DE2043335A1 - Method of diazotype multi-color reproduction and color material for its implementation - Google Patents

Description

PATE NTAN WALTE

Dr. D. Thomsen Dipwng. H. Tiedtke G. Biihling Dining. R. Kinne

MUNICH 2 VALLEY 33

TEL. 0811/226834 295051

CABLES: THOPATENT TELEX: TO FOLLOW

W. Weinkauff

ÖD / * 5 * 3 OC RANKFURT (MAIN) 50 L U 4 O O O 0 UCHSHOHL 71 I TEL. 0811/514668

Answer requested to: Please reply to:

8000 Munich 2 September 1, 197c T 38o7 / case K-15 (Mita) / IS

Mita Industrial Company Limited Osaka (Japan).

Procedure for multicolor diazotype reproduction and coloring material for its implementation

The invention relates to a coloring material for use in multicolor diazotype reproduction; In particular, the invention relates to a dye material for use in diazotype multi-color reproduction, which contains a substance volatile in heat which can selectively dye parts of a photosensitive paper according to predetermined parts of an original into different hues or colors without substantial color mixtures. ·

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There has already been a method of diazotype color reproduction proposed, which is based on the knowledge that given points of a template are reproduced in different colors can be, regardless of different or similar light transmission in the template by following the process steps carries out: (A) Exposure of the light-sensitive diazotypic material with a content of at least one diazonium salt (c) and (B) heating a layer of at least one in the Heat volatile or sublimable coupler (a), which is the photosensitive Diazotype material is applied at a location that corresponds to a predetermined location of the original, this both stages are carried out simultaneously or in the order (A) - (B) or (B) - (A), and then the exposed photosensitive material developed in the presence of a coupler (b) which has a slower coupling rate under the developing condition as the heat-volatile or sublimable coupler (a).

In this diazotype multicolor reproduction process a heat-volatile or sublimable coupler is applied to the back of one or more predetermined locations applied to a transparent or semi-transparent template.

This screen transferable coupler comes in the form of a ink-like mixture, waxy mixture or the like. on the back of an original by coating, transferring or others Mothodon applied, but in general are in the heat

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volatile or sublimable couplings chemically unstable and tend to discolor easily. When the coupler applied to the back of an original discolors and the light transmission is decreased, the development treatment causes coloring of places other than those specified Positions correspond to the original, with the result that an image reproduction with excellent separation sharpness cannot be achieved is.

In this diazotype multicolor reproduction process, the heat-volatile or sublimable coupler becomes heat-volatile transferred from the EchichtwdescKüpplers on the back to a light-sensitive diazotype material. It was experimentally determined that under the same reproduction conditions only a few multicolored copies of a treated original are achievable.

According to the invention it has been found that one can avoid this limitation can by creating a volatile or sublimable in the heat Acid addition salt of a heat volatile or sublimable azo coupler component with an amino group is used.

Accordingly, it is an object of this invention to provide a coloring material for use in the multicolor diazo printing process to create which is inherently chemically stable and therefore has excellent storage stability.

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It is also an object of the invention / a

To create coloring material for use in the diazotype multi-color reproduction process, which does not significantly impair the transparency or semi-transparency of the original when eg is applied to the back of the original by coating, description, transfer or gluing, and which "only colors those areas that predetermined locations of the original match, and provides multi-color copies that give an accurate picture of the pros W position image.

Another object of the invention is to provide a coloring material for use in the diazotype multicolor reproduction process create that makes it possible to consistently produce a large number of multicolored copies of one with the one by heat transferable coupler treated original.

The aforementioned object of the invention is .by fc eir; Coloring material for use in multicolor diazotype reproduction dissolved, which is volatile or sublimable in the heat .Acid addition salt of a heat-volatile or sublimable azo coupler component with an amino group contains.,

Suitable / in the heat volatile or sublimable Azokupplerkomponenten having an amino group are amino phenols, aromatic amines, and active methylene group-containing amines ".. Typical examples of such azo coupler are the following:

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Benzene-type aminophene and amine

meta-aminophenol

para-aminophenol

ortho-aminophenol

meta-phenylenediamine

para-phenylenediamine

2-aminoparacresol

3-aminoorthocresol

3-aminoparacresol

5-aminophosphorus cresol

para-chloroaniline

meta-aminobenzoic acid and

3,4-diaminoparatoluene

Amino compounds containing active methylene groups

1-Pheny 1-3-methylpyrazolone- (5) 1-Pheny1-3-carboxypyrazolone 3-methylpyrazolone acetoacetic anilide Acetoacetic acid-o-chloroanilide and

para-carboxyacetanilide (para-carboxyacetoaceto-

anilide)

Each of the above-mentioned couplers can be used according to the invention, but preference is given to using those which have a melting point of 100 to 15 ° C. Among these are preferably those whose ability to be scratched or sublimated is considerably increased, v * ·· ^ - ^; · ^{3 3} ^ ^ ^ai "

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nem. · Acid addition salt. As a typical representative such coupler components can be meta-aminophenol and phenylmethylpyrazolone to be named.

meta-aminophenol melting point. = 122 ° C

meta-aminophenol hydrochloride

Schiaelzpunkt = 119 C

,O.

l-phenyl-3-methylpyrazolone- (5) -

Melting point = 127 ^W C

l-phenyl-3-methylpyrazolone- (5) -

hydrochloride melting point - 96 C

If you do the staining experiments using the above Coupler components in connection with a light-sensitive diazotype material with a content of 4-diazo-IT, TI-dimethylaniline chloride'1 / 2ZnCl ^ double salt and 2,7-dihydroxynaphthalene-3,6-disulfonic acid, sodium salt performs, it turns out that while free meta-aminophenol can result in 10 to 20 copies Hydrochloride can produce 30 to 40 copies under the same conditions, and that the use of the hydrochloride salt of l-bhenyl-3-raethylpyrazolon- {5) the number of copies by 20 to 30 leaves opposite, the free l-phenyl-3-methylpy-

razolon * (5) can increase.

According to the invention, the above-mentioned couplers are used in the form of acid addition salts. Every acid becomes an education of the acid addition salt of the coupler components used, sofera the salts obtained are volatile or sublimable in the heat are.

As an acid to be used preferably in accordance with the invention

w-fctes the following links $$ nar.nt;

Inorganic acids such as: hydrogen chloride
Hydrobromic acid and other hydrochloric acid η Organic sulfonic acids such as: p-toluenesulfonic acid and o-toluenesulfonic acid; and

Carboxylic acids such as:

Chloroacetic acid (ClCH ₂ -COOK) chloropropionic acid (ClCH ₂ CH ₂ 'COOH) acetic acid (CH ₃ COOH) salicylic acid (CgH ₄ (OH) (COOH)) 2,6-dichlorobenzoic acid (CgHfL ₂ (COOH)) a, 4-dimethy Benzoic acid (CgH ₃ (CH ₃ ) ₂ COOH) oxalic acid ((COOH) ₂ ) oxalic acid hydrate ((COOH) ₂ '2H ₃ O) o-sulfobenzoic acid (CgH ₄ (CO ₂ H) (SO ₃ H) trichloroacetic acid (CCl ₃ COOH) formic acid (HCOOH) benzoic acid (CgH ₅ COOH) methacrylic acid (CH ₂ = C (CH ₃ ) COOH) and butyric acid (CH ₃ CH ₂ CH ₂ COOH)

The production of seed addition salts <& £ azo couplers components can be checked according to a conventional method by Ver mixing an azo coupler component with one in a suitable medium.

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According to the invention, the acid addition salt of the azo coupler component is used converted into a coating mixture by placing the salt in a liquid, semi-solid or solid dispersion medium dissolves. The preparation of such a coating mixture is described below with the aid of a few examples. The acid addition salt can before! Preparation of the coating mixture, or one forms it while making the coating mixture manufactures. In the latter case it is possible that an excess P of acid is present in the mixture.

(1) Ink-like mixture:

Acid addition salt volatile in the heat

of the heat transferable coupler 5.0 to 25.0%

Binder 0 to 5.0%

Coloring material 0 to 3.0%

Dispersing aid 0 to 5.0%

Dispersion medium residual amount

W Aliphatic alcohols such as

Dimethylformamide, ethanol, n-rpropanol, isopropanol and isobutyl alcohol, aromatic solvents such as benzene, toluene and xylene, Esters, neutral liquids containing OH groups with a boiling point of 100 to 240 ° C can be used, such as water, alcohols with a high boiling point, e.g. n-hexyl alcohol, η-heptyl alcohol, 3-heptanol, 4-heptanol and octanol, and glycols, e.g. glycerine, Ethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, 1,4-butanediol and 2,3-butctidiol ,. You can use these solvents

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use either individually or in combination. Than in the heat volatile "acid addition salts can be used those mentioned above. It is possible to add a coloring material to the To promote film formation of the mixture, or to use a binder, to achieve a good fixation of the coupler.

The mixture according to the above approach is applied to the back a place on the template that is to be given a different color, using a brush, a built-in felt pen, a Ballpoint pen, coating roller, sprayer or a printing device.

(2) Waxy mixture:

Acid addition salt of the heat transferable coupler, volatile in the heat, 5 to 25%

Wax '' '85 to 15%

oil 10 to 40%

Coloring material 0 - 20.0%

The mixture according to this approach is given a pencil-like or piece of chalk-like shape and coated with it on the back of a part of the template that is to be given a different color. It is also possible to use a pressure-sensitive sheet or sheet. to form gea transfer material by bringing the above mixture to melt or in a suitable solvent: dissolving and the melt or solution to a substrate or a support such as plastic or zBPapier Im applying!. That formed

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.- ΙΟ -

The pressure-sensitive transfer sheet is placed on the back of an original sheet and then pressed with a typewriter or writing medium to form a heat transferable layer on the back of an image intended for a different color.

(3) Coupler transferring sheet or sheet Material:

The ink-like mixture according to (1) or a mixture obtained by incorporating a binder or a stretch into such an ink-like mixture is applied to a transparent or semitransparent sheet, such as paper, plastic film or nonwoven material. The thus formed heat transferring coupler sheet is cut to the desired size, if necessary, and then placed on the back of a position of an original intended for a different color. It is possible to have a pressure-sensitive adhesive layer on the back W. of the coupler transferring layer to prevent it from peeling off from the original.

treated with the coloring material according to the invention The original for multicolor diazotype reproduction is placed on a light-sensitive diazotype material containing at least one diazonium salt (c); the whole is exposed to light and subjected to the heat transfer treatment of the coloring material. The exposed and heat-transferred photosensitive material is then developed in the presence of a coupler (b) which

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- ■ 11 -

has a slower coupling speed than the coloring material under the same developing conditions.

The multicolor reproduction using the coloring material of the present invention is carried out according to the following procedure carried out.

At least one layer of the coloring material according to the invention is applied to the reverse side of one or more predetermined areas of a transparent or semitransparent original in order to produce an original for multicolor reproduction. The master thus formed for multicolor reproduction is placed on a light-sensitive diazotype material containing at least one diazonium salt (c) in such a way that the light-sensitive surface of the light-sensitive material confronts the layer of the heat transferable coupler; the exposure and heating are either simultaneous or performed one after the other in this order or in the opposite order. In this way, the heat transferable coupler (a) is transferred by heat to the surface of the predetermined position of the photosensitive material and the light decomposition of the diazonium salt (c) in the photosensitive material is effected depending on the light transmission of the original. If the exposed photosensitive material is developed in a manner known per se, the diazonium salt (c) in the unexposed area is selectively and preferably deposited at the predetermined point to which the coupler (a) of the coloring material was transferred by heat with the coupler around, around

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to form a dye (c) - (a), and put elsewhere the diazonium salt (c) reacts in the unexposed area with the coupler (b), which has a lower coupling rate than the heat transferable one Coupler (a) has to give a dye (c) - (b)

Ip

form. In this way you get a multicolored reproducible Copy in which the specified point is colored in a different shade or a different color than the other point.

What is essential is that between that fleeting in the fawns or sublimable acid addition salt, coupler (a) of the coloring material, coupler (b) and diazonium salt (c) according to the invention are to be used, the following relationships are established:

I. The heat-volatile or sublimable coupler (a) has a higher one under the developing conditions Coupling speed than the coupler (b).

II. The dyes (b) - (c) formed during development, * (a) - (c) and (a ') - (c) .... differ from one another

lichen colors.

As coupler component (b) with a slower coupling speed as the coupler component (a) of the coloring material according to the invention one can use phenol derivatives, naphthols, active methylene groups containing compounds, heterocyclic compounds and others commonly used in diazotype photosensitive material Use coupler. 'Specific examples of these couplers

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- ¹³ - 2 (M 33 3

are the following:

Phenol derivatives . ^#

2,5,6-trimethylphenol

2-hydroxymethylphenol

ß- (2-hydroxyphenyl) propionic acid 2- (w -phenylaminomethyl) -phenol ß- (4-methyl-2-hydroxyphenyl) -glutaric acid 2,5-dimethyl 1- 6- (N-dimethylaminoiriethy 1) -phenol 1 , 3-dimethyl ether of pyrogallol CX -resorcinsäureäthanolamin

ß-resorcic acid. '

N-lauryl-p-aminophenol N-acyl-iti-arainophenol

meta- i ^ droxy-ace ^ anilid '· ortho-N-hydroxyphenyl-monoguanidine para-N-hydroxyphenyl-biguanidine 2 , 5-dimethyl-4-morpholine methyl phenol.

2-methyl-5-isopropyl-morpholinmethy! Phenol 4-Morpholinmethylresorcinmonomethyläther 3,3 ', 5-Trihydroxydiphenyl 3.3 X, 5,5'-Setrahydroxydiphenyl 2,2', 4, 4 × -Tetrahydroxydipheny1 2, 4, 4 '-Trihydroxydiphenyl-2'-sulfonic acid 2, 4, 6, 3 ^f, 5 "-Pentahydroxydiphenyl ^and 2, 2 ', 4/4' -Tetrahydroxydiphenylsulfid.

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Naphthols

2,3 ~ dihydroxynaphthalene-6-sulfonic acid 2-naphthol-3,6-disulfonic acid 2,7-dihydroxynaphthalene-3-sulfonic acid 2,8-dihydroxynaphthalene-6-sulfonic acid 1,8-dihydroxynaphthalene-8-sulfonic acid 1,8-aminonaphthol-5-sulfonic acid 2,7-dihydroxy-3,6-disulfonic acid 1,8-benzoylarainonaphthol-2-sulfonic acid 1,8-dihydroxynaphthalene-6-sulfonic acid 2-Hydroxy-3-naphthione-N-ß-hydroxyethylamide 2-Hydroxy-3-naphthione-N, N-bis-ß-hydroxyl ether amide 8-Hydroxy-2-naphthione-hydroxyethylamide 1- (N-carbethoxymethylamino) -8-naphthol-4-sulfonic acid 5- (para-nitro) -benzamido-1-naphthol 1-hydroxynaphthyl-7-phenylguanidine 2-hydroxynaphthy1-8-biguanidine l-Napthol-3- (N-ß-hydroxyethyl) sulfonary acid 1-naphthol-3- (N-o-methoxyphenyl) sulfonamide

Bis - / "5-hydroxy-7-sulfonaphthyl '(2) J-amine

N ^ N-Bis ^ l-hydroxy-S-sulfonaphthyl-iö) J -thiourea

Compounds containing active methylene groups

Acetoacetic acid cyclohexyl arid Acetoacetic acid benzylamide Cyanoacet anilide
Cyanoacet morpholine

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Heterocyclic compounds

1- (3'-SuIfoamid) -phenyl-3-methylpyrazolone-5 1- (4-Carboxy-ethylphenyl) -3-dodecylpyrazolone-S 3-Hydroxy-1,2-naphthylimidazole 2-Hethy1-4-hydroxybenzimidazole 7-24ethyl-4-hydroxybenzothiazole 1,7-dimethyl-4-hydroxy-benzotriazole S-hydroxythiophene-S-carboxylic acid and 1,3 ^ -cyclopentadione. .

As the diazonium salt-containing light-sensitive material, a one-component light-sensitive material comprising a diazonium salt and an optical aid can be used contains, as well as light-sensitive two-component material, that is, a diazonium salt, a coupler (b) and an optical Contains tools. Selects suitable photosensitive materials depending on the development method. The photosensitive materials usually consist of a carrier such as paper, Plastic film, fiber fabric, non-woven material and metal foil and an applied sensitizing mixture together. The manufacture of such a photosensitive material is now being carried out described using a few examples.

A. Photosensitizing Mixture for Dry Developing:

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Azo coupler component (b)
, (with a slower coupling rate than the heat transferable coupler component (a). of the coloring material) 0.4 to 4% diazo compound (c) 0.2 to 4% non-volatile organic acid 0.1 to 5.0% coloring material, 0 to 0.025% development accelerator, 1 to, 10% _: extender 0 to, 2.5%. Solvent, residual amount

The photosensitizing mixture according to the above Approach is applied to a support, such as paper and plastic film, and dried to form a photosensitive sheet to build.

B. Photosensitizing mixture of the. Zw.eikompo- ™ nent type for wet development:

Azo coupler component (b)
(with a slower coupling rate than the heat transferable coupler component (a) of the dye material). 0.5 to 4 p

Diazo compound (c) 0.2 to 4%

organic acid (non-volatile) 0.1 to 5.0% extender 0 to 2.5%

1 0 9 8 1 3 /. U 9 8 -

Coloring material 0 to 0/025%

Remaining solvent

The photosensitizing mixture according to approach B. are applied to a support such as paper and plastic film and dried to form a photosensitive sheet.

Any conventional photo-decomposable diazonium salt can be used for the mixture given above, provided it is under. ä the development conditions is able to with the heat transferable 'coupler component (a) of the coloring material. and to couple the coupler (b), which has a slower coupling rate than the coupler component (a).

Examples of such diazonium compounds are as follows:

para-phenylenediamine-N, N-substituted compounds λ of the following general formula:

where mean »

X «in anion,

R 'and R "each represent an aliphatic group,

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Z and Y groups which can be inserted into the benzene yarn.

Specific examples of this type of connection are as follows;

4-Diazo-N, N-dimethylaniline (simplified "MA-Salz") 4-Diazo-N _/ N-diethylaniline (simplified ¹¹ EA-Salz ") 4-Diazo-N-ethyl-N-ß-hydroxyethylaniline

(simplified ¹¹ EH-SaIz ")

4-Diazo-N / N-bis-ß-hydroxyethylaniline.

4-Diazo-N-methyl-N-β-hydroxyethylaniline 4-diazo-N-ethyl-N-ß-hydroxypropylaniline,

other diazonium salts of alkyl or hydroxyalkyl groups N, N-substituted p-phenylenediamines, '

■ 4-diazo-N-ethyl-N- (ß-diethylamino) -ethylaniline 4-diazo-2-chloro-N, N-diethylaniline 4-diazo-2-methyl-N _/ N-diethylaniline '4-diazo-2 - iodine-N, N-diethylaniline

4-diazo-2-trifluoromethyl-N, N-diethylaniline;.

4-diazo-N-ethyl-N-benzylaniline and 4-diazo-N-methyl-N-benzylaniline ( simplified methylbenayl "

Aminohydrochinonätherartige compounds of the following general formula: ·

COPY

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where mean:

R, R ¹ and R "are alkyl or aryl groups and ■ · ■ X is an anion."

Specific. Examples of this. Connection types are as follows:

4-Diazo-2,5-dibutoxy-N, N-diethy! Aniline

4-Diazo-2,5-diethoxy-N-benzoylaniline (simplified "BB-Salz") 4-Diazo-2,5-diethoxy-N-ethyl-N-benzoylaniline. 4-Diazo-2,5-dibenzyloxy-N-benzoylaniline 4-Diazo-2-chloro-5-methoxy-N-benzoylaniline 4-Diazo-2,5-diethoxy-I-benzoylinethylaniline -. 4-diazo-2,5-diethoxy-N-benzoyloxymethylaniline and other 4-diazo-2 _/ 5-dioxyalkyl (or-dioxyarl) -H-alkyl- (or-aryl) compounds, and their derivatives.

Aminodiphenyl compounds , aminodiphenylamine compounds and their analogues according to the following general formulas:

which: ·

X is an anion, · COPY

R is a divalent aryl group,

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R ^{1 is} a monovalent or divalent aryl or

Alkyl group,

A is a divalent group or a direct bond, RAR ¹ e.g. diaryln (A; -NH-), diphenyl (A: direct bond), diphenyl oxide (A; -0-), diarylmethane (A: "CH ₂ * stilbene (A ; -CH = CH-) and diaryl or dialkyl sulfide (A: -S-).

Fe specific examples of this type of connection are as follows :

para-diazophenyl arain

4-diazo-2,5,4'-triethoxydiphenylamine

4-diazo-2,5,4-triethoxydiphenyl

4,4'-bis-diazo-2,2 ', 5,5'-tetrahydroxydiphenylmethane

Bis-diazo-8,8't: dichloro-5,5'-dimethoxybenzidine

4-diazo-2,5-dimethoxyphenylethyl sulfide and

4-diazo-2,5-diethoxy-4'-methyldiphenyl sulfide.

Heterocyclic amine derivatives of the following general formula:

2 ~ 2 '

where mean:

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X an anion,

Y and Z groups that can be inserted into the benzene nucleus, A is a direct bond (phenylpyrrolidine) or a divalent group such as -O- (morpholine), -S- (thiomorpholine) and methylene (phenylpiperidine).

Specific examples of this type of connection are as follows:

4-diazo-2,5-dibutoxy-N-phenylmorpholine, 4-diazo-2,5-diethoxy-N-phenyliaorpholin 4-diazo-2-methoxy-N-thiomorpholin 4-diazo-N-phenylpiperidine '■

. 4-diazo-N-phenylpyrrolidine

4.-Diazo-2 _/ 5-di-n-butoxy-N-phenylpiperidine and other derivatives of the heterocyclic 4-diazo-N-phenyl- · amines.

N, N-substituted ortho-phenylenediamine derivatives and ortho-aminophenol derivatives.

Specific examples of this type of connection are as follows:.

2-diazo-4-methylmercapto-N, N · dimethylaniline ^ -Diazo-S-benzoylamino-N / N'-diinethylaniline and 2-diazo-1-naphthol-5-sulfonic acid.

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The above diazonium compounds can be used in the form of a relatively stable sulfuric acid or hydrochloric acid salt. They can also be used in the form of a double salt with zinc chloride, tin chloride, aluminum sulfate or the like. Furthermore, they can 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. These diazonium salts can be used either individually or in the form of a mixture of two or more of them .

Citric acid, tartaric acid, oxalic acid, sulfamic acid, Use boric acid, phosphoric acid, etc. As an extender one can use dextrin, gum arabic, colloidal silicon dioxide, etc. use. 1,3,6-Naphthalene-sodium trisulfonate can be used as stabilizers and other aryl sulfonic acids. Polyhydric alcohols such as glycerine and ethylene glycol act as development accelerators taken. Coloring material is used to mark the light-sensitive area and to increase the whiteness of the Used, whereby blue dyes such as methylene blue and patent blue are used for this purpose. As a solvent you can use water and organic solvents such as alcohols, acetone, Use toluene, xylene and esters.

The photosensitive sheet thus formed is placed on an original, on the back of which the above- mentioned coloring material has previously been applied to one or more predetermined locations

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in such a way that the reverse side of the original which has been treated with the coloring material confronts the photosensitive layer of the photosensitive sheet. If the whole thing is exposed to light and heated, then the coupler component (a) of the coloring material is transferred by heat to the areas of the photosensitive sheet corresponding to the specified areas of the original and the decomposition of the diazonium salt (c) occurs due to light depending on the light transmission of the original . The photosensitive sheet thus treated is in the presence of an A coupler (b) which has a slower coupling rate than that in the. ; Coupler component (a) present in the coloring material has been developed in a manner known per se. The coupler (b), which has a relatively low coupling rate, may be supplied in advance in the light-sensitive material or may be in a developing liquid. -

Developing either ν with \ the will dry or carried out with the wet method. In the dry process, development is achieved by exposing the heated and exposed photosensitive sheet to a gas mixture of ammonia and steam. In the case of a photosensitive paper for wet developing which is of a one-component type, a liquid developer is made according to, for example, the following approach

Coupler (b) (with a slower coupling rate than that by heat 109813/1498 transferable coupler component (a)

des Färäremat'erJaJ s. 0.2 to 1.5%

alkaline agent 0/5 to 20 %

Reducing agent 0 to 20%

surfactant 0 to 0.5%

Water remaining

onto the heated and exposed photosensitive sheet according to an ordinary method such as dipping, rolling and Spray Coating Applied In the case of a two-part photosensitive sheet, developing is accomplished by the heated and exposed photosensitive sheet with an aqueous liquid developer containing an alkaline agent brings in touch.

According to the invention, when the heat-volatile or sublimable coupler (a) is used in the form of a Acid addition salt possible, v / effective discoloration of the material for multicolor reproduction during storage or after its application to a template to prevent and to avoid the disadvantage of the known product that the light transmission the area of the original which has been treated with the coloring material as a result of the contamination of the treated original is reduced. Thus, according to the invention, sharp multicolored reproducible copies can be obtained in which areas the specified areas of the original correspond to ^ are selectively colored in different colors or hues.

Furthermore, according to the invention, it is possible to make a large number of copies, for example 30 to 100 sharp copies, from a treated original

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χ ■

Copies, to get.

Examples of the production of ink-like mixtures for treating the original

example 1

It becomes an ink-like mixture according to the following approach as a yellow color forming agent for back treatment

■ a template etc. produced:

Acetoacetic anilide acetate salt 25 g

Ethylene glycol 15 g

Alkyd resin 5g

Ethanol 100 ml

This mixture is used immediately as a material that is applied to the back of an area of the original, which "should be reproduced in yellow, applied with a brush, a coating roller or a spray device, or after being inserted into a felt-tip pen or ballpoint pen, it is used as a material for treating the back of an area of the original is used, which should be displayed in yellow.

Example 2

An ink-like mixture is produced according to the following approach as a red color-forming agent for treating the reverse side of a ν template:

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1-phenyl-3-methylpyrazolone- (5). 20 g Hydrochloric acid (36%) IO ml glycerin IO g Ethanol 50 ml water 50 ml

This mixture is used immediately as a material that is applied to the back of an area of the template that should be reproduced in red, with a brush, a coating roller or a spray device is to be applied, or it is inserted into a felt pen or used a ballpoint pen as a material for treating the back of an area of the original that was reproduced in red is.

Example 3

It is an ink-like mixture according to the following approach as a brown color-forming agent for treating the reverse side made from a template:

meta-aminophenol hydrochloride 30 g

Ethylene glycol 15 g

Vinyl acetate resin 5 g

Methanol 100 ml

The above mixture is immediately used as a material

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rial used on the back of an area of a template, which is to be reproduced in brown, with a brush, a coating roller or a spray device is to be applied, or it is after use in a felt-tip pen or a Ballpoint pen as a material for treating the back of a Area of the original used, which is to be reproduced in brown.

Example 4

It becomes a yellowish-brown color forming agent made by using meta-phenylenediamine hydrochloride instead of meta-aminophenoIiydrochloiriid the mixture according to Example 3 used will.

Example 5

A yellow color forming agent is made by adding 3-amino-ortho-cresol hydrochloride instead of meta-aminor phenol hydrochloride of the mixture according to Example 3 is used.

Examples of the manufacture of waxy agents to treat the back of

templates

Example 6

It is a waxy llischung that forming as a yellow color agent for treating the back of a template to use manufactured by:

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meta-phenylenediamine hydrochloride 30 g

Stearic acid 100 g

Paraffin 50 g _

Terra alba 50 g

Diatomaceous earth 20 g

are hot melted and the melt is solidified.

This mixture is given a pencil-like shape; it is used as a material to be applied to the back of an area of an original that is in another Color tone is to be reproduced.

Example 7

It becomes a v / ax-like mixture that acts as a brown color-forming agent for the treatment of the reverse side of an original to be used, produced by:

meta-aminophenol hydrochloride 40 g

Paraffin 50 g

Terra alba 70 g

cloudy wax 20 g

Stearic acid 100 g

Magnesium carbonate 20 g

are hot melted and the melt is solidified.

1 0 9 8 1 a / U 9 8

The mixture produced in this way becomes a given pencil or chalk-like shape; it is used as a material for coating the back of an area of an original used, which is to be reproduced in a different hue.

Example 8

It becomes a waxy mixture according to the following approach manufactured as a red color forming agent to treat the reverse side of an original: ™

1-phenyl-3-methylpyrazolone (5) hydrochloride ν 20 g Stearic acid 100 g

Paraffin ~ 50 g

Diatomaceous earth. 30 g

cloudy wax. ' 20 g

The above mixture is given a pencil or chalk-like shape; it is used as material for coating the back of a portion of a template, the ren On the other in a% tint to be reproduced ..

Example 9

To the mixture according to Example 8, 100 g of mineral oil, 50 g Given oleic acid and 20 g permanent red; the mixture is kneaded in a bowl mill to uniformly disperse the additive components. After that, the kneaded mixture is turned on Substrate, such as paper, for making a pressure-sensitive

10 981 37 U98

Copy sheet applied. That on this. Many copy sheets formed is placed on the back of a template and pressed on with a typewriter or other writing device. Accordingly the sheet is used as a material to form a layer of wax agent on the back of the image of the original, that is to be reproduced in a different shade.

Examples of the manufacture of coupler transferring sheets for treating the back side of originals

Example 10

It is a mixture according to the following approach as a brown color forming agent for treating the back of a Template made:

meta-aminophenol hydrochloride 30 g

Triacetate resin 10 g

Methanol 50 ml

Acetone 50 ml

This mixture is applied to a transparent or semi-transparent sheet such as a polyester film with a roll coater and dried at a relatively low temperature (40 ° to 50 ° C) to form a heat transfer sheet of the coupler to manufacture. After cutting to the desired size as required, the Blattials material is used that is based on the reverse side of the area of an original that is to be reproduced in a different color tone is to be applied.

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- '31 -

Example 11

It becomes a mixture forming a red color Agent for treating the reverse side of an original -used ' to be prepared by l-phenyl-3-methylpyrazolone- (5) -hydrochloride instead of raeta-aminophenol hydrochloride (Example 10) is used. A sheet 2ur is made from this mixture Heat transfer of the coupler made to achieve a red color. ^

Application example 1

Multi-color forming photosensitive diazo type paper for use in dry developing

A solution is prepared according to the following approach: 4-Diazo-III-ethyl-N-hydroxyethylaniline chloride.

1/2 ZnCl ₂ 15 g Diethylene glycol 60 g citric acid 20 g 2,3-dihydroxynaphthalene-6-sulfonic acid 7 g Zinc chloride 50 g Thiourea 25 g Patent blue 0.1 g water Remaining amount all in all 1 liter

10 9 813/1498

The solution is made according to a known coating procedure on a paper as a basis, a.B. with an air knife coating device, applied and dried to form a photosensitive sheet.

This sheet is placed on an original with the back of an area with an ink-like mixture according to Example 1 and the back of another area is treated with the ink-like mixture according to Example 2. After that, will the whole thing heated at 70 ° to 100 ° C. and exposed to a mercury lamp to form a latent image of the diazonium salt.

The sheet treated in this way then becomes a development '. subjected to gaseous ammonia and steam. Thus, to obtain a clear multi-color copy, the diazonium salt is yellow in the NEM in är area corresponding to the group treated with the ink according to Example 1 region, and wherein in a range corresponding to the with the ink Example 2 treated in accordance with the field , the diazonium salt is colored red, and in the "other ... areas, which correspond to the untreated areas, the diazonium salt is colored bluish purple. The resulting copy is very clear and shows excellent color separation.

Application example 2

In repeating Example 1 using 4-diazo-M, N -dimethylanilinchlorid.1 / 2ZnCl ₂ instead of 4-diazo

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N-ethyl-N-hydroxyethylaniline chloride.1 / 2ZnCl ₂ , a multicolored reproducible copy similar to that of application example 1 is obtained.

Application example 3

Multi-color forming photosensitive paper for use in dry developing

A solution is prepared according to the following approach: i

^ Diazo-NjN-diethylaniline chloride. 1/2 ZnCl ₂ 15 g Ethyienglykol 50 g

Citric acid 20 g

2,7-dihydroxynaphthalene-3,6-disulfonic acid

Sodium salt. 8g

Zinc chloride 20 g

Thiourea 100 g

1,3,6-Naphthalenetrisulfonic acid sodium salt 20 g patent blue * ■ 0.1 g ^

Water remaining

total of 1 liter

According to a known coating method, e.g. with a. Air knife coating device, becomes a photosensitive Paper made from this solution. The photosensitive paper is placed on a template / with an area of the Back with the ink-like mixture according to Example 2 and another area of the back with the mixture according to the example

1 0 9 B 1 3/1 4 90

• 3 is dealt with. The whole thing is exposed to a mercury lamp and heated. After that, the sheet treated in this way becomes developed with gaseous ammonia and steam. In this way a clear three-color reproducible copy is obtained an area corresponding to the area of the template treated with the mixture according to Example 2 is colored red, ain Area that corresponds to the area treated with the mixture according to Example 3 is colored brown, and the other areas, which correspond to the untreated areas of the original are colored blue. The copy is very clear and shows excellent Color separation.

Application example 4

Multi-color forming photosensitive paper for dry developing

A solution is prepared according to the following approach:

4-diazo-N, N-diethylaniline chloride. 1/2 ZnCl ₂ 20 g

Diethylene glycol citric acid

Zinc chloride thiourea hydrochloric acid (36%) patent blue water

all in all

1 0 0 Γ! Π / 1 A Π Π

50 G 3 G - (2) 7-amine 14 G 30th G 25th G 10 ml 0.1 G Remaining amount 1 liter

This solution is applied by a known coating method, e.g. with an air knife coating device,
applied to a substrate for photosensitive paper and dried. The photosensitive paper produced in this way is placed on an original in which an area of the back is covered with the wax-like mixture according to Example 7
and another area of the back is treated with the v / axle-like mixture according to Example 8. After that the whole thing
heated with a mercury lamp and printed, after which it is developed with gaseous ι ammonia and steam. In this way
a clear three-color reproducible copy is obtained, in which an area which corresponds to the area treated with the treatment agent according to example 7 is colored brown, another area which corresponds to the area treated with the treatment agent according to example 8 is colored red, and the remaining areas, which correspond to the untreated areas,
are colored dark blue. The copy is very clear and shows excellent color separation.

Application example 5

Multi-color forming photosensitive paper for use in dry developing

A solution according to the following formulation was prepared:

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50 G 20th G 8th G 3 G 10 G 50 G 20th G 0.1 G Remaining amount 1 liter

^ Diazo-NfN-dimethylaniline chloride. 1/2 ZnCl ₂ 20 g

Diethylene glycol tartaric acid

2,7-dihydroxynaphthalene-3,6-disulfonic acid, sodium salt

Resorcinol monoethyl ether sink chloride thiourea

1,3,6-naphthalenetrisulfonic acid sodium salt

Patent blue Via s s er

all in all

From this solution, in the same manner as in Example 1, a photosensitive paper is made by coating and Drying made. The photosensitive paper is placed on a template with an area of the back with the Coupler heat transfer sheet according to Example 10 and another area of the back with the treating agent according to Example is treated. Then the whole thing is heated with a mercury lamp and exposed to light, after which one with gaseous ammonia and Steam develops. In this way a clear three-color reproducible copy is obtained in which an area corresponding to the corresponds to the area treated with the treatment agent according to Example 10, colored yellowish brown .is, another area, which corresponds to the area treated with the treatment agent according to Example 11 is colored red, and the remaining areas

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corresponding to the untreated areas., colored black are. The copy is clear and precise with no color mixing.

Application example 6

Multi-color forming photosensitive paper for dry developing

A solution is prepared according to the following approach:

4-diazo-N, N-dimethylaniline chloride tartaric acid Ethylene Glycoi 2,4,2 ', 4' -Tetrahydroxydiphenylsulfid Thiourea zinc chloride patent blue water

all in all '

This solution is applied to a semitransparent paper, for example tracing paper, and dried to produce light-sensitive paper. The photosensitive paper is placed on an original in which an area of the back has been treated with the ink-like mixture according to Example 2, in such a way that the treated area of the original confronts the photosensitive layer of the photosensitive paper. The whole thing is heated and exposed with a mercury lamp, after which gas form ammonia and steam are added to the atmosphere. H. _c \ uF

■ 1 Π Ί H U / ι. '♦ μ. ·; 0AD

30th G 20th G 50 G • 11 G 25th G 50 G 0.1 G Remaining amount 1 liter

this way becomes a clear two-tone reproducible, as Intermediate carrier or intermediate usable copy obtained in which an area that corresponds to that with the mixture according to Example 2 The treated area of the template is colored red and the other areas are the untreated areas of the template are yellowish-brown in color. The intermediate is clear and shows excellent color separation.

_ Application example 7

Multi-color forming photosensitive paper for use in dry or 1-pass development

A solution is prepared according to the following approach:

4-diazo-2 _/ 5-dibutoxy-N-phenylmorpholine.1 / 2ZnCl ₂ 15 g citric acid 30 g

Diethylene glycol 40 g

ß-Hydroxynaphtionsäureaminoäythylaminhydrochlorid 7 g ψ Thiourea 40 g

Zinc chloride 30 g

Patent blue 0.1 g

Water remaining

total of 1 liter

A photosensitive paper is made from this solution, by being coated in the same manner as in Application Example 1 and dried. The photosensitive paper produced in this way is placed on a template with an area i> M * Γη -:! -; t? i ':; πLt dnr tIntfüiactiqen Mifishunf -T- ηι ';:> B ^ hsriU ·! 1

10 9 0 1 \ n vna

BATH ORIGINAL

and another area of the back with the treatment material is treated according to Example 2, placed in such a way that the treated area of the original, the photosensitive layer of the photosensitive Paper faced. Then the whole thing is heated with a mercury lamp and exposed, after which one with gaseous Ammonia and steam or with an alkaline liquid developer developed according to the following approach:

Potash carbonate ..2Og

Sodium thiosulphate '40 g I.

Sodium bicarbonate 30 g

Potassium tetraborate 5g

Water remaining

total of 1 liter

In this way a clear three-color reproducible copy is obtained without significant color mixing Area of the area treated with the mixture according to Example 1 corresponds to the template, is colored yellow, an area that f corresponds to the area of the template treated with the mixture according to example 2, is colored red and the remaining areas, which correspond to the untreated areas of the original are colored blue.

Application example 8

Multi-color forming light-sensitive paper for use in dimensional winding

1098.13 / U9-8

A solution is prepared according to the following approach:

4-diazo-2,5-diethoxy-N-benzoylaniline. 1/2 ZnCl ₂ 15 g citric acid 10 g

Dextrin 20 g

Methylene blue 0.1 g

Water . Remaining amount

total of 1 liter

This solution is prepared on paper as a photosensitive paper base by a known method with an air knife coater or the like. applied and dried. The photosensitive paper produced in this way becomes on a template in which the back of an area has been treated with the wax-like mixture according to Example 8, such applied so that the photosensitive layer of the photosensitive paper confronts the treated original surface. Thereafter the whole thing is heated with a mercury lamp and exposed to light, and it becomes a liquid developer with the following approach

NW acid 15 g

Potassium carbonate 80 g

Sodium bicarbonate 30 g

Sodium thiosulfate 50 g

Borax 10 g

Water remaining

total of 1 liter

rolled onto the heated and exposed photosensitive paper for developing the photosensitive paper or

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sprayed. In this way, a two-tone copy of r.it Obtained clear color separation, in the area of the Eereigh -der- "template treated with the mixture according to Example 8 is colored red and the other areas, which correspond to the untreated areas of the original, are bluish-purple are colored.

Application example 9

Multi-color forming film · 'f

A solution is prepared according to the following approach:

^ Diazo ^^ - dibutoxy-N-phenylmorpholine. 1/2 ZnCl ₂ 15 g

Citric acid 10 g

ß-Hydroxynaphthoic acid ethanolamine 7 g

Triacetate resin · 15 g

oil blue ■ 0.2 g

Acetone '400 ml

Methanol 700 ml ä

This solution is coated on a polyester film with a bar coater and dried at a relatively low temperature (40 ° to 50 ° C) with warm air to form a photosensitive film. The film is placed on an original in which an area of the back of the original image is treated with the ink-like mixture according to Example 1 and another area on the back of the original image is treated with the ink-like mixture according to BoiupLeL 2. R Quacks LLberLampe Eraj t.'it, the whole v / ill with n el; in I böliciitot. The ILahter.ipEind-

borrowed film is with the latent diazonium salt Eild with gaseous Ammonia and steam evolved. In this way a Clear three-color reproducible copy obtained without significant color mixing in an area identical to that with the treatment mixture corresponding to the area treated according to Example 1, is colored yellow, an area which corresponds to that with the treatment mixture corresponding to the area treated according to Example 2, is colored red and the other areas, which correspond to the untreated areas of the Template, are colored blue.

1 (t ^! I rt ί l / \ * «ι

Claims (11)

Claims Process for diazotype multicolor reproduction, characterized in that one stepwise (Λ) a diazotype photosensitive material with a content exposed to at least one diazonium salt (c) and (B) a layer of coloring material is heated which has one in the ^ Contains heat volatile or sublimable coupler (a) and the light-sensitive diazotype material is applied in an area which corresponds to a predetermined area of an original, the steps being carried out simultaneously or in the order (A) (B) or (B) - (A), after which the exposed photosensitive Material is developed in the presence of a coupler (b) which, under the developing conditions, has a lower coupling rate than the heat-volatile or sublimable coupler (b), wherein the coloring material with a content of heat-volatile or sublimable coupler (a) is a " the heat-volatile or sublimable acid addition salt of a heat-volatile or sublimable azo coupling component is used which contains an amino group. 2) Process according to claim 1, characterized in that the acid addition salt which is volatile or sublimable in the heat is used the hot-volatile or sublimable coupling component meta-aminophynol hydrochloride or .-Phenyl-3-methyl-pyrazolone- (5) -hydrochloric used. 109813/1498 3) coloring material for carrying out the method according to a of the preceding claims, characterized in that it is a heat-volatile or sublimable acid addition salt according to claim 1 contains. 4) coloring material according to claim 3, characterized in that that it is an amino as the azo coupling component according to claim 1 ^ phenol, aromatic amine or an active methylene group containing amine. 5) coloring material according to any one of the preceding claims, characterized in that it is a volatile in heat or contains sublimable azo coupling component with a melting point of 100 ° to 15o ° C. 6) coloring material according to any one of the preceding claims, characterized in that it is volatile or volatile in heat ψ sublimable azo coupling component contains meta-aminophenol or 1-phenyl-3-methylpyrazolone (5). 7) coloring material according to any one of the preceding claims, characterized in that it is volatile or volatile in the heat sublimable acid addition salt a salt of a heat volatile or sublimable azo coupling component, which is a Contains amino group, with an acid such as hydrohalic acid, organic sulfonic acid, chloroacetic acid, chloropropionic acid, Acetic acid, salicylic acid, 2,6-dichlorobenzoic acid, 3,4-dimethyl-benzoic acid, Oxalic acid, oxalic acid hydrate, o-sulfobenzoic acid, 109813 / U98 Contains trichloroacetic acid, formic acid, methacrylic acid or butyric acid. 8) coloring material according to any one of the preceding claims, characterized by an ink-like mixture of 5, o to 25.0% acid addition salt which is volatile or sublimable under heat an azo coupling component that is volatile or sublimable under heat, ο to 5, o3> binding agent, ο to 3, o% coloring agent ■ and ο to 5, o% dispersing aid where a dispersing " sion medium makes up the rest. '■ 9) coloring material according to any one of the preceding claims, characterized by a waxy mixture of 5 to 25% an acid addition salt which is volatile or sublimable in the heat of an azo coupling component which is volatile or sublimable in the heat, 85 to 15% wax, Io to 4o% oil and ο to 2o, o% coloring agent. 10) coloring material according to one of the preceding claims | before, characterized in that it contains a heat-volatile or sublimable acid addition salt according to claim 2. 11) coloring material according to any one of the preceding claims, characterized in that it is in the form of a transparent or semi-transparent layer on the back of a predetermined Area of an original is applied 1st. ■ ORIGINAL INSPECTED