DE1797315A1 - Developer for the diazotype process - Google Patents

Description

179731S

LAW LAWS

DR. JUR. DIPL-CHEM. WALTER BEIl «« _Cen inco ALFREDHOEPPENER ι ii.oep.uoo

dr. jur. dlpl-chem. h.-j. wolfp.
dr. jur. hans chr. by j

623 FRANKFURT AM MAIN-HOCHSf

ADElONSIRASSi SS

Our No. 15 041

General Aniline & Film Corporation New York, N.Y., V.St.A.

Developer for the diazotype process

The invention relates to liquid developers for diazo type photosensitive copying material. Conventional developers for diazotype used for copying can be divided into three categories, namely ammonia-like development ler, moist or semi-dry iJntwickler and thermal developers.

Diazotype materials made with ammonia or semi-dry developers are used as two-component or one-component materials known.

In the ammonia development process, a solution containing a diazo sensitizer, i.e., a diazonium compound, becomes one or more Contains coupling agent and an organic acid as an overcoat applied to a sheet serving as a base.

009ÖSO / 0965

BATH ORIGINAL

The coated sheet is covered with the translucent original and so exposed to light. That won in this way latent image is developed by exposing the sheet to ammonia vapors, which neutralize the acidic stabilizer and activate the coupling agent, so that a color image of the original results.

In the wet or semi-dry process, it is common to use the Dlazo sensitizer together with stabilizers to be applied as a layer to the sheet serving as a base. The Belich ™ Processing is carried out as described above, and the latent image is developed by puffing the sheet through an aqueous buffer which contains one or more coupling agents; if necessary, it is also possible to apply the solution to the surface of the sheet.

Both procedures show. Disadvantages on. The ammonia process is it is necessary because of the ammonia vapors on the machine used Install drains and provide additional ventilation in the rooms in which the procedure is carried out. The on The drains present in the machine make it impossible to transport the machine easily and, moreover, increase considerably the cost of installation.

The known developer solutions, which are used for the wet or semi-dry process, have due to the in them contained water has disadvantages, because water can evaporate from the solutions, which leads to crystallization of the developer chemicals and the resulting sticking or blockages leads to the apparatus. Because of this fact and because of the tendency of the developer solutions to react with the formed To contaminate dye, it is common to end the processing equipment; emptying the vat every working day and wash out the rollers of the applicator system of the apparatus. The copies made by this process must also be dried and tend to curl up, especially if the developer solution is only on one side of the sheet

lit will ». . . .

^ΰ 009850/0985

The disadvantages outlined above occur with thermal Development process does not involve all of the components required to form the image in the copy paper are present, in which the latent image produced during exposure is developed through the application of heat. With this one However, there are disadvantages to the process due to the effect of heat on the 'copy paper and from the difficulty of a premature To prevent coupling at ambient temperatures.

Kit aid animal invention, the disadvantages described in detail above are to be avoided.

The invention relates to an improved developer for the so-called one Koraponenteii system, in which the diazonium compound there is no coupling agent in the layer of the paper, as well as for the so-called two-component system, in which the Diazonium compound is present together with one or more coupling agents in the layer of the copy paper Developer consists of a developer and - as a Solvent - from at least one liquid or low melting point water-soluble compound such as formamide, monoalkyl and dialkyl formamides, 2-pyrrolidone, H-substituted and other derivatives des 2-pyrrolidone, suIfolan, dimethyl sulfoxide, ethylene carbonate, / -Butyrolactone and other-organic ^ compounds which the Structures ^ G = 0, ^ S = 0 or ^ S ^ and have a Have solvent action.

According to a preferred embodiment of the invention, there is Solvent from at least one compound of the formula

0 R

H - CN -f ¹

Much more R ^ and R ^ can be the same or different and water substance or an alkyl radical, preferably with 1 to 4 carbon atoms mean.

In this preferred embodiment of the invention, there is Developer from a non-aqueous mixture and di ^ solvent-

component is composed entirely of organic materials of the type mentioned above. Preferably, the solvent is selected from formamide, Pur is a two-component material containing the developing agent is generally a Base \ with a one-component material further contains a developing agent, couplers and an antioxidant. ->.

Formamide, in which according to the above general formula Rj and Rp means hydrogen, is used as a solvent for most approaches preferred, however, the developers of the present invention can also contain more than one of the above-mentioned compounds, if this appears necessary.

Other organic solvents which used in the invention can Werder, that solvents other than the above-mentioned amides are organic substances of different structure, containing all the at least one doubly bonded oxygen atom, and a melting point which is only slightly above Cleans emperefcur and preferably below 25 ⁰ C. , and have a high dielectric constant; It is also necessary that the substances have good solubility for common azo couplers such as resorcinol and phloroglucinol and have low volatility; A considerably lower vapor tension than that of the water is also desirable; after all, the substances must be soluble in water.

These other organic solvents which can be used according to the invention, all of which have a typical double bonded oxygen atom, correspond to the following formulas:

I 2-Pyrrolldon II N-IIIethyl-2-pyrrolidone III IT-Vinyl-2-pyrrolidone

_/ s = o

CH _x

* ■ 009850 / M6S IV SuIfolan V dimethyl sulfoxide

Il

VI ethylene carbonate

VII Gamma Butyrolaoton

Some properties of these solvents (compared to water) are compiled in the following table:

solvent Kp, ⁰ O
r'- i ^1. , ⁰ O Dielectrics
constant solubility
by Phloro
glucine Developing
lung
dizzy, water 100 0 80/20 ⁰ O Well bad I. 245 25th sufficient very good II 202 -24 slowly sol
borrowed - bad III 96/11
mm Hg 13.5 Well very good IV 285 28 44/30 ⁰ O Well bad V 100 (d) 6th Well very good VI 243 36 97.5 / 2O ⁰ O * Well slow VII 206 -42 excellent
net moderate

* obtained by extrapolation

Following the discovery according to the invention that a water-soluble Organic solvent or several water-soluble organic solvents are beneficial in diazo printing development can be used, it was further found that it only is necessary, small amounts, e.g. in the order of 5 percent by volume and more, to use the "or the organic solvents, to achieve effective and satisfactory development; the remainder of the solvent can consist of water, where the water content can be changed within wide limits, as can be seen from the following examples. It could even be fixed that will arise from the presence of water in the developer at various points in the development process or related result in advantages on various aspects of the diazotype system. According to the invention, both non-aqueous and water-based

0098S0 / 096S

BATH ORIGINAL

term developers considered; the choice between the two The skilled person will meet the species according to the particular advantages he wants to achieve in individual cases.

The invention also relates to the method that for developing Using one-component and two-component diazotype material the developer according to the invention is used.

In the development method of the present invention, for production a copy of any original a sheet of copy paper, which is coated with a material containing a diazo sensitizer, exposed to light, so that a latent image forms. The exposed side of the sheet is then treated with a diazo type developing agent treated in which a solvent is present, which consists of formamide or its ΪΓ-monoalkyl or F, F-dialkyl derivatives in association with certain organic developing solvents.

A developer liquid according to the invention, which is preferably used for one-component material, consists, for example from resorcinol, phloroglucinol or a simple derivative of the latter as an azo coupler, an antioxidant? and either one Nitrogen base of the type mentioned above or an alkali metal salt a carboxylic acid or other weak acid (or both); suitable salts are, for example, sodium benzoate, formate, acetate, propionate, succinate and maleate; suitable Carboxylic acids that contain basic nitrogen are aminopropix » acid (alanine), 4-aminobutyric acid and piperidine-4-carboxylic acid. All conventional azo couplers can be used, with preference being given wise phenols, phenol derivatives, naphthols, baphthol derivatives, aromatic Amines and aliphatic compounds, which are little one contain activated methylene group, uses. Specific Azokupp Other than the mentioned phenols which are useful are 4-chloro < resorcinol, 2,3-mhydroxynaphthalene, 2-oxy-3-naphtholic acid-et $ anolarnid, -4,4-methylenedianiline dihydrochloride and aoetoacetbenzylamide.

ORIGINAL O09SSO / & S85

Other weak acids whose salts can be used are Boric acid and di- and triphosphates, and in general any Acids whose K-Yfert is less than 2 lo "**. These salts are used for Added to achieve a buffer effect.

A developer according to the invention is characterized by a larger one Developing speed from than usual aqueous developer and gives full development even in smaller quantities, e.g. 5 - 6 g / m instead of 10 - 11 g / m. The developer can also be adjusted so that it is more stable than conventional aqueous developers, and well the evaporation of the organic solvent (s) which the developer contains, can be neglected, can be developed ™ win, in which, even after a long period of storage, Crystallization of the dissolved components can be observed and in which no contamination by the dye of the diazotype material entry. If the developer is a non-aqueous mixture based on one or more organic substances Solvent is built up, and this developer is applied in controlled, limited amounts with the help of a suitable apparatus, thus a substantially dry copy can be obtained which even when the developer is applied to only one side of the sheet shows no tendency to roll.

The invention is further illustrated by the following examples, * where:

Examples 1 - 23 and A - D focus on the development of a one-component

refer to nenten material;

Examples 24-35 and E and F focus on developing a two-

Relate component materials.

All quantities are given in parts by weight.

Example 1 *

Formamide 90 parts

Phloroglucinol 5 parts

Sodium formate 5 parts

Thiourea dioxide (Imlno-aminomethaasulfinic acid) 0.5 parts

009850/0965

Example 2

Formamide
Phloroglucinol Sodium Acetate Thiourea Dioxide

Example 3

Formamide
Phloroglucinol Sodium Benzoate Thiourea Dioxide 90 parts 5 parts 7 parts 0.3 parts

85 parts 5 parts

10 parts 0.5 parts

Example 4

Formamide

IT-Me thy! Formamid Phloroglucinol sodium maleate Thiourea dioxide 80 parts 10 parts 2.5 parts 5 parts 0.25 parts

Example 5

Formamide

N, II-dimethylfoamamide Phloroglucinol Sodium Propionate Thiourea Dioxide

Example 6

Formamide

Resorcinol

1, 2-dimorpholine ethane thiourea dioxide 85 parts 5 parts 5 parts

5 parts • 0.25 parts

90 parts 5 parts 5 parts. 0.5 parts

Example 7

Formamide

BATH ORIGINAL

^{90 part} 809850/0965

H, if-Bi-ß-hjä r.Qxy ä; t hy Ip iperazla

2 parts

3 IeIXβ ' 5 parts 0.5 leile

Example 8

Phlprogluoin.

9Q
5 parts 5 parts

Bpraix

Thi p.haras t qf f d ipxy d

Example 10

iOrmamid lurfuraldehy d Bprax

ifatriummplybdat Elesprcin phproglucin.

Tlii pharns t of f ä i oxy d

Example it

2-pyrrolidone Phloroglucine

AtEfpiel 12

-2-pyrrolidone phloroglucinol

BATH ORIGINAL 83 parts 7 parts 5 parts 5 parts 0.5 parts

Parts 5 parts 5 parts 2 parts 2 parts 2 parts 0.5 parts

Share 5 pieces

Share 5 pieces

009850/0965

Example 13

| F- ¥ ip.y, l-2-pyr.: CpH3Pii 95

5 axes

14th

Example I

f-B ^ tyrplactpn 95

Example 17

Xthyleapar] 3pnat 95

Phloroglucinol 2,

Example 18

Ethylene carbonate 45

2-pyrrolidori 50

Resproin 5 ropes

■ i ■ - ,. * ■■> ■ · ι. '.

Example 19

Dimethyl sulfoxide 50 files

(Jannna-Butyrolactpn 45 If ile.

Resprcin 5

BAD ORfQfNAL Example 2ü

Dimethyl sulfoxide gamma butyrolactone SuIf olari

Phloroglucine

Example 21

Formamide 2-pyrrolidoti Sodium benzoate Thiourc tof f d loxyd (imino-amino methanesulfinic acid)

4ü parts 30 parts 25 parts

3 parts

60 parts 35 parts

5 parts

0.25 parts

Example 22

Formamide SuIfolan Sodium as well as thiourea dioxide

Parts parts 7 parts 0.4 parts

Example 23

2-pyrrolidone water

Sodium as well as phloroglucine

Parts parts 3 parts 2.5 parts

The developers of the aforementioned examples develop conventional one-component aiazotype files very quickly at room temperature and give a dark picture on a white background. Examples 6, 7, 18 and 19 are particularly suitable for developing Print on sensitized tracing paper. Examples 9 and 10 are suitable to develop one-component diazotype material that Contains polyvinyl alcohol in the surface coating. The borax and the aldehydes combine with the polyvinyl alcohol and yield a dry surface.

009850/0965

BAD ORlGtNAt

Examples of conventional one-component materials are:
Example A.

A white paper pad is coated with a sensitizing liquid coated with the following composition:

2,5-Mmethoxy-4-p-methylphenyl-thiobenzene-diazonium chlorozincate 1.5 parts

Tartaric or citric acid 0.5 parts

Water ed 100 parts

™ Example B

A copy paper comes with a sensitizing liquid coated with the following composition:

2,5-diethoxy-4-p-methylphenyl-thiobenzene diazonium chlorozincate 2.5 parts

Citric acid 0.5 parts

Gelatin 1.5 parts

Water 70 parts

Ethanol 25 parts

n-butanol 10 parts

^ Example C

A copy paper comes with a sensitizing liquid coated with the following composition:

2,5-diethoxy-4-p-methylphenyl-thiobenzene diazonium borofluoride 3 parts

Polyvinyl alcohol ("Elvanol" 51-05) 5 parts

("Elvanol" is a trade name of Fe «,
du Pont)

Water 70-100 parts

Ethanol 30 parts

Example D

A copy paper with a partially hydrous cellulose acetate Surface is covered with a sensitizing liquid with the composition 009850/0965

3-chloro-4-aimethylaminobenzyl-diazonium chlorozincate 2.5 parts

Water ethanol citric or tartaric acid

■ coated.

70-100 parts

50 parts

0.5 parts

Example 24

Formamide 1,2-dimorpholine ethane

Example 25

Formamide U-methylformamide U, H'-Dihyäroxyäthylpiperazin

Example 26

Formamide triisopropanolamine 80 parts 20 parts

80 parts

5 parts

18 parts

80 parts 20 parts

Example 27

Formamide N-methylformamide 2-aminopyride in 80 parts

5 parts

15 parts

Example 28

Formamide 4-aminopyridine Diisopropanolamine

Example 29

Formamide sodium acetate 2-aminopyrine in 80 parts 10 parts 10 parts

009850/0965

80 parts 10 parts 10 parts

Example 30

Formamide

1,2-dimorpholine ethane

Triisopropanolamine

Example 31

Formamide

N, N-dimethylformamide
1,2-dimorpholnethane
borax

80 parts 10 parts 10 parts

75 parts 5 parts

15 parts 5 parts

Example 32

Dimethyl sulfoxide
Diethanolamine

85 parts 15 parts

Example 33

Ethylene carbonate
Diethanolamine

90 parts 10 parts

Example 34

2-pyrrolidone

1,2-dimorpholine ethane

Example 35

Sulfolane
4-aminopyride in
Diisopropanolamine

80 parts 20 parts

80 parts 10 parts 10 parts

All developers of Examples 24-35 develop conventional two-component materials as given in Examples S and 7 below and produce a blue image (Example) or a black image (Example 7) on a willow background,

009850/0966

IAD ORIGINAL

loc

Example Ά

A white paper pad comes with a sensitizing one Liquid coated with the following composition:

p-Diethylaminobenzene-diazonium chlorozincate 1.9 parts

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

Calcium chloride 10 parts

Citric acid 1 "

\ up to 100 parts

* Alternatively, the disodium salt can also be used.

Example F

A white paper pad comes with a sensitizing one Liquid coated with the following composition:

p-DiethylarainobenBol-diazoniumchlorzincat 2,7-dihydroxynaphthalene-3,6-disulfonic acid

ß-Hydroxyäthylresorc in resorcinol

We i list in acid calcium chloride urea

Water ad

* Alternatively, the disodium salt can also be used. Example 36

2 ,3 parts 2 Parts 5 Parts 1 part 1 part 10 Parts 3 Parts 100 Parts

The following approaches represent ^ SO ^ ige aqueous mixtures:

Formamide 100 ml phloroglucinol. 4 g

Sodium benzoate 10 g thiourea dioxide 0.5 g

Sodium isopropyl naphthalene sulfonate 0.5 g

The above mixture was prepared and diluted with an equal volume (about 1.05 g) of water. Using this

009850/0965

BAD ORJQINAt

Developer had the advantage of having the somewhat greasy handle «1er Copies after developing, which are calibrated for developers who do not have a Contains water !, results in reducing.

Examples 37 to 42

The following approaches, which are identical except for the lack of water (Example 37) and the presence of various WasBeimengen were made as follows:

22nd 30 39 40 41 42

100.0 ml 95.0 ml 75.0 ml 50.0 ml 25.0 ml 5, ObI. 5.0 ml 25.0 al 50.0 ml 75.0 ml 95.0 ml 4.0 g 4.0 g 4.0 g 4.0 g 4.0 g 10.0 g 10.0 g 10.0 g 10.0 g 10.0 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g

one
Using fluted Y / alze as an applicator, the

Formamide 100.0 m ' water - Phloroglucine 4.0 G Sodium benzoate 10.0 G Thiourea dioxide 0.5 G Aerosol OS 0.5 G

sunken is used to develop neutral ϊΨίψα standard paplers. The way of working was always satisfactory. The developer solutions then remained steneri in open vaporization trays for 24 hours. The solutions were used again to develop prints. The way of working was always satisfactory. Then allowed to stand offeu ψ 72 hours. The solutions of Examples 57 to 41 were essentially unchanged in their appearance, while the solutions of Examples 40 and 41 had lost some of the oil, and the prints developed were very good. The solution from Example 42, 4t.e, which was most dilute at the beginning, showed considerable crystal formation and loss of volume, but was still able to develop the bridge.

On the basis of the results obtained, it was shown that 5 % ine-boiling water-miscible solvent in a moist film developer is sufficient to prevent crystal formation. publishers. The ifbchine for the moist diazotype process came to work for longer periods of time, without cleaning, than that of a moist developer that only works as a solvent

were. OeMWMfS

BAD OBiOtNAU

Examples 43 and 44

43 44 Gamma butyrolactone 50 ml 10 ml V / ater 50 ml 90 ml Phloroglucine 4 g 4 g Sodium benzoate 10 g 10 g Thiourea dioxide 0.5 g 0.5 g Aerosol O.S. 0.5 g 0.5 g

The above two solutions were found to be satisfactory.

Obviously, the invention has a number of very advantageous advantages Provides developer for both the one-part and two-part diazotype material.

009850/0965

Claims (19)

Claims 1) Developer which iat suitable for developing diazotype material, characterized in that the developer is a diazotype Developing agent and, as a solvent, at least one liquid or low-melting water-soluble compound contains, which from pormamide, monoalkyl or dialkyl formamides, 2-pyrrolidone, N-substituted or other derivatives, of the 2- · Pyrrolidons, SuIfolan, Dimethylsulfoxyd, Ethylencarbonat, Gamma-butyrolactone or other organic compounds that contain the structures ^> C = 0, ^ 3 = 0 and ^ T S ^^ and have a solvent effect, exists? 2) Developer according to claim 1, characterized in that the solvent is a compound of the formula ti H-O- ^ ^R 2 is, in which R ^ and R _{2 are the} same or different and can represent hydrogen atoms or alkyl radicals. 3) developer according to claim 2, characterized in that the alkyl radicals contain 1 to 4 carbon atoms. 4) developer used for developing a diazotype printing material is suitable, characterized in that it is a developing agent suitable for the diazotype process and formamide contains. 5) developer according to claims 1 to 4, characterized in that that he has at least one base, namely monoethanolamine, diethanolamine, Triethanolamine, 1,2-dimorpholine ethane, diisopropanolamine, Contains triisopropanolamine or 2-aminopyridine. 6) The developer according to claim 5, characterized gekfi "Ik% icfenet that the base in an amount of 15-20 Gewichtap-rcent yorhandeja _c IFLT. j / tWSJtf? O GAB 009850/0965 WAO 7) ülntwiekler according to claim 5 or 6, characterized in that the base is present in Pormamidlüsung. 8) developer according to claims 1 to 7, characterized in that that these?' at least contains an azo coupler and an antioxidant. 9) -Üntwici.l ^ r according to Anepruch 8, characterized in that the Azo couplers made from a phenol, a phenol derivative, a naphthol, a unphuholderivat, an aromatic amine or an aliphatic one Compound which has at least one activated Ketliy- ^ has lengruppe, exists. K) iJn; .wic.; Lov according to claim 8 or 9 _f, characterized in that it contains at least one alkali metal salt of a weak acid. 11) ^ ntwic.: Ler according to claim 10, characterized in that the Salt from sodium benzoate, sodium formalate, acetate and propionate, succinate or maleate. 12) developer according to claim 10, characterized in that the Salt from an alkali metal: ζ of aminopropionic acid, of 4-aminobutyric acid or the piperidine-4-carboxylic acid. 13) developer according to claims 1 to 12, characterized in that that this is not watery. 14) developer according to claims 1 to 12, characterized in that that it contains water in an amount such that no less than 55% organic solvent is present. 15) developer according to claims 1 to 12, characterized in that that the organic solvent or digforganischen solvent is present in an amount of about 5 percent by volume with the remainder of the solvents being water. 009850/0965 BATH ORIGINAL «Ο 16) method of developing one-part or two-part diazotype material, characterized, that a developer according to claims 1 "to 15 is allowed to act on the material. 17) method for copying an original, characterized in that that a sheet of copying paper, which contains a diazo sensitizer in the sensitive layer, is interposed of the original to be copied exposed so that a latent image is formed in the copy paper, and that one ^ finally on the exposed side of the copy paper a developer is allowed to act, which is a developing agent suitable for the diazotype process and as a solvent Formamide or its N-monoalkyl or N, N-dialkyl derivatives or other liquid or low-melting solvents according to claim 1, so that one copy of the original. 18) Method according to claim 17, characterized in that the developer is on there
is applied. Developer on the copy sheet in an amount of 5-6 g / m 2 19) ancestors according to claim 17 or 18, characterized in that the developer is not aqueous and is applied so that a practically dry copy is obtained directly. PUr "General Aniline & Film Corp. New York, N.Y., V.St.A. Lawyer 009850/0965 ORIGINAL.