atoms;

(B) at least one diazonium compound selected from the group consisting of compounds expressed by the general Formula I coon 14 wherein Y is a member selected from the group consisting of -N H ,-N H o,-N H s,-N H

wherein R" is a radical selected from the group consisting of hydrogen, cyclohexyl radical, alkyl radicals having 1 to 4 carbon atoms, hydroxyalkyl radicals having 2 to 4 carbon atoms, cyano radical and aralkyl radicals having 7 to 11 carbon atoms;

R' is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, aralkyl radicals having 7' to 11 carbon atoms, cyclohexyl radical, hydroxyalkyl radicals having 2 to 4 carbon atoms and benzoyl radical; and

X is the radical identical with that of said X expressed in the general Formula I; and

(C) at least one diazoniurn compound selected from the group consisting of compounds having the general Formula II N Nor" 6 wherein R"" and R"' each is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, hydroxyethyl radical, hydroxypropyl radical and benzyl radical; and

X" is the radical identical with that of said X expressed in the general Formula I; and general Formula III V1! wherein R and R each is a radical selected from the 15 group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen; R is a radical selected from the group consisting of hydrogen and alkyl radicals having 1 to 3 carbon atoms; and X' is the radical identical with that of said X expressed in the general Formula I.

2. A diazotype copying material according to claim 1, wherein said light-sensitive layer further contains an organic acid, thiourea and a member selected from the group consisting of guanidine sulfate, pentaerythritol, O-methyl-isothiourea and guanylurea.

3. A diazotype copying material according to claim 1, wherein said light-sensitive layer further contains a small amount of a salt selected from the group consisting of sodium citrate, calcium citrate, magnesium citrate, sodium tartrate, calcium tartrate and calcium gluconate.

4. A heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group C OOH COOH HO- OH HO- OH Br- -C2H Ol- (CHz)3CH3 C O OH O OH C O OH 5. A heat developable diazotype copying material of claim 1 wherein the coupler is HO OH Br- C2 5 6. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH C1- (CH2)aCHa 7. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH 8. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH 9. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO- OH 10. A heat developable diazotype copying material 16 of claim 1 wherein the coupler is a compound of the group coon coon noon noon CHzCHQCOOH Br ore-Q coon coon coon HO OH HO- OH HO- OH CH: Ha

11. A heat developable diazotype copying material of claim 1 wherein the coupler is HO OH CHQCHQCOOH 12. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH 14. A heat developable diazotype copying material of claim 1 wherein the coupler is CIJOOH 15 A heat developable diazotype copying material of claim 1 wherein the coupler is on -Q 16. A heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group coon coon coon no on no on no on I I Br Cl CH:

0 0on, n,on n

23. A heat developable diazotype copying material of claim 1 wherein the coupler is coon 00011 no or: no 011 I Br arm 01 Br 5 17. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH COOH

20. A heat developable diazotype copying material of claim 1 wherein the coupler is OOOH HO OH Br 02H:

21. A heat developable diazotype copying material of claim 1 wherein the coupler is OOOH HO- OH Cl Br 22. A heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group C O OH ('30 OH O O OH HO OH HO OH HO- OH I 9 Br Br 01- (J1 Br Br CH: 47H: H;

G O OH O O OH HO- OH HO OH Br Br Br- Br HIOH H 7 COOEI HO- OH Br Hr 24. A heat developable diazotype copying material of claim 1 wherein the coupler is 25. A heat developable diazotype copying material of claim 1 wherein the coupler is COOEI 26. A heat developable diazotype copying material of claim 1 wherein the coupler is OOOH 27. A heat developable diazotype copying material of claim 1 wherein the coupler is COOH 1/1957 Slifkin 96-91 1/1957 Pop 96-91 5/1957 Sanders et al. 96-91 12/1963 Bialczak 96-91 1/1965 Behmenburg et al. 96-49 4/1966 Van Rhijn 96-91 7/1967 Pope et al. 96-49 7/ 1967 Sosnovsky et al. 96-49 7/1967 Krueger 96-91 X 11/1968 Welch 96-49 X 11/1967 Landoau 96-91 X 2/ 1971 Usbeck et al. 96-91 R 2/ 1969 Halperin 96-91 R X 11/1971 Desjarlais 96-91 R X 12/1971 Iwaoka 96-91 R X FOREIGN PATENTS 8/1967 Great Britain 96-91 3/1967 Netherlands 96-91 (Other references on following page) 19 20 OTHER REFERENCES Chemical Abstracts, vol. 72, Feb. 23, 1970, 37,753k. Benbrook, H Diazotype Process, received Chemlcal Abstracts, vol. 72, May 4, 1970, 95, 3206. June 1954, pp. 8 and 9.

Derwent Japanese Pat. Reports, vol. 7, No. 7, p. 6 of CHARLES BOWERS Pnmary Examiner Section 3, March 1968 (Japanese Pat. 4127/68-Ricoh, 5 US. Cl. X.R,

February 1968). 9649 Docket 8332 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3595885 Dat October 3. 1972 Shnji MHT'UETBTHHJ 91'. a!

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line t, change 'Maryama" to read Margyama ---3 Column 1, line 7, after "Japan" insert Assignor to Ricoh Co. Limited, Tokyo, Japan Signed and sealed this 3rd day of April 1973 Q (SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents ORM PC7-1050 (IO-69) USCOMM-DC 60376-P69 1 us. GOVERNMENT PRINTING OFFICE: lass o3as-334