US2298444A

US2298444A - Light sensitive diazotype material

Info

Publication number: US2298444A
Application number: US361263A
Authority: US
Inventors: Weissberger Arnold; Vanselow Waldemar
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1940-10-15
Filing date: 1940-10-15
Publication date: 1942-10-13
Anticipated expiration: 1959-10-13
Also published as: FR907964A; GB554921A; GB554998A

Description

Patented Oct. 13, 1942 I Rochester, N. E,

Company, Rochester, N. Y.,

New Jersey ..Arnold Weissberger and Waldemar Vanselow, assignors to Eastman Kodak a corporation of No Drawing. Application October 15, 1940, Serial No. 361,263

6 Claims.

This invention relates to the preparation of wherein R represents a phenyl nucleus having the amino group in position para or ortho to N, and

Z represents the non-metallic elements necessary to complete a heterocyclic nucleus selected from the group consisting of a morpholine nucleus, and a piperidine nucleus. In addition to the amino group, R can contain one or more nuclear monovalent substituents such as an alkyl group represented by methyl, ethyl, propyl, butyl for example, an alkoxy group represented by methoxy, ethoxy, propoxy, butoxy for example, a halogen such as chlorine, bromine, fluorine, iodine, or a sulphonic acid radical.

We have found that the above described diazo derivatives of N-p-aminophenyl-morpholines and -piperidines are stable compounds under ordinary conditions, but are highly sensitive to light, decomposing more or less completely in proportion to the intensity of the light and the period of exposure. Since they are also capable of condensing with certain aryl compounds, as well as with their own partial decomposition products in the presence of alkaline substances to form intensely colored azo dyes, we have furthere found that these diazo derivatives are valuable as light sensitive components in diazotype copying materials. In the presence of selected coupling components on a suitable support, they yield on exposure to light behind a pattern such as a line drawing, printed matter or similar contrasty subject matter and subsequent alkaline processing, images having dark lines and tones contrasted to almost white or slightly gray or tan fields. As will be more fully apparent from the examples given, we can prepare our new diazotype materials by a number of methods. For example, the base or support carrying or containing the light sensitive compounds can be a paper, a cloth, a film such as prepared from an organic derivative of cellulose, synthetic resin such as a polyvinyl acetal, regenerated cellulose, a glass plateor a sheet of metal, the sensitizing materials being applied by coating, dipping, brushing, spraying, dusting or by any other means known to one skilled in the art. Ordinarily, the sensitizing compounds are applied from solutions containing them, either alternatively with a solution of one or more of the diazo compounds of our invention and a solution of the selected coupling component, or, the compounds can be dissolved in a common solvent and applied as above, usually with an acid compound present as a stabilizer. In some cases, it may be desirable to add a thickening or emulsifying agent to the solution or solutions such as gelatin, polyvinyl alcohol, gum tragacanth, a higher fatty acid glycerylsulfate, and the like. The solution concentrations of the sensitizing compounds can be varied within wide limits, the preferred range being up to about 2% by weight of the diazo compound, and about the same concentration of the coupling compound.

It is an object of the invention, therefore, to provide a light sensitive diazotype copying material which combines the advantages of good keeping qualities, high degree of sensitivity to light, and provides prints which are characterized by good stability, sharpness and contrast.

The aminophenyl piperidine compounds may be prepared by reducing the nitro piperidine compounds prepared in general by the method described in Journal Chemical Society (1927) pages 1113 and 1122. The aminophenyl morpholine compounds may be prepared by condensing the desired aniline compound with a beta-beta-dihalogen alkyl ether such as beta-beta'-dichlorodiethyl ether, sym. dichloro-di-isopropyl ether and other similar kind of haloalkyl ethers.

The following examples further illustrate the preparation and application of our new light sensitive diazotype copying materials.

-EXAMPLE 1 A diazo solution was prepared by treating 5.43 grams of N-p-(aminophenyl) -morpholine hydrochloride dissolved in 0. cs. of water with a slight excess of nitrous acid. A piece of white paper was dipped in this solution for a short period, the excess of solution removed, the paper dried and then dipped in a 1% solution of B-naphthol in ethyl alcohol. The dried sensitized paper was exposed behind a positive to a quartz mercury vapor arc. After a few minutes, the image was developed in an atmosphere of ammonia maintained at slightly higher than room temperature. The positive image obtained at once was dark brown in color on an almost white field.

In place of N-p-(aminophenyl) -morpholine hydrochloride, there may be substituted 9 grams of N-p- (amino-m-tolyl) -m o r p h o l i n e sulfate which produces a dark brown black image on an almost white field turning tan colored after several months, or, there may be substituted approximately 2 grams of N- (4-aminophenyl) morpholine-2-sulfonic acid which yields a dark red image on a pale pink field, or, there may be pholine which, with p-naphthol coupler produces a red image on a pale pink field, and with resorcinol coupler an orange image on a pale tan field.

ExAMrLn 2 The diazo solution prepared as in Example 1 was allowed to stand until a suflicient quantity of the diazonium compound had hydrolyzed to provide a coupler. A piece of white paper was then bathed in the solution, the excess solution removed, and the paper dried. Upon exposure and development, an image was obtained which was dark brown on a tan field turning with time to a black image on a pale gray field.

ExAMru: 3 '7 grams of N-p-(aminophenyl) -piperidine dihydrochloride CHI-CH,

OKs-CH! were diazotized with nitrous acid in 100 0. cs. oi! I aqueous solution. A piece of white paper was treated in this solution, dried, and then treated in a 1% alcoholic solution or fl-naphthol and again dried. After exposure and development as in Example 1, a blue black image on a white field was obtained.

In place oi. N-p-(aminophenyD-piperidine dihydrochloride, there may be substituted 7.5 grams oi N-(2-chloro-4-aminophenyl) piperidine sulfate which produces a bright red image on an almost white field.

EXAMPLE 4 5 grams of N-p-(amino-m-anisyl) -morpholine were diazotized in 100 c. es. of aqueous solution, and a piece of paper treated in this solution, dried, and then treated with a 1% alcoholic solution of 2,4-dichloro-1-naphthol, and the paper again dried. After exposure through a positive pattern and development in ammonia vapor, an image was obtained which was very dark brown on a pinkish gray field, turning after five months to a black image on a slightly draker field.

EXAMPLE 5 added to 80 c. cs. of solution containing 0.5 gram of tartaric acid and the diazonium salt of 2.5 grams of N-p- (aminophenyl) -piperidine dihydrochloride. Several pieces of filter paper and rag stock paper were sensitized in three diiferent ways: by dipping the papers into the solution; by brushing the solution onto papers; and by spraying the papers with the solution. The products in general were similar having dark brown images on tan fields and appeared to be quite stable.

EXAMPLE 6 0.2 gram of oxalic acid and 10 grams of barium chloride were added to 100 0. cs. of aqueous solution containing the diazonium compound of 2 grams of N-p-(aminophenyl) morpholine hydrochloride. Paper sensitized by this solution and then dried was exposed to light behind a pattern and the print developed in a feebly alkaline solution of p-oxynaphthoic acid anilide containing 0.4% of formaldehyde. The images obtained were dark purple, but the field showed some bleeding and running due to the wet development of the images.

1 gram of rescorcinol in 20 c. cs. of water was 5 3 98.444. substituted 2 grams or N-(2-aminophenyl) mor-' Exam: 7 v 2.7 grams or N-p-(aminophenyl) morpholine hydrochloride were diazotized-in- 100 0. cs. 0! solution. Paper was first bathed in this solution and then in a 1% alcoholic solution. of p-naphthol and allowed to dry. After exposure of the sensitized paper behind a pattern, the image was developed by bathing the exposed paper in a 0.5% aqueous solution of triethanolamine. The dried print had a red brown image on a reddish tan field, but the contrast was somewhat interior to that obtained by ammonia development.

ExAmI8 2.0 grams of N-(3.-methyl-4-aminophenyl piperidine sulfate were diazotized in 100 c. cs. oi solution. Samples oi clear, lightweight paper were first coated with this solution and then with a 1% alcoholic solution of phloroglucinol and allowed to dry. Exposure and processing were carried out as in Example 1. A brown black image on a white field was developed almost immediately.

Exam 9 0.2 gram of oxalic acid and 10 grams of barium chloride in 20 0. es. of water and 0.4 gram of phloroglucinol in 4 c. es. of alcohol were successively admixed with c. es. of aqueous solution containing the diazonium salt of 2.15 grams oi. N-p-(aminophenyl) morpholine hydrochloride. A piece of white, light weight paper was sensitized with this solution, dried and exposed as.in Example 1.

The-image wasdeveloped in one case with gaseous ammonia, and in another case with a 0.2% aqueous sodium hydroxide solution containing in addition 0.4% formaldehyde.

ExAMrLr: 10

The zinc chloride double salt of the diazonium 1" EXAMPLE 11 The zinc chloride double salt oi! the diazonium compound of 2.15 grams oi. N-p-(aminophenyl) morpholine hydrochloride was dissolved in c. cs. of water. 2.0 grams of concentrated hydrochloric acid, 2.0 grams of boric acid, 4.0 grams of tartaric acid and 0.2 gram of thiourea were added to this solution. Suitable papers were bathed in the above solution and then in B- naphthol. The sensitized and dried papers were then exposed and developed in the manner described in Example 1. The images obtained were dark red on a white field and showed good keeping qualities. Samples oi paper prepared with the omission of hydrochloric, boric, and tartaric acids and of thiourea produced darker red images on very pale gray fields.

While the invention has been illustrated more particularly in connection with azo color images formed from various N-p-aminophenyl-morpholines and piperidines with coupling components such as p-naphthol, resorcinol, phloroglu-- cinol, 2,4-dichloro-1-naphthol, or p-oxynaphthoic sensitized with a number 01' u-naphthol derivaacid anilide,1t will be understood that other coutives and N-p-aminophenyl piperidine. These pling components are likewise included within the examples were prepared in general by one of the scope of the invention. For example, Table I processes previously described, but contain no shows examples of prints obtained with papers 5 stabilizing substances.

TABLE I Coupling compound Preparation of coupling compound gfigggghg 4-benzoyl-l-nnnh hnl Dark brown.

Moro-l-nnphfhnl 4-chloro-1-nsphthol Very dark brown. 2, 4-dibromo-5-(N-benzyl-N-naphthalene-fi-sulfon) amido-l-naphthoL- Procedures I-l-IIA Brown.

-SO Ha-CoHs 16 2, 4-dichloro-E-(N-benzyl-N-a-naphthoyl) amino l-naphthol Procedures I+IIA Do.

l]I--C O OHr-CaHn V 17 2, 4-dichloro-5(N-benzy1-N-fl-naphthoy1) amino-l-naphthol Procedures I+IIA Dark brown. 18 5-hydroxy-l-naphthoic acid Do. 19 Methyl-l-naphthol-ssulfonare By heating 1-acetoxynaphthalene-5- Do.

' sull'onyl chloride with excess of methyl alcohol. 20 4'suIiouenilide-1- p Do.

Table 11 illustrates the color of the image of naphthol coupling components as specified. No dia'zotype prints obtained with papers sensitized stabilizing substances were added. with N-p-aminophenyl morpholine and various u- TABLE II Diazo compound of N-p-aminophenyZ-morpholine coupled with E Z P Coupling compound Preparation of coupling compound g g z gg g g 21 5-[p-(p-acetaminobenzene sulfonamido)-benzamido] l-naphthol Procedure V Brown.

NHC OC NHSO,-NH-C 0 on;

Z-acetyl--chloro-l-naphthol Dark brown. 2-ecetyl-1- ap ol Brown. 4-acetyl-l-naphthol Dark brown.' 2-acetyl-l-naphthol-a-methyl-a-phenyl hydrazone By refluxing together 2-acetyl-1- Brown.

naphthol and a-methyl-a-phenylhydrazine in alcoholic solution. OH: OH

I|-TNCnHs C-CHa 26 Z-acetyl-l-naphthol semi-car .0

4 mean Tsnu: II-Continued gg Coupling compound V Prcpuntionolcoupling compound 27 4-bcnzoyl-l- Dllk brown. 28 o-(N-benzyi-N n-smylmphthslene-aorp-suifon) omIdO-I-nIphthoL..- ProcodumI+I1A Brown,

OH C @CHH N-BO: Hz-CnHr 5- -benzyl-N-mphthalene-crsullon) omido-l-ns hthol -.do Do. 6- N-benzyl-N-p-tert. amyl-benzeno-sulion smi o-l-nsphtholdo Dc. 5- N-bcnzyl-N-n-vaieryl) amido-l-mphtho dn Do.

N-OO-CrHo Hr-CIHI 2-hromoacetyl- -na phthol Dark brown.

z-chlorc Do.

{-chloro-l-nnnhfhnl D0. #cinmmoyl-l-naphthol Brown. 2,4-dibromo-5-(N-benzyl-N-ns hthaicno-fisulfon) ami Procedures I+IIA+III Do. 2,4-dich1oro-5-I (g-bcnzamido -benum1do]-l-naphthol--.. Procedures V+VI Do. 2,4-dichioro-6- enzyl-N-a-nsphthoyl) smino-i-naphthoL. Procedures I+IIA+III.. Do. 2,4-dichloro-5- N-benzyl-N-fi-naphthogl) umino-l-naphthoi. 0 D 2,4-dichloro-5-palmityl-amino-l-napht o1 Procedures IIA-l-III--. Do. b-fimm-dinitrobenzoylamin Ml Procedures IIB Dc.

D -piperidinomethyi-1,fi-dihydroxynaphthaiene B treating 1,5-dihydroxym Du'k brown.

' one with formalin and piperidine. l-hydroxy-z-(N-isoamyl-N-phenyD-nsphthamida Procedure IV Polo brown.

co-i iw-ciml CIHI i g l-hydroxy-z-N-cthyi-N-a-nsphthyb-mphthsmide ProooduroIV Brown. l-hydroxy-Z- N-methyD-naphthanilido do Do.

(IJH: 00-N-0lHl 'i"iocod""h 3'iiii.' I

By hoot l-acctoxyns hthulene- Do.

o-sulrony chloride w th excess methyl sicohol. 62 5-methy1 lulfon lamino-l-naphthol cII r Psie brown. 53 l-naphthoi-B, (sulfon-N-mcthylanilida) By condensing 1naphth0i-3,6-di- Brown.

I sulionic sold with lodium scotatc OH and scetic anhydridc, treating the 7 product with P01; and the istter product with mcthyisnilinc and lodium ocetatc, llld then hy- (3H1 (3H1 draining with NsOH.

CiHr-NSO Oz-N-Cfls i' fiifighcuu fx iil hthdido) B co d in4- r i i h kbbmwn' on y nens po on owns e rown; p thslene lullonyl chori& with aethyinaphthyhmino and sodium izoetsto Ind hydrolyzing with s 5- nitrobcnumido)-l-mphthol Procoduro IIB.. Brown. o-ggsuifamylbenzamidoyl-mphthoi Procedure 11A. Dsrk brown. I-nwnleryi-l-mphthol... By hating mmph oiwi Bro 4- n1 11 hthai n fl i i i i x n' l n D n- -na 1 arms 0 o. w w p thliene with vuleryl chloride 31d duminum chloride.

In the above tables, reference has been made to the procedures for preparing some of the coupling compounds disclosed. These general procedures are briefly described in the following:

I. -benzylamino-1-naphthol was prepared by condensing 5-amino-1-naphthol. with benzaldehyde and reducing the resultant Schifl base catalytically or chemically.

lI(A) 5-acylamino-l-naphthols were prepared by condensing 2 moles of 5-amino-l-naphthol or 2 moles of a 5-alky1amino-1-naphthol with 1 mole of XCl, wherein X represents an acyl group.

(B). By condensing -1 mole of the naphthol compound with 1 mole of XCl in the presence of sodium acetate and acetic acid.

III. Halogenated 5-acylamino-l-naphthols of procedure II were prepared by treatment with sulfuryl chloride or bromine in a suitable solvent.

IV. l-hydroxy-2-naphthamides were prepared by condensing 1 mole of l-hydroxy-2-naphthoyl chloride with 2 moles of a compound having the formula RNHR' wherein R and R may be hydrogen, alkyl or aryl.

Y. 5 (p acylaminobenzamido) -1 naphthols were prepared by condensing a 5-amino-l-naphthol with p-nitrobenzoyl' chloride. reducing the nitro group and then reacting with sodium acetate and X01, wherein X represents an acyl group.

VI. Halogenated 5-(p-acylaminobenzamido) -1- naphthols were prepared by treatment with sulfuryl chloride or bromine in a suitable solvent.

Although the examples of Tables I and II refer particularly to coupling with the diazo derivatives of N-p-aminophenyl piperidine and N-paminophenyl morpholine, respectively, it will be apparent from all the foregoing that similar results can be obtained with the various methyl, halogen, methoxy and sulphonic acid substituted diazo derivatives of these compounds.

we claim:

1. A light sensitive diazotype material comprising a light sensitive diazo derivative of a compound the general formula:

wherein R represents a benzene nucleus, and Z represents the non-metallic elements necessary to complete a morpholine nucleus.

2. A light sensitive diazotype material comprising a light sensitive diazo derivative of a compound having the general formula:

wherein R represents a benzene nucleus.

3. A light sensitive diazotype material comprising a light sensitive diazo derivative of a compound having the general formula:

/C Hr-C H. O

CHrC:

wherein R represents a benzene nucleus, and Z represents the non-metallic elements necessary to complete a morpholine nucleus, and a coupling component selected from the group consisting of a phenol compound, and a naphthol compound.

ARNOLD WEISSBERGER.

WALDEMAR VANSELOW.