DE2325579A1 - METHOD AND DEVICE FOR PRODUCING DIAZOTYPE COPIES - Google Patents

Description

ig. RWIRTH Dr. V. SCHM5ED-KOWARZIK DIpWn ₈ . G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 β FRANKFURT AM MAIN

TELEF N 0 11) _{287 {m} Q [£ ESCHENHEIMER STBASSE

Case 328
Wa / Sch

QeS van der Grinten St ", Urbanusweg 102

Teal ο
Holland

Process and device for the production of clay siazotype copies .

309850/1 109

The present invention / relates to a method for Production of copies in which a diazotype material, which consists of a carrier material with a Diazosch.icht, after The imagewise exposure is developed by applying a buffered aqueous solution of an azo coupling component evenly over it the diazo layer is distributed.

In the diazotype processes, which are described in _{detail in J 9} Kosar's book "Light-. Sensitive Systems", "edited by John Wiley and Sons Inc., Kiev York / London / Sydney (1965), on pages 194 et seq , two different systems are well known.

In the dry or ammonia process, a diazotype material is used used in which a photosensitive diazonium compound and an azo coupling component in one layer are present. This layer also contains an acid stabilizer. After the imagewise exposure, this becomes Material developed by exposure to γοη wet ammonia gas, so that the diazonium compound remaining on the unexposed parts with the azo coupling component. clutch and gives an azo dye.

The unpleasant and pungent ammonia smell is the main disadvantage This procedure represents. To avoid that too much ammonia gas penetrates into the working space, should be in this Process used copiers equipped with a trigger system will. However, the copies still smell of ammonia for a long time.

The semi-wet process uses a diazotype material, whose light-sensitive layer only contains the diazoniura compound, either with or without a stabilizer and other additives. The copy is developed by a thin layer of a buffered, aqueous solution, an azo coupling component is evenly distributed over the diazd layer. . . .

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In practice, the amount of azo coupling used is

3 2 component solution or developer approx. 7 = 8 em per m each Page. This amount is necessary for an even application of the developer as well as a fast and complete development with the usual development devices and diazotype materials to reach. In general, almost the same amount of developer is also applied to the back of the copy material applied to prevent curling or curling of the material.

■ A copy developed this way contains a lot of moisture. A few copies can be air-dried, but if you are making a large number of copies one at a time a drying device is essential. Such Drying equipment requires a high heating capacity, especially in high-speed copiers. It also takes a considerable amount of time Time before the drying device has reached the required drying temperature. This creates undesirable waiting times before the copier can be used. For this reason, a development process has long been used wanted, with which one can make dry or as good as dry copies, but not the disadvantages of the Having ammonia process.

For this purpose it is proposed in US Pat. No. 1,841,653 to apply the developer liquid with the aid of press rollers. An excess of developer is applied by means of two rollers covered by rubber, and this is then immediately removed again from the same rollers. According to this patent, the copies made in this way appear practically dry. In reality, the developer is ^1, however, has completely penetrated into the copying material so that it contains a considerable amount of moisture. A drying device is therefore indispensable for high-speed copiers.

Another solution has been suggested in British Patent No. 1,143,702. According to the procedure described therein is.a two-component diazotype material used, exactly

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as in the ammonia process. However, the development takes place by applying a regulated amount of a maximum of 3 cnr per m of an alkaline liquid which contains at least about 20 % of an aliphatic amine.

The copies obtained in this way are instantly dry, but they feel a little bold. There is another disadvantage in the relatively slow development caused by the generally slow coupling diazonium compounds used in your two-part material, and presumably also in that the viscous developer penetrates rather slowly into the material to be developed.

It is an object of the present invention to provide a copying process "in which instant dry copies are obtained and which does not have the disadvantage parts of the above mentioned copying methods. The method according to the invention exists in that a diazotype material, which consists of a carrier material with a diazo layer, after the imagewise Exposure is developed by applying a buffered, aqueous solution of an azo coupling component evenly over the diazo layer is distributed, and is characterized in that the solution of the azo coupling component in a pre-dosed amount

■ ζ ρ
of about 1.5-4.5 cm per τη is used.

The copies developed in this way immediately feel dry; the small amount of moisture that is applied evaporates by itself very quickly, so that no drying device is necessary even with high-speed copiers *

Both the known alkaline developers and the weakly acidic to weakly alkaline developers can be used as developers for the process according to the invention. because they have a better shelf life.

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Such developers are for example in the British Patent Hr. 957 836 ". It is of course also possible to use other buffers than those mentioned in this patent specification as long as they have the desired pH and have a sufficient buffering effect.

A very suitable buffer is, for example, in French U.S. Patent No. 1,347,703.

According to the invention, a developer is preferably used which is more concentrated than that in the above-mentioned patents described developer. This makes it possible, despite the low applied amount of developer about the same amount of azo coupling component v / ie in the known semi-wet development to raise. This ensures rapid and complete development.

According to British patent specification 957 836, the amount of phloroglucin used in this case as the azo coupling component is at most about 50 millimoles per liter and the amount of buffer salt is about 150-650 millimoles per liter. In the developer preferably used according to the invention, the amount of azo coupling component is about O ₅ 1-0.6 mol per liter and the amount of buffer salt is about 0.5-3 g equivalents per liter.

In addition, the developer can use common substances for prevention des Yergilben, antioxidants, development accelerators and wetting agents.

In addition to phloroglucine, which is generally used as azo coupling component, other azo coupling components can of course also be used, such as resorcinol, optionally in conjunction with phloroglucin, can be used.

In the method according to the invention, Ein ™ component diazotype materialsj, the fast coupling diazonium compounds contain, used »

30th

When such diazonium compounds are used, rapid and complete development takes place, as does when the aforementioned neutral to weakly acidic developers are used.

Therefore, the diazo layer preferably contains a diazonium compound, which have a stronger coupling activity in vitro than p-Diazo-o-chloro-diethylaniline possesses. This definition of Coupling action is described in British patent ITr. 957 836 given. .

Such fast coupling diazonium compounds are e.g. the aforementioned patents as well as in the British patent Hr. 957 838 called. Preferably be for example uses the following compounds:

1 ~ Diazo-4-'benzoylamino-2,5-dibutoxy-benzene 1-Diazo-2,5-diethoxy-4- (4'-methoxy) -phenyl-benzene 1-Diaz 0-2,5-dimethoxy-4- (4'-methyl) -phenylthio-benzene 1-Diazo-2,5-diethoxy-4- (4'-methyl) -phenylthio-benzene 1-Diazo-4-dimethylamino-3 ~ (4'-chloro) -phenoxy-6-chloro-benzene i-Diazo - ^ - dimethylamino ^ - (4'-chloro) -phenoxy-2-chloro-benzene i-Diazo-2- (ethoxycarbonyl) (benzyl) amino-4- (methyl) (cyclohexyl) amino-3-methoxy-benzene 1-Diazo-4-benzoylamino-2- (ethoxycarbonyl) (methyl) amino-5-

methoxy benzene

1-diazo-2- (ethoxycarbonyl) (methyl) aniino-5-methoxy-4- (4'-

methyl) -phenylthio-benzene.

For the reason λ '/ mentioned below, the diazonium compounds are grounded preferably used in the form of a readily water-soluble salt, e.g. as hydrogen sulfate or as chloride. The diazo layer can contain several diazonium compounds. In addition, the usual auxiliaries, such as acids and stabilizers, e.g. the sodium salt of 1,3,6-haphthalenetrisulfonic acid. Reducing agents, thioureas, etc., be present.

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Those described in British Patent Specification No. 957836 " Film layers in which the diazonium compound is present in a hydrophilic film layer of about 4 "to 5 yu-ro very suitable for development according to the method according to the invention.

For opaque materials used in the semi-wet process and whose carrier material consists of paper that can optionally be provided, some of the diazonium compound is much deeper in the material. This is upon it attributed that the diazonium compound in an amount of

■ ζ ο Diazo solution of about 10 to 15 cur per m is applied. This can cause the diazonium compound to penetrate deeply into the material.

Since the development according to the method according to the invention is only

3 is carried out with an amount of developer of about 1.5-4 »5 cm per m, the azo coupling coraponent cannot penetrate so deeply into the material. As a result, the development does not take place completely. In general, v / ground only et converted \ tfa 70 i * of the diazonium compound in azo dyes.

This problem can be solved by first coating the paper with a hydrophobic barrier layer and then applying it applies a hydrophilic layer of the desired thickness. The diazonium compound can be applied either simultaneously with the hydrophilic layer or afterwards. In this way too deep penetration of the diazonium compound is prevented. The composition of the material is then the same as that in the British Patent No. 957,836.

It has now been found, however, that too deep penetration of the diazonium compound can also be prevented by treating the material with a small amount of a diazo solution which

a diazonium compound in a correspondingly higher concentration

. - 8 30 9 8 50 / T 109

contains, sensitizes. A suitable amount is, for example, about

■ zp 3 2

2-8 cnr per m, preferably about 3 cnr per m. To this Art, the dia ζonium connection penetrates about just as deeply and openly in the same way as the azo coupling skorap onent e. With such Sensitized materials develop almost completely (around 95-100 ^).

^: In order to show the effect of this sensitization process, a series of diazotype papers, which were made in a known manner with

• ζ ρ

about 10-15 cnr per m had been sensitized, and one Series of diazotype papers, the erfindungsgetnäß with about

■ ζ 2 ■ '■■'

3 cm ^J per m had been sensitized, completely developed with the developer solution described in Example I. Parts were then cut out of the developed materials so that the cross section of the azo dye layers could be viewed under the microscope. It was found that the thickness of the dye layer was very different in places. Therefore, the layer thickness was measured at many different points and the arithmetic mean was calculated from the results of these measurements. This average is referred to here as the average maximum layer thickness. The one with about

3 2

10-15 cm per m of sensitized diazotype paper an average maximum layer thickness of about 9-12 µm on.

The average maximum layer thickness of the diazotype papers, according to the invention with about 3 he was about 5.5 - 7.5; Ura. '

3 2

papers which, according to the invention, are sensitized at about 3 cm per m

The diazotype papers used according to the invention preferably have an average maximum layer thickness of at most about 8itm, in particular at most about 7mm.

Palis the diazo layer is applied directly to the paper, the surface structure of the paper can be seen on the copy in the form of an uneven distribution of the azo dye. This can be prevented by opening the paper

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coated in "known manner before". Such a layer "consists generally of an inorganic pigment such as silicon oxide, aluminum oxide, a metal silicate, or a organic pigment such as starch, rice starch, etc., in one Binders such as casein, polyvinyl alcohol, polyvinyl acetate, and like that.

It has surprisingly been found that "with materials, in many cases the biazonium compound in a hydrophilic one Film layer is present, raising awareness with a

■ ζ ο Diazoniura salt solution in an amount of about 2-6 cbt per m

■ 5 instead of the 8-15 cm per m 'usual for these materials beneficial to the development speed and the complete The development of the diazotype material.

As can be seen from the cut surfaces of the developed material, the diazonium compound was also in this case

^v ) closer to the surface when the material has been sensitized to 2-6 cm per ra. This allows the azo coupling component to reach the diazonium compound more easily.

The amount of developer that is used in developing the diazo layer is applied depends on the surface structure, the hydrophilic behavior and the porosity of the material to be developed Diazotype material. A smoother layer will absorb less developer than a slightly coarser layer.

On lacquered materials, the backing of which is made of a synthetic film, e.g. a polyester film, or a transparent one Paper consists, which with a hydrophilic film layer and optionally with a hydrophobic intermediate layer, for example a superficially saponified cellulose acetate layer,

■ 2 ρ

is provided, an amount of about 1.5 - 5 _s 0 cm per m is applied. These film materials contain a greater amount of diazonium compound per unit surface area than diazotype papers. To fully develop these materials must

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a "certain minimum amount of developer can be applied. Compared to the appropriate amount to be applied to which the developing device is set for such film materials a larger amount is applied to paper, which means "that there is an excess on diazotype paper is applied to azo coupling component.

Consequently, "is the amount of developer that can be used on ordinary -L borrowed, opaque materials with a paper backing with or

3 is applied without pre-coating, about 2.5 - 4.5 cm

2 ¹ ^ 2

per m, preferably about 2.5-3.5 cnr per m.

The mentioned minimum ranges result from the IT need to distribute the developer evenly over the diazo layer and to moisten the entire surface. The top Limits are dictated by the need for the material to feel dry when it leaves the processor.

Various devices have already been described in the literature with which it is possible to have such a small amount of liquid evenly on a surface to distribute. The best results are obtained with the one according to the invention However, the method is achieved with the device described below, i.e. one can use it to do all of the above Process materials well and apply the developer evenly and continuously.

This device is shown schematically in the accompanying drawing. 1 is a metering roller that comes with a textured surface provided eats and partially immersed in the developer 3. The structure can be preserved by moving the roller over the entire length with a spiral Provides groove. 2 is the applicator roller. The surface is elastic, non-porous, and has a suitable one Hardness, generally about 10 - 50 ° Shore hardness A, preferably about 25 - 35 ° Shore hardness A. 4 is a pressure plate, "where preferably at least the part that comes into contact with the applicator roller is made of an elastic Material, e.g. Teflon, is made. To the

- - - 11 -

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Formation of a fluid meniscus and the back side becoming wet To counteract the copy, the edge of the pressure plate is preferably provided with U-shaped notches.

A device can also be attached to hold the pressure plate lifts off the applicator roller when there is no copy between this plate and the roller.

A pressure roller can also be used instead of the pressure plate the surface of which is provided with bumps to prevent the pressure roller from getting wet and thus the back side getting wet of the developed material.

5 and 6 are the lead-in and lead-out slots for the diazotype material. 7 is the copy material to be developed. 8 is a housing that serves to prevent water from evaporating to prevent the developer.

The copy to be developed is between the applicator roller 2 and the pressure plate 4 with the photosensitive side down transported.

When the device is in operation, the metering roller 1 applies developer to the applicator roller 2. This takes up part of the developer liquid and conveys it to the copy to be developed. The copy takes up part of the developer from roller 2, the amount taken up depending, among other things, on the material to be developed. The Entwieklermenge which is to a certain Matorial, for example, paper, is applied, amongst others depends on the surface structure of the metering roller 1, the hardness and the hydrophilic behavior of the surface of the applicator roll 2, the pressure between the applicator roll and the ⁼ metering roller 1 and the pressure between the printing plate and the applicator roller 2. All of these factors must therefore be related to one another, and many suitable combinations are possible. For example, a developing device has been manufactured whose metering roller is equipped with a

- ■ ■ - 12 -

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Provide a groove with a depth of 25 / xm and a groove spacing of 0.3 mm was. The groove had a triangular cross-section. the

upper width "was 50 .mu.m. The surface of the applicator roller was

/ ο

was made of a polished rubber with a hardness of 25 Shore A.

The pressure between the metering roller and applicator roller was 7 g per running millimeter, and the pressure between the pressure plate and applicator roll was 4 g per running millimeter.

With this developing device one received a developer application, which remained constant up to a transport speed of 20 m / min of the material to be developed, namely

• χ ρ
between 3.5 and 4 cm per m for paper and between 1.5 and

" ³ S 2
2 cnr per m for film material.

In general, the pressure between the pressure plate and. Applicator roller about 2-10 g / mm, preferably about 3-5 g / mm. There should be a certain minimum pressure to ensure a good, to get even moistening. If the pressure is too high, too little developer will be applied to the film material. The application roller should be coated with a material that has a hardness of at most 50 ° Shore A, preferably 25-35 ° Shore A, owns. This is necessary in order to obtain uniform moistening of material with differences in thickness and tolerances of the pressure plate and the rollers used. The pressure between applicator roller 2 and metering roller 1 is about 3 to 9 g / mm, preferably about 5.5 to 7.5 g / mm. The surface structure of the metering roller, i.e. the overall cross-section of the depressions per running millimeter, should finally be chosen so that the desired pressure at the pressure used Amount of developer applied. This structure shouldn't be too coarse, otherwise it would be more or less visible on the final copy, because the developer would then not be able to could distribute itself sufficiently evenly over the applicator roller. In the case of the above-mentioned device, the total depression was of the grooves over the longitudinal section of the roller about 2,000 am / mm. '·

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In the method of the present invention, the developer is preferred only applied to the diazo layer i. That's why that tends Diazo paper to curl backwards, i.e. with the light-sensitive side facing outwards «This ripple disappears after a short time. If necessary, it can be reduced or the duration of this state shortened. The paper can for example be made more water repellent by "coating it beforehand; thereby" forming practically a barrier layer on the surface of the paper. In this way too deep penetration of the diazoniuta compound is avoided prevented.

Example · I

A Trfigerpapier for the diazotype process \\ oirde in well-known Way pre-coated on one side »This layer consisted of:

10 g of a crystalline silicon oxide with a particle size of 5 ijLTn ^,

6 era of an emulsion of 50 wt .- $ polyvinyl acetate »with Water was made up to a total of 100 get.

The coating was carried out by distributing 15 cm / m of this mixture evenly over the paper and then this dried. The precoated side was then sensitized by adding 3 cior / m of a 0.14 molar diazole solution in water applied evenly to the surface and dried. A mixture of two diazonium compounds was found in the diazole solution used, namely:

4-Dimethylamino-3'- (4 ¹ -chlor) _T phenoxy-e-chlorobenzene-diazonium hydrogen sulfate and

2,5'-Diethoxy-4- (4 ¹ -methyl) -phenylthio-benzene-diazonium hydrogen sulfate

in a weight ratio of 2; 1, The obtained in this way Diazotype material was transparent through a

- 14 -

Original exposed and then developed by

■ Z p

3 cm / m of a solution of the following composition with the in the developing device shown in the drawing evenly distributed on the diazo layer:

260 g dipotassium succinate (calculated anhydrous)

25 g phloroglucinol 2 aq.

6 g resorcinol -

1 g aerosol AY (wetting agent eggs Ab er ic an Cyanaraid Co.)

cur water.

The pH of this solution was adjusted by adding succinic acid set to 6.8. The solution contained 0.9 mol of succinate and 0.2 mol of azo coupling component per liter.

Immediately after developing, the copy felt dry and showed a strong black image that contained so well no unreacted diazonium compound.

Example II

A cellulose acetate film of about 20 g / m

Natural transparent paper of about 80 g / m 2 was superficially hydrolyzed to a depth of about 3 lim by treating it with a solution of KOH in a mixture of water and methanol, after the chemicals used for the hydrolysis removed by washing with water and dried the paper, it was sensitized by applying 3 cm / m 3 of a 0.35 molar solution of a diazonium salt to the hydrolyzed side of the paper. A similar result can be achieved if an excess of diazo solution is applied and it is removed again after about 1 second, for example with a high pressure air blower.

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As a diazoniuro salt, dice 4-Benzoylamino-2- (ätboxy-carbonyl) (methyl) amino-5-methoxy-benzoi-diazonium hydrogen sulfate is used. The resulting diazotype material was "imagewise" exposed and developed in the manner described in Example I. 2.5 ctn / m developer were applied. The on this Well-preserved copy felt instantly dry and showed a strong purple to brown image with a very good one UV absorption on a clear background.

Example III

A polyester film was made with a layer of 10 g / m 2 of cellulose acetate and a non-crystalline silicon oxide provided in a weight ratio of 3: 1. This layer was superficially saponified in the manner described in Example II. The carrier obtained was then prepared as in Example II sensitized. The copying material obtained in this way was exposed imagewise and with that shown in the drawing Device developed by applying 2 cm / m of the developer solution described in Example I to the diazo layer applied. The same results as in Example II were obtained,

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Claims (17)

Claims 1. A method of making copies in which a diazotype material, that consists of a carrier material with a Diazo layer "consists of a buffered, aqueous solution after the image-wise exposure is developed an azo coupling component evenly over the diazo layer is distributed, characterized in that the Solution of the. Azo coupling component in a pre-dosed Amount of about 1.5 - 4.5 cm. Vm is used. 2. The method according to claim 1, characterized in that a diazotype material is used in which the diazonium compound is present in a surface layer with an average maximum thickness of at most 8 μm , 3. The method according to claim 1-2, characterized in that a diazotype material is used in which the diazonium compound is present in a surface layer with an average maximum thickness of 7 µm. 4. The method according to claim 1 - 3, characterized in that daS the buffered solution of the azo coupling component has a pH of about 5.5-8, 5. The method according to claim 1-4, characterized in that the buffer efficacy of the solution of the Az © coupling component at least largely of at least one salt from the group: alkali, magnesium and ammonium salts of succinic acid, glutaric acid, adipic acid, ß-methyladipic acid, maleic acid, malonic acid or citric acid. - 17 - 309850/1109 6. The method according to claim 1-5, characterized in that the developer solution contains about 0.1-0.6 mol of azo coupling component per liter and about 0.5-3 g-equivalents of buffer salt per liter. .7. Method according to claims 1-6, characterized in that the diazo layer contains a diazo compound, which in -vitro a stronger one. Coupling activity as p-diazo-o-chlorodiethylaniline owns. 8. The method according to claim 1-7, characterized in that for the development of diazotype material, which consists of a paper carrier with or without pre-coating, v / elche from einin Pigment and a binder composed, and a Diazo-r layer consists of the azo coupling component solution in one An amount of about 2.5 - 3.5 g / m is applied. 9. The method according to claim 1-7, characterized in that for the development of diazotype material, which consists of a carrier made of polyester or transparent paper, which optionally is covered with a hydrophobic lacquer layer and on which there is a hydrophilic film layer with a diazonium compound is located, the solution of the azo coupling component in an amount of about 1.5-3.0 g / m 2 is applied. 10. Procedure according to. Claim 1 - 9, characterized in that a diazotype material is used, which by equal- τ? ρ moderate application of about 2-8 cnr / m of an aqueous Solution of a diazonium compound has been sensitized to the surface of the material. - 18 - 3098S0 / 1109 11. diazotype material for use in the method of claim 1 -10, characterized in that the diazonium ver bond in a surface layer with an average maximum thickness of hö ch st s s / a il m is present. 12. Diazotype material according to claim 11, characterized in that the diazonium compound is present in a surface layer with an average thickness of at most about 7 µm. 13. Diazotype material according to claim 11-12, characterized in that it is by uniform application of about • ζ ρ 2-8 cm / m of an aqueous solution of a dia ζ onium compound has been sensitized to the surface of this material. 14. Diazotype material according to claim 11-12, characterized in that it consists of a paper carrier, optionally with a pre-coating with a pigment in a binder, and a diazo layer and by the same ρ moderate application of about 2-8 cnr / m of an aqueous, about 0.05-0.25 molar solution of a diazonium compound has been sensitized to the surface of this material. 15. Diazotype material according to claim 14, characterized in that that the paper support is provided with a moisture-protecting layer. 16. Diazotype material according to claim 11-13, characterized in that it consists of an embossing made of plastic or transparent paper, optionally with a hydrophobic lacquer layer, and a hydrophilic film layer, and it by evenly applying about 2-6 cm / m of a aqueous, about 0.15-0.6 molar solution of a diazonium compound sensitized to the hydrophilic film layer has been. - 19 -309850/1109 17. Apparatus for performing the method according to claim 1 - 10, characterized in that it has a metering roller (1) which is provided with a structured surface, that is, the cross-section of the depressions over a longitudinal ¹ 2 cut of the roller is about 1000 - 40QO ^ m / mm, one Application roller (2) with a non-porous and flexible surface with a hardness of about 10-50 Shore A, a Pressure plate (4), a container for the developer solution (3) and material import and discharge instructions for the copy material, wherein the pressure between the printing plate and the applicator roller is about 2-10 g per running Millimeter and the pressure between application roller and metering roller is about 3 - 9 g per running millimeter . 309850/1109 so . Blank page