DE2021181A1 - Heat developable diazotype material - Google Patents

Description

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DR.VISCHMIED-KOWARZEEC - BR. P. WEEMHOLD * DR.D.GÜDEL

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. feel Erw ^ naii ^ e ^ fo »@ <$ © r & tmm <lie förcierrtäe alkaline sixbstana forms or a medium. ec & afft * In the world the Kiipp; l.ü.ngs: reak.tl.o ». seirä.ell continued; -

"A * B" xlilslle & ft Ixtetelojiraceitme * He Verweaung βölchen easily waeaerlöslieheη development agent, intimately mixed: it is present with the coupling components ^ and the formation of the azo dye in a single layer leads to diazotype material, which. 8

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poor storage capacity has * if, is not added to an excess of stabilizing "satire," The Verwendimg of excess acid stabilizing but has a tendency · _r give an incomplete development "

Biazotypiematerialien heat-developable, in which the light-sensitive layer or a layer adjacent thereto contains a water-insoluble, diispergiertes developing agent, have a good storability ^s. Salehe materials are, for example. has been described in British patents Kr. 1 Q66 1Q5 and 1 1115 496 «

The heat developable biazotype material described in British patent specification 1,115,496 has good storage and storage capabilities. enables very good copies. The material contains a product as a devolatilizing agent which is obtained by reacting imino-1,3t 5-triazine and an aliphatic bicarboxylic acid which has at least 5 carbon atoms in a straight chain between the carbonic acid groups. This developing agent is in the form of dispersed ones. Particles with a Bureh section size between. Q "t and to jm before. When heated, the developing agent turns into a. Medium created _f in welekem a quick coupling; ier MazoniiBffiv ^ rMnduiig an € dier Az © - coupling components without the formation of a strongly ... alkaline reacting product causes value

The aollSnjiiec & e Batei ^ registration no. 65 0848S heat developable diazotype materials, the black

III this MadrerialieiE. ScMclit ziEaitzlicii for one

compound, a blue-coupling Azokupplungskomponentβ, aauer reacting compound, a wasaerunlösliches devel opment Smitt el and a yellow © ^ iEappelnde Kömp <3nffat * "the waaeerunlöaliohe developer a acylacetamide in IORM of diepergitrten particles tiner BurchBchnitt · - · gröfl iwiiohen 0.1 and 10> u is present. B »a development · -

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medium, in the light-sensitive layer or in a the adjacent layer must be present.

In general, the development temperatures of diazotype materials with a water-soluble developer and those with a water-insoluble developer are quite high, that is, the material must be held at temperatures of 150 ^° C. or more for a number of seconds in order to achieve complete development. Neither paper nor plastic substrates are very resistant to such high temperatures.

U.S. Patent No. 3,360,369 describes the use of dimethyl sulfoxide in two-component heat developable diazotype material (ie, a material containing both the diazonium compound and the coupling component therefor) which contains urea, guanidine or an alkyl derivative of these compounds as a water soluble developing agent. The presence of dimethyl sulfoxide lowers the temperature necessary for good development and thus avoids scorching of the paper support and reduces the tendency for deposits to form in the development device. Diazotype materials in which a water-soluble developing agent such as urea is present in the photosensitive layer or the adjacent hydrophilic layer have poor storability. The presence of dimethyl sulfoxide makes this even worse.

In U.S. Patent No. 2,717,832, the application of. Diresorcyl sulfoxide has been described as an azo coupling component in two-component diazotype material for development with ammonia vapor.

In diazotype stocks which contain a water-insoluble developing agent, dimethyl sulfoxide either ^: "has no useful effect or is only when used in

^Ί * 00 9884/14 31. ^ " ^m

effective in large quantities. If large amounts are used, the durability of the material is deteriorated. Finally, it should still be noted that dimethyl sulfoxide is volatile (boiling point 189 ° C, flash point 95 ⁰ C).

It has now been found, surprisingly, that certain sulfoxides, in contrast to dimethyl sulfoxide, not only Significantly lower the temperature at which the development can be carried out successfully, but this without any significant effect on the shelf life of the products.

According to the present invention, therefore, there is a heat developable diazotype material created which in the photosensitive Layer or in an adjacent layer, a non-coupling sulfoxide of the formula

It

contains, wherein R ₁ and Rp are each alkyl, aralkyl or aryl and at least one of the groups R ₁ and Rp is an aralkyl or aryl group. The sulfoxides of the above formula used in the present invention are preferably in the heat-developable diazotype material in an amount of

ρ At least about 0.1 g of sulfoxide per m of sensitized upper

p,

area and preferably greater than about 0.25 g / m 2 present.

Suitable sulfoxides for use in the present invention are, for example, (methyl) - (benzyl) sulfoxide, dibenzyl sulfoxide, bis (2-phenyl) ethyl sulfoxide, bis (2-phenoxy) ethyl sulfoxide, (phenyl) - (methyl) -sulphoxide, (4-hydroxy) phenyl- (methyl) -sulphoxide, (benzyl) - (phenyl) -sulphoxide, (carboxymethyl) - (phenyl) -8ulphoxide, (n-butyl) - (phenyl) -sulphoxide, diphenylsulphoxide, Bis (4-hydroxy) phenyl sulfoxide _t (4-chloro) phenyl

■ 009884/1431

(4-hydrox; $ phenyl sulfoxide, bis (p-tolyl) sulfoxide, bis («C-naphthyl) sulfoxide, Bis (ß-naphthyl) sulfoxide.

In order to obtain a diazotype material with optimum durability, a water-insoluble developing agent is preferably used. chosen medium, which is present in the photosensitive layer or in an adjacent layer in the form of dispersed particles with an average size between about 0.1 and 10 Al . Particularly good results are achieved when using a water-insoluble developing agent,

by reacting an aliphatic dicarboxylic acid with an amino-1,3 »5-triazine can be obtained. Such developing agents are described in British Patent 1,115,496.

Thus, a preferred developing agent is the reaction product of an aliphatic dicarboxylic acid with at least three carbon atoms between the carboxyl groups with an amino-1,3,5-triazine of the formula

X - (X ^ X-

where X »hydrogen, straight or branched alkyl, Aralkyl or a group of the formula -Nr ^ 1, and Y = water-

/ ^R 3 is substance or a group of the formula -N (-, where R ₁ and R ₂ '.

■ ' ^E 4

in each case a hydrogen atom or a straight or branched alkyl group, unsaturated aliphatic hydrocarbon group, cycloalkyl or aralkyl group or together represent the atoms that represent the nitrogen atom to which they are bonded

'ORIGINAL INSPECTED

009084/1431 _

are, complete a heterocyclic ring, and IU and R. each represents a hydrogen atom or a straight or branched one Alkyl group, unsaturated aliphatic hydrocarbon group, cycloalkyl or aralkyl group or together one with the nitrogen atom to which they are attached represent heterocyclic ring, or R. for hydrogen atom and R. is an aryl group.

The diazotype material according to the invention can be prepared by coating a suitable carrier material with a single transmitter W ■ sibilisierenden liquid comprising a diazonium compound, an azo coupling component, a stabilizing acid, a developing agent and a sulfoxide of the above formula. The various components just mentioned can also be applied one after the other to a suitable carrier material by means of a suitable liquid medium. In a very convenient method, the carrier is treated first with a liquid comprising the developing agent and the sulfoxide and then with a second liquid in which the other components are contained.

The carrier material can, for example, be opaque or transparent paper, opaque or transparent linen, bleached kraft paper, synthetic paper, plastic foils or metal foils and optionally provided with a hydrophilic or hydrophobic film layer, or in some other known manner, e.g. with a pigment (silicon oxide) or a plastic dispersion, -precoated seia _o

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ORK3rNAL INSPECTED

For blue developing diazotype materials are 2,3-dihydroxynaphthalene-6-sulfonic acid (and its salts) and the amides of 2-hydroxynaphthalene-3-carboxylic acid, such as that 2'-Hydroxy-ethylamide and the 3'-morpholinopropylamide, very much suitable azo coupling components. Pure black evolving Diazotype materials become water-insoluble yellow coupling agents Acy! Acetamide as described in the Dutch patent application 65 08488 are preferably used in addition to such blue-coupling azo components.

To prevent the premature coupling of the diazonium compound and the azo coupling componentelji) and the diazonium compound to stabilize, acidic compounds such as tartaric acid, citric acid, boric acid, Maleic acid, gluconic acid, phosphoric acid, oxalic acid, potassium hydrogen sulfate, Malic acid, aluminum sulfate, alum and zinc chloride are used. In addition to "such an acid can be an aromatic sulfonic acid, e.g. benzenesulfonic acids 2-toluenesulfonic acid, "naphthalene (1 or 2) sulfonic acid, Naphthalene-1,5-sulfonic acid, naphthalene-1,3,6-trisulfonic acid or diphenyl-4,4 »-disulfonic acid (or a water-insoluble one Salt thereof) can be used. A water-soluble hydrophilic binder can preferably be used as the binder organic binders such as polyvinyl alcohol, methyl? - · 'pilose, polyvinylpyrrolidone and hydrolyzed Thickness of the photosensitive layer (or optionally the adjacent layer) are incorporated. It it goes without saying "that in general. mixtures of more than one diazonium compound, an azo coupling compound, a stabilizing agent, a sulfoxide, a developing agent and a binder can be applied.

The following examples serve to further illustrate the invention:

BATH 00988 4 /

- 8 Example 1

A dispersion was made with the following ingredients:

10 g of 4-dimethylaminobenzene diazonium chlorozincate 4 g of tartaric acid
1 g boric acid

5 g sodium 2,3-dihydroxynaphthalene-6-sulfonate 50 g polyvinyl alcohol
200 g melamine sebacate
^ 1 ml of wetting agent

* and water to 1000 ml

25 g of dibenzyl sulfoxide were dispersed in 500 ml of this dispersion

The separate dispersions (one contained sulfoxide and the other not) were used to senisbilize sheets of white backing paper with a weight of 80 g / m and of a kind suitable for the diazotype process. After drying, a strip was made from each paper exposed imagewise under a transparent ink drawing until the diazonium compound is under the white parts t of the drawing was mostly faded.

The strips were developed by passing them through a roll having a surface temperature of 13O ⁰ C in such a manner that their non-sensitized surfaces in contact with the roller surfaces'. The contact time was 5 seconds. The strip containing sulfoxide showed an intense blue image on a veiled blue background. The image on the other strip was barely recognizable. If an equimolecular amount of dimethyl sulfoxide was used instead of the dibenzyl sulfoxide, the image on the strip containing sulfoxide was also barely visible. Tripling the amount of dimethyl sulfoxide did not give a noticeably better result.

009884 / U 3.1

Example 2

It became a dispersion containing the following ingredients manufactured:

10 g of 4-bis (2'-acetoxyethyl) amino-2,5-diethoxy

benzene diazonium chlorozincate 15 g N-2'-H, hydroxyethyl-2-ii-hydroxynaphthalene-3-carboxamide

25 g sodium 2,3-dihydroxynaphthalene-6-sulfonate 10 g of caffeine

5 g citric acid
30 grams of thiourea
50 grams of polyvinylpyrrolidone
10 grams of polyvinyl alcohol
150 g melamine aelate
and water to 1000 ml

25 g of (phenyl) - (methyl) sulfoxide was in 500 ml of this Dispersion dispersed.

The separate dispersions (one contained sulfoxide and the others not) were used to sensitize leaves of

bleached kraft paper with a weight of 50 g / m is used. Strips of both papers were imagewise exposed and developed as described in Example 1 except that the temperature was the developing roller 12O ⁰ O. The image on the sulfoxide-containing strip was much more visible than on the sulfoxide-free strips.

If an equimolecular amount of dimethyl sulfoxide was used instead of the (methyl) - (phenyl) sulfoxide, the image on the sulfoxide-containing strip was not more visible than that on the sulfoxide-free strip.

Example 3

Ee became a dispersion containing the following ingredients

009884 / U31

- ίο -

manufactured!

10 g 4-morpholino-2,5-diethoxybenzene-diazoniuia-

chlorzincate
50 g sodium 2,3-dihydroxynaphthalene-6-sulfonate

2 grams of 2,3-dihydroxynaphthalene 50 grams of polyvinylpyrrolidone

3 g oxalic acid

30 grams of thiourea

10 g trisodium naphthalene-1,3- * 6-sulfonate

.Balz
150 g melamine / methylene bis (-3 ~ thiopropionic acid)

1 g of saponin
and water to 1000 ml.

Pausleinen- was made with an aqueous dispersion of 55 g (Benzyl) - (phenyl) sulfoxide precoated in 1000 ml of water to which 100 ml of an aqueous dispersion of a styrene / butadiene copolymer (Gesami; solids content $ 48, Particle size 0.2 / u) 20 g citric acid and 1 ml wetting agent

had been admitted. The pre-coated tracery linen was sensitized with the dispersion described above. After drying, a strip of the photosensitive obtained became Linen imagewise exposed and developed as described in Example 2. The copy showed an intense blue image on a hazy blue background.

Instead of the one used in the above composition (Benzyl) - (phenyl) -sulfoxyds can be one of the following compounds Bia- (4-chloro) phenyl sulfoxide, bis (4-methyl) phenyl sulfoxide can be used with equal success or (phenyl) - (carboxymetixylj-sulfoxide.

Example 4

Ea, a dispersion prepared with the following ingredients t ...

'0098847U31

20 g of 4-bis ^ '- acetoxyäthylJamino ^ jS-diethoxybenzoldiazonium-chlorozincate 15 g citric acid 50 g sodium 2,3-dihydroxynaphthalene-6-8ulfonate 75 g resorcinol

20 g of N, N'-dodecamethylene-lDis (acetyiacet) diamine 30 g thiourea 50 g polyvinylpyrrolidone 10 g polyvinyl alcohol • 200 g melamine sebacate 50 ml of ethanol and water to 1000 ml.

50 g of diphenyl sulfoxide were added to this dispersion. Natural transparent paper: Dispersion sensitized.

Natural tracing paper (80 g / m) was made with this

After drying, a strip of the photosensitive material was exposed imagewise and developed as described in Example 1. The surface temperature of the developing roller was HO ⁰ C.

The copy showed an intense black image on a hazy gray background.

Example 5

A dispersion was made with the following ingredients:

10 g of 4-bis (2 ^l acetoxyethyl) amino-2,5-diethoxy-benzene

diazonium chlorzincate 50 g polyvinylpyrrolidone 10 g polyvinyl alcohol 5 g citric acid 50 g sodium 2,3-dihydroxynaphthalene-6-8ulfonate 30 g talc powder g melamine sebacate and water to 1000 ml.

00988A / H31

25 g of dibenzyl sulfoxide were added to 500 ml of this dispersion and 50 g of dimethyl sulfoxide are added to the remainder of the dispersion. Dimethyl sulfoxide is opposite to dibenzyl sulfoxide present in six times the molar amount.

The separate dispersions were used to sensitize '

Sheets of white backing paper (70g / m), which is suitable for the diazotype process is suitable. The material with the dimethyl sulfoxide was significantly less ^ Shelf life as the material with the dibenzyl compound. A strip of each paper became imagewise exposed and developed as described in Example 1. Both strips developed into an intense image.

If, according to Example 1, a three-fold excess of dimethyl sulfoxide based on dibenzyl sulfoxide is used slightly better shelf life was achieved, but development was compared to / 6 usage of the sixfold excess is significantly less satisfactory.

Example 6

™ It became a dispersion with the following ingredients manufactured:

10 g of 4-bis (2 ^l -acetoxyethyl) amino-2,5-diethoxy-

benzene diazonium chlorozincate 40 g polyvinylpyrrolidone 20 g polyvinyl alcohol

50 g sodium 2,3-dihydroxynaphthalene-6-sulfonate 14 g N, N, '- octamethylene bis (acetylacet) - diamine 5 g citric acid
30 g talcum powder
175 [beta] melamine-3ebacate
1 ml whetting agent
and water to 1000 ml.

009884 / U31.

40 g of diethyl) ("benzyl) sulfoxide became given to the dispersion.

White backing paper (70 g / τα) is used with this dispersion sensitized. After drying it became a strip of the paper Mldweise "exposed and - as in. Example "written - developed. The copy showed an intense black UiId on a veiled gray Background.

009884/1431

Claims (3)

- 14 claims / Π) Heat developable diazotype material, characterized in that that it is in the photosensitive layer or in an "adjacent layer" non-coupling sulfoxide of the formula Il R ₁ -SR ₂ contains, in which R ^ and IL are alkyl, aralkyl or aryl and at least one of the groups R ₁ or R _{2 is} an aralkyl or aryl group, 2. Heat development "ble diazotype material according to claim 1, characterized in that the developing agent is in the form of water-insoluble dispersed particles with an average size between about 0.1 and 10 / u is present. 3. Heat developable diazotype material according to claim 2, characterized in that it contains as a developing agent such that by reacting an aliphatic Dicarboxylic acid having a chain of at least 3 carbon atoms between the carboxyl groups an amino-1,3,5-triazine of the formula \ ²
G i Il X - CJV JO - X where X = hydrogen, straight or branched alkyl, R ₁ R, Aralkyl or a group aex? Formula -N ^ .1 and Y « ⁴ 2 009884/1431 Is hydrogen or a group of the formula -JK ^, where Rj and R ₂ each represent a hydrogen atom or a straight or branched alkyl group, "unsaturated aliphatic hydrocarbon group, cycloalkyl or aralkyl group or together represent the atoms which complete a heterocyclic ring with the nitrogen atom to which they are bonded, and R, and R. each represent a hydrogen atom or a straight or branched alkyl group, unsaturated aliphatic hydrocarbon group, cycloalkyl or aralkyl group or together with the nitrogen atom to which they are attached, a heterocyclic ring, or R, represents a hydrogen atom and R ^ represents an aryl group. 00988A / U31