DE1693062A1 - Diazotype material - Google Patents

Description

PATENT LAWYERS

dr. w. Schalk dipl-ing. Peter Wirth

DIPL-ING. G. E. M. DANNENBERG · DR. V.SCHMIED-KOWARZIK

,, _T - / 6 FRANKFURT AM MAIN _Λ -, _ j, r ^ rr

^SI - / ^ör o ,. _E , c " _EN " _EIMEB st, ₃₉ 23.9.1966

CHEMISCHE PABRIEK L. VAN DER GRINl ¹ EIT HV V e ti 1 ο / Netherlands

Diazotype material

The invention "relates to diazotype material which is a contains novel diazo compound. This diazotype material is preferably single-component diazotype material, that is developed with a liquid developer. But it can also be two-component diazotype material with Help e-evolved from ammonia vapor, or heat evolving Be diazotype material.

The German Auslegeschrift 1 174 612 describes diazotype material which is a p-aminobenzene diazo compound the formula

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contains, where X is an anion, Y is hydrogen, halogen, Methyl, alkoxy or phenoxy denotes, Z denotes a hydrogen atom or one or more substituents from the group: Halogen, methyl, alkoxy and dialkylamino, and N is a tertiary amino group including saturated heterocyclic groups such as morpholine, piperidine, etc. is.

This diazotype material is very light sensitive and very suitable for the visual determination of the end point exposure when copying with the light of actinic fluorescent mercury vapor lamps he follows. The bleached background of the copies is clean and only slightly yellows in the light. One component diazotype material according to the German interpretative document 1 174 612 gives when developed with weakly acidic

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Phloroglucinol developers very dark, in the diazotype as black viewed azo dye images. The azo dye will but often viewed as a bit too reddish. A more blue- or green-black azo dye shade is often preferred.

The invention relates to diazotype material sensitized with a benzene diazo compound which is in para division to the diazo group a tertiary amino group, a substituted or unsubstituted phenoxy group in the opposite position to the diazo group and in the para position has a further substituent to the phenoxy group, the latter substituent being a group of the formula

CO-R ₂

is where R ^. a substituted or unsubstituted alkyl branched Alkyl, or unsaturated alkyl group, a cycloalkyl or aralkyl group and CO-Ro represents an acyl group.

More particularly, the invention relates to a diazotype material with a diazo compound of the formula

wherein X is an anion, R * is a substituted or unsubstituted alkyl, branched alkyl or unsaturated alkyl group, a cycloalkyl or aralkyl group, CO-R _{2 is} an acyl group, R, and R ^ is substituted or unsubstituted alkyl, branched alkyl -, aralkyl or cycloalkyl groups or together with the nitrogen atom a saturated heterocyclic group

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Form ring and Z one or more substituents of the group: Represents halogen, methyl, alkoxy and dialkylamino, sensitized is.

In the above definition, “acyl” is to be understood as meaning the radical COR in which R is hydrogen or an organic radical. One · such a conception of the term acyl is in the diazotype literature common (see British patents 615.774, 347.4-30 and 539.031).

The diazotype material according to the invention is very light-sensitive; and it develops rapidly. Diazotype material sensitizes with compounds of the above formula the one para-standing Carry non-cyclic amino group gives with the buffered weakly acidic phloroglucinol copies with less reddish tinges black azo dye images as the known comparable diazotype material according to the German Auslegeschrift 1,174,612. The diazo compounds of the above formula with a Because of their lighter color, para cyclic amino groups are more suitable for sensitizing transparent ones Diazotype materials, which are used for making intermediate copies should serve.

Diazo compounds which can be used in the diazotype material according to the invention are, for example:

4-Diazo-5-N-methyl-N-formylamino-2-phenoxy-N _t N-dimethylaniline 4-Diazo-5-tf-methyl-N-acetylamino-2- (4 · '-chlorophenoxy ) -N, N-dimethylaniline

4-Diaz o-5-N-methyl-N-butyryl amino-2- <4'-chlorophenoxy) 4i, N-dimethyl aniline

4-Diazo-5-N-methyl-N-phenacetylamino-2- (4 ^I -chlorphenox ^ -i ^ N-dimethylaniline

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4-Diazo-5-N-methyl-N-benzoylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline

dimethylaniline 4-diazo-5-N-methyl-N-methoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4-diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4-chlorophenoxy ) -N, N-dimethylaniline 4-Diazo-5-N-methyl-N-propoxycarbonylamino-2- (4 · -ctlloroplienoxy) -N, N-dimethylaniline 4-diazo-5-N-methyl-N-isobutoxycarbonylamino-2 - (4'-chlorophenoxy) '- N, N-dimethylaniline 4-diazo-5-N-methyl-N-allyloxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4-diazo-5-N- methyl-N-cyclohexyloxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4-diazo-5-N-methyl-N-benzyloxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4 -Diazo-5-N-methyl-N-phenoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4- J3iazo-5-N-methyl-N-chloroacetylamino-2- (4'-chlorophenoxy) - N, N-dimethylaniline 4-Diazo-5-N-methyl-N-morpholineethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4-diazo-5-N-ethyl-N-ethoxycarbonylamino-2- ( 4'-chlorophenoxy) -N, N-dimethylaniline 4-diazo-5-N-propyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-di methylaniline 4-Diazo-5-N-isopropyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline 4-Biazo-5-Nn- ^ utyl-N-ethoxycarbonylamino-2- (4'- chlorphenoxy) -

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N, N-dimethylaniline

4-Diazo-5-N-cyclohexyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy ) -N, N-dimethylaniline

4 ~ Diazo-5-N-benzyl-N-ethoxycarbonylamino-2- (4'-malophenoxy) -N, N-dimethylaniline

4-Diazo-5-N- (2'-hydroxyethyl) -N ~ ethoxycarl) onylamiiio-2- (4 · · - chlorphenoxy) -N, N-dimethylaniline

4-Diazo-5-N- (2'-chloroethyl) -N-aetlioxycarbonylamino ^ -C ^ 'chlorophenoxy) -N, N-dimethylaniline

4-Diazo-5-N- (2'-diethylaminoethyl) -N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-dimethylaniline

4-Diazo-5-N-allyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) N, N-dimethylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4'-methylphenoxy) N, N-dimethylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (2'-dimethylaminophenoxy) -N, N-dimethylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (2 ', 4'-dibromophenoxy) -N, N-dimethylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4-chlorophenoxy) -: N, N-diethylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-di-n-propylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-di-n-butylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-di-n-hexylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4 ^l -chlorophenoxy) -N-methyl-N- (2'-acetoxyethyl) aniline

4-Diazo-5-N-methyl-N-ethoxycarbonylamino-2- (4'-chlorophenoxy) -N, N-bis (2'-acetoxyethyl) aniline

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4-Dia zo-5-N-methy1-N-ethoxy carbonyl amino-2-r (4-chlorophenoxy) -N, N-bis (2'-chloroethyl) aniline

4-Diazo-5-N-methyl-N-thoxy carbonyl amino-2- (4-chlorophenox ^ -N, N-bis (2'-hydroxyethyl) aniline

4-Diazo-5-N-methyl-N-ethoxy carbonyl amino-2- (4- '-chlorophenoxy ^ N-me ethyl-H-benzylaniline

4-Di azo-5-N-methyl-N-ethoxy carbonyl am ino-2- (4- '-c hi orphe nox ^ -N-butyl-N-benzylaniline

4-Diazo-5-N-methyl-Na * thoxycarbonylamino-2H ( ⁱ 4 -'-chlorophenox ^ -N-methyl-N-cyclohexylaniline

4-Diazo-5-N-methyl-N-ethoxycarbonylajnino-2-0l- ^l -chlorphenox ^ -N-benzyl-N-cyclohexylaniline.

These diazo compounds are preferably used as diazonium salts such as diazonium chlorides, sulfates, nitrates and metal chloride double salts (e.g., diazonium chlorostannates, chlorozincates), diazonium borofluorides and the like. They can be applied individually or mixed with one another to the diazotype material according to the invention. Of course, they can also be used in admixture with other types of diazo compounds. However, since such mixtures contain a smaller amount of diazo compound as defined above, a diazotype material according to the invention which is produced with these mixtures has the advantages described to a lesser extent. ^!

Particularly noteworthy among these diazo compounds are those which is a slight dialkylamino group in the para position to the diazo group, in the para position to the phenoxy group an N-alkyl-N-alkoxycarbonylamino group and wherein the phenoxy group is halogen-substituted. Sensitizing with such compounds

t diazotype material produces copies with beautiful black lines

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when using a buffered weakly acidic phloroglucinol developer is developed and copies with azo dye images that use the untraviolet light used in the diazotype are excellent absorb when using a buffered alkaline phloroglucinol developer I. developed: ■ is.

The diazotype material according to the invention can be opaque Carrier material, such as white paper or linen, or a transparent carrier material, such as tracing paper, tracing linen, Cellulose ester film, polyester film, transparent paper, etc., contain. The diazo compound can be applied directly to the surface of the carrier or it can be applied in a hydrophilic .Filmschicht, which optionally by means of one or more Sublayers can be bound to the carrier, be embedded.

The diazotype material according to the invention can also be two-component diazotype material be. In such a material, it is preferred to use a slowly coupling azo component such as 2-hydroxy-8-biguanidinonaphthalene, 2-hydroxynaphthalene-3> 6-disulfonic acid or 7'-hydroxy-1 ', 2 *, 4,5-naphthimidazole, is used. The diazotype material According to the invention, diazotype material to be developed by means of heat, for example material as described in FIG British patent specification 815 · ΟΟ5 or the Dutch patent application 64-024-52 is described.

The diazotype material according to the invention can contain the auxiliaries usually used in diazotype materials, for example acids such as citric acid, tartaric acid and boric acid; Stabilizers such as benzene and naphthalenesulfonic acid, p-phenolsulfonic acid and their water-soluble salts; Metal salts "such as" \ -. Nkchloride, magnesium chloride, nickel sulfate, and alum; Sub-

punch that of an increase in the speed of development serve as glycerin, polyethylene glycol and urea; Surface improvers, such as finely divided, colloidal or non-colloidal silicon dioxide, aluminum oxide, barium sulfate, Rice starch etc .; Binders such as gelatin, gum arabic, gelulose ether, starch derivatives, polyvinyl alcohol, Dispersions of polymers such as dispersions of cationic, nonionic and anionic polyvinyl acetate; Substances, which serve to improve the background of the copies, such as thiourea.

The phloroglucinol developers used in the one-component diazotype process used, often vary in their composition and acidity. The following are two weakly acidic phloroglucinol developers and a weakly alkaline phloroglucinol developer, which are used in practice and those in the following examples for the development used is described:

Developer A is a solution of:

4 grams of phloroglucine
0.1 g acetoacetanilide

5 ml of 2-ethyl-i-hexyl sulfate
15 g beet sugar

2.5 grams of benzoic acid
14 g sodium benzoate
135 S sodium formate
in 1000 ml of water.
The pH of this liquid is around 5.8.

Developer B is a solution from:
6.5 grams of phloroglucine

4 g resorcinol

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ORIGINAL INSPECTED

AO

10 g thiourea 2 g of the i-sodium salt of dibutylnaphthalenesulfonic acid

14 g sodium formate 22 g sodium benzoate

4-9 ζ Crinatriuacite (2 ag.) 1.2 g citric acid

in 1000 ml of water.
The pH of this liquid is 6.5

Developer C is a solution of: 30 g thiourea

5.4 g of phloroglucine

6.5 S resorcinol

1 g of the potassium salt of hydroquinone monosulfonic acid 5 g of sorbitol

15 g beet sugar

50 g potassium tetraborate (5 aq.)

1.5 g of isopropylnaphthalenesulfonic acid in 1000 ml of water.
The pH of this liquid is about 9 »0.

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BATH ORIGINAL

example 1

vWhite base paper for the diazotype process of 60 g / m is sensitized with a solution that

36 g of 4-dimethylamino-5- (4 ^l -chlorophenoxy) -2-N-methyl-N-ethoxycarbonylaminobenzene-diazonium chloride / zinc chloride double salt
5 g of tartaric acid
30 ml polyvinyl acetate dispersion Vinnapas H.60 (der

Wacker Chemie 'GmbH, Munich) in 1000 ml of water
contains, and dried.

A sheet of the diazotype paper thus obtained is under a Pencil drawing on tracing paper exposed image by image until the slide connection is completely under the non-image parts of the drawing is faded, and then developed with Developer B.

The copy shows a black image on a white background.

A second sheet of this diazotype material is made in the same V / ice exposed and then developed with developer C. The copy shows a brown image on a white background and can Excellent further copying on diazotype material.

The diazo compound used in the above example was manufactured as follows:

4-N, N-dimethylamino-5 - (^ ¹ -chlorophenoxy) -2-chloromitrobenzene was reacted with methylamine and the product obtained was acylated with ethyl chloroformate. The 4-N, N-dimethylamino-5 - (^ ^l -chlorophenoxy) -2-N-methyl-N-ethoxycarbonylamino-nitrobenzene Schmi32fc at 78 ⁰ C. The above-mentioned diazonium salt in the usual V / eise was reduced from this nitro compound and diazotization obtained. 109840/1841

White base paper for the diazotype process of 80 g / m is sensitized with a solution that

27 g of 4-bis (acetoxyethyl) amino-5 - (^ ^l -chlorophenoxy) -2-N-methyl-N-acetylaminobenzene diazonium chloride / zinc chloride double alc
30 g naphthalene-i ^ jö-trisulfonic acid, sodium salt

5 g of tartaric acid
in 1000 ml of water
contains, and dried.

A sheet of the diazotype material thus obtained is placed under a ™ India ink drawing on tracing paper exposed until the entire diazo connection is bleached out under the non-image parts of the drawing, and then developed with Developer B.

The copy shows a black image on a clear white background.

The diazo compound used in the above example was made as follows:

4-N, N-bis (2'-hydroxyethyl) amino-5-C ^ ^l -chlorophenoxy) -2-chloro-A nitrobenzene, prepared from 2- (4 * -chlorophenoxy) -5-chloroaniline by reaction with ethylene oxide and Nitration, was reacted with methylamine. The product thus obtained, which melts at 99 °, was acylated with acetyl chloride. The above-mentioned diazonium salt was obtained in the usual way by reduction and diazotization from the 4-N, N-bis (2 ^l -acetoxyethyl) amino-5- (4 ^{l -chlorophenoxy) -2-N-methyl-N-acθtylaminonitrobenzene.}

Example 5 '

ρ Glued natural tracing paper of 80 g / m sensitized with a solution that

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35 S ^ -toorpholino-5K4'-clilorphenoxy) -2-N-methyl-N-

ethoxycarbonylaminobenzene diazonium chloride / zinc chloride double salt
5 S tartaric acid
30 ml Vinnapas H.60
. in 1000 ml of water
contains, and dried.

A sheet of the transparent diazotype paper thus obtained is exposed imagewise as described in Example 1 and developed with developer C .;

The copy shows a brown image on a clear background. and is very suitable as an intermediate copy for the production of further copies on diazotype material.

The diazo compound used in the above example was made as follows:

5- (4 ^f -Chlorophenoxy) -2-chloroaniline was acylated, nitrated and deacylated. The 4-nitro-5-chloro-2- (4 ^l -chlorophenoxy) aniline was reacted with methylamine. The primary amino group was diazotized and replaced with a chlorine atom using the Sandmeyer method. This chlorine atom was exchanged for a morpholino group and the product obtained was acylated. The above-mentioned diazonium salt was obtained in the customary manner by reduction and diazotization from 4-morpholino-5- (4'-chlorophenoxy) -2-M-methyl-N-ethoxycarbonyiaEiinonitrobenzol, which melts at 135 ° C.

Example 4

Paper of 150 g / m, which is provided on one side with a cellulose acetate layer with about 50 weight percent bound acetic acid of about 10 / U thickness, which is fixed to the paper by means of an adhesive and to a depth of about 4 , n to

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ORIGINAL INSPECTED

1693U5Z

to an acetyl content, calculated as bound acetic acid, of on average about 20 percent by weight, which corresponds to an average number of 0.7 acyl groups on the OH groups, hydrolyzed is, is impregnated on the hydrolyzed side of the cellulose acetate layer for 3 "5 minutes with the following solution:

28 g of 4-N-methyl-N-cyclohexylaraino-5- (4- ¹ -chiorphenoxy) -2-

N-methyl-N-ethoxycarbonylaminobenzene diazonium chloride / zinc chloride double salt 5 g citric acid
250 ml ethanol, 96%
750 ml of water.

The excess fluid is squeezed out and the sensitized Layer dried.

A sheet of the diazotype material is exposed as in Example 1.

The latent diazotype copy thus obtained is developed with developer A. The developed copy shows a strong black Image on a white background.

The diazo compound used in the above example was made as follows:

^ -N-Methyl-N-cyclohexylamino ^ - (4- ¹ -chlorphenoxy) -2-chloronitrobenzene was reacted with methylamine. The product obtained, which melts at 180 ° C., was acylated with ethyl chloroformate. The above-mentioned diazonium salt was obtained in the usual way by reduction and diazotization from the ^ -N-methyl-II-cyclohexylaiaino-5- (4'-chlorophenoxy) -2-N-methyl-N-ethoxycarbonylaminonitrobonzene.

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His paper flat printing plate of the Hotaprint CjjJ type comes with a solution of:

36 g of ^ N-Iaethyl-N-benzylamino - ^ - C ^ -'- chlorpherioxy) - ^ - N-methyl-N-ethoxycarbonylaminobenzene diazonium chloride / sinking chloride double salt 200 ml of ethanol (96 %) and
800 ml of water
sensitized, and dried.

The photosensitive printing plate has excellent durability. It becomes image-wise under a transparent one Ink drawing exposed until the diazo compound is underneath the non-image parts of the drawing are completely faded. The image on the printing plate is made by wetting the Image side of the plate with a solution of 12 g of phloroglucinol

11 g citric acid

87 g of disodium phosphate - 2H ₂ O in 1000 ml of water
developed.

The plate is then weighted off with water using a sponge.

The plate has a very dark black image, which takes up printing ink very selectively. 200 good offset prints can be made from the plate.

The diazo compound used in the above example was made as follows:

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4-N-Methyl-IjT-benzylamino-5 - (^ '- chlorophehoxy) -2-chloronitrobenzene was reacted with methylamine and aaylated with ethyl chloroformate. From 4 ~ N-Methyl-N-benzylamino-5 - (^ ^l -chlorphenoxy) -2-N-methyl-N-äthoxycarbonylaminonitrobenzol which melts at 123 ⁰ C, the diazonium salt mentioned above in the usual manner by reduction and diazotisation obtain.

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Claims (3)

PATENT CLAIMSΛ ~ \ 1. diazotype material sensitized with a benzene diazo compound, the group para to the diazo group is a tertiary amino group in the meta position to the diazo group, a substituted or unsubstituted phenoxy group and para to the phenoxy \ a further substituent, characterized \ that the latter substituent is a group of the formula j ^ CO-R ₂ wherein R. is a substituted or unsubstituted alkyl, branched Alkyl or unsaturated alkyl group, a cycloalkyl or aralkyl group and CO-Rp represents an acyl group. 2. diazotype material according to claim 1, characterized in that it is with a diazo compound of the formula wherein X is an anion, R. a substituted or unsubstituted one Represents an alkyl, branched alkyl or unsaturated alkyl group, a cycloalkyl or aralkyl group, CO-Ro an acyl group is, R, and R ^, substituted or unsubstituted alkyl, mean branched alkyl, aralkyl or cycloalkyl groups or together with the nitrogen atom form a saturated heterocyclic ring and Z has one or more substituents of Group: represents halogen, methyl, alkoxy and dialkylamino, is sensitized. 10984 0/1841 3. Sinkomponentendiazotypiematerial according to claim 1, characterized characterized in that the diazo compound is in para position to Halogen-substituted phenoxy group an N-alkyl-N-alkoxjcarbonylgruppe and carries a light dialkylamino group in the para position to the diazo group. The patent attorney 109840/1841