DE1284292C2 - SINGLE COMPONENT DIAZOTYPE MATERIAL - Google Patents

Description

Y ^s This diazotype material is very light-sensitive

lo hch and very suitable for visual detection the end point of exposure when copying is done with mercury-vapor lamps. Copies based on this material show in practically all parts of the picture in which the azo dye is present, is in both the strong and the weak and in the unexposed parts, the same azo dyes since the light decomposition product of the diazo compound does not occur during development

contains, in which X is an anion, R · is a methyl or undesired dyes with still present di-ethyl radical, R = a methyl or ethyl radical or, ao forms azo compounds. Even if R ^{1 is} a methyl radical, the azo dyes are also a Cyclohexyl radical can be very beneficial to a drop in pH, R ^{3 is} a chlorine atom and the phenoxy radical. ",""..,,

remainder once or twice by halogen, methyl or a diazotype material according to the main patent,

Alkoxy can be substituted, characterized in that with a diazo compound which characterizes a benzyl group that it additionally carries between * 5 and an alkyl group on the amino lip, 5 and 40 mol percent has been sensitized to another diazo compound (cf. claim 1 of the main compound of the general formula patents), is suitable for development with ⁶ weakly acidic, buffered phloroglucose developers. The waß- _N χ Rieen solutions of these diazo compounds comprise ² 30, however, a considerable capillary and

can consequently penetrate rather deeply into the paper used as the carrier material before the sensitized material has dried. Diazotype paper into which the sensitizing liquid has penetrated deeply, ^OR 35 is considerably less light-sensitive and less

Y suitable for the visual determination of the end point

exposure than similar diazotype paper, while

in which X is an anion. R * and R ^{5 are} alkyl groups with the production of which the sensitizing liquid is not at most 3 carbon atoms and Y has penetrated one or only a little bit into the carrier. The background of copies on 1 to 3 carbon atoms or phenoxy-substituted diazotype paper, which may be underexposed once or twice with alkoxy at 40, also has an unequal phenyl group or an optionally distribution of the azo dye that is undesirable or doubles with Is alkoxy of 1 to 3 carbon. .

atoms, methyl, chlorine or phenyl substituted A one-component dtazotype material according to

Phenylthio radical contains. 45 main patent showing a diazo compound of the above

2. One-component diazotype material according to the general formula in which R ^{1 is} a methyl or atnyl claim 1. characterized in that the further radical is, R ^{2 is} a methyl or ethyl radical or, if the diazo compound is p-diazo-2,5 -diäthoxy- (4'-methyl- W is a methyl radical, also a cyclohexyl radical is phenyO-mercaptobenzene. can, R ^{3 is} a chlorine atom and the phenoxy radical is a

50 or twice by halogen, methyl or alkoxy may be substituted is not so good for

the development with weakly acidic, buffered

Phloroglucinol developers. These diazo compounds couple too slowly for this purpose, so that if

The invention relates to a one-component diazo copy on this one-component diazotype paper typiemateriai, which is a diazo compound according to the main with the weakly acidic, buffered Phloroglucmpatent 1 174 612 the general formula developers develop the picture only gradually-

Hch becomes visible.

N * ^x In fact, practically all diazo molecules are in

R3 I 60 the copies after drying the

V ^ X killed developing liquid in azo dye

j! changed so that the picture then has strong contrasts

X J \ (I) points and is clearly visible, however this conversion is

Difficult to determine, especially at the beginning. "5 This is a disadvantage in making copies. It is then not possible immediately after applying the

^ ₇ developer liquid to determine whether the copy

^ / is peaceable. It is obvious that these over-

. ^pii J ^ one-component dii

picture-size exposure takes place at high speed.

The object of the invention is to find a

One-component diazotype material, which is also Y _n __ / \ _Y

so good for a development with a weakly acidic ⁸ \ /

PhloroglucinenUvickler is suitable like a diazotype j

material according to the main patent, which with a Diazo- ίο OR «

compound containing a benzy group and an alkyl

group on the Ajmno group, has been sensÄilized, where X is an anion, R ₁ and R _{8 show} alkyl groups with without the night, deep m the carrier are at most 2 carbon atoms and Y a paper used by Bjatenal. Methoxypbenyl, ethoxypbenyl, dimethoxypjienyl,

The task of preventing the penetration of the aqueous solutions _1S diethoxyphenyl, pbenoxypnenyl, tolyl mercapto, the diazo compounds in the paper used as the carrier material, xylyl mercapto, bypbenyl mercapto or chlorine, is also of particular importance in the nyl mercapto group. vd G. BuIL, 15. maert 1957 «(van der Gnnten BuUe these connections can no longer be sufficiently resolved in the tin). The solution becomes, according to this light, sensitizing liquids and couple “very active with temperature point> .n a certain selection of the substances phloroglucinol in a weakly acidic, buffered tuent on the benzene nucleus of a diazo compound with the formation of fine black azo vision the dyes according to the invention. If compounds with larger sub-goals are used particularly suitable for development with substituents such as those in which R _{1 is not} weakly acidic developers and R 1 are propylene groups, depending on the case

The subject of the invention is a one-component a ₅ which composition the sensitizing liquids diazotype material, which have a diazo compound according to, solubility difficulties occur. If main patent 1 174 612 of the general formula less or more easily substituted compounds ver

are used, such as those in which Y is a phenyl

^ 2 ^ · group is, the picture can be used during development

R ³ _v j 3o with a weakly acidic, buffered phloroglucinol

'^ developers bleed out, as the diazo molecules are in the

Dissolve developer liquid and pour over the surface Λ, ~. of the copy migrate before they are converted into azo dye

Q * ■ 'be converted.

'\ / \ 35 Very good results are obtained with the single-component

'nenten diazotype paper according to the invention, the

χι ^{y X} R2 i 'p-diazo-2,5-diethoxy- (4'-methylphenyl) mercapto-

- .. ·· 'contains benzene than the other Koiuponente.

Even if the content of this diazo compound

in which X is an anion, R ^{1 is} a methyl or ethyl radical 40 is relatively low, which is on the copy, R ^{2 is} a methyl or ethyl radical or, if R ^{1 is} a methyl radical with a weakly acidic, buffered developer, can also be a cyclohexyl ^{radical, the image developed quickly visibleT The diazo compound R 3 is} a chlorine atom and the phenoxy radical does not cause or bleed the image in or out. In addition, twice substituted by halogen, methyl or alkoxy, it is easily accessible and can be one of the cheapest diazotized, contains and is characterized by 45 compounds that are used as the other component in that it is additionally between 5 and 40 mole percent of diazotype paper according to of the invention can be used a further diazo compound of the general.

Formula Of the diazo compounds that make up the main part

in the diazotype paper according to the invention

^ "2 ^ 50 turns are particularly those in which

R60 “one of the hydrogen atoms of the phenoxy group

\ / f \ a chlorine atom is replaced, is of interest. In the long-

'jj (II) seeds conversion to azo dye during the

■. / - .. Development with a weakly acidic, buffered

ι ⁷ OR ⁴ 55 Phloroglucin developers cause a still low

Y less bleeding of the image than the corresponding

Compounds without a chlorine atom in the phenoxy group.

in which X is an anion, R * and R ^{6 are} alkyl groups with In addition, the possibility of a

are at most 3 carbon atoms and Y is an optional substitution in the phenoxy group on the main one referenced once or twice with alkoxy with 1 to patent.

3 carbon atoms or phenoxy substituted Phe- The one-component diazotype material according to

nyl group or an optionally single or double of the invention does not offer the difficulties with alkoxy having 1 to 3 carbon atoms, methyl, difficulties with regard to the penetration of the chlorine or phenyl substituted phenylthio radical, 65 sensitizing liquids in the paper, as Ue contains. the production of the diazotype paper according to

The preferred further diazo compound is p-di- Spruch 1 of the main patent can occur. the azo-2,5-di-ethoxy- (4'-methylphenyl) * mercaptobenzene. Light sensitivity of the one-component diazotype

paper according to the invention is reduced by the addition the phenylraereaptobenzene or bipbenyldiazo compound very little, although these diazo compounds are considerably less opaque than those that make up the bulk of the mix. Also the possibility of an exact visual determination the end point of the exposure is retained. The mixture of azo dyes that is formed during the development with the acidic, buffered phloroglurine developer forms, has the same hue in all parts of the picture and is opposite to a drop the pH value sufficiently stable. When developing, however, is contrary to the corresponding Material according to the main patent, the image quickly enough visible, so that the desired surveillance is possible during the production of the copies. Of course, it all depends on the proportions the constituents of the mixture. If the mixture consists of less than 60% of the main part, is the light sensitivity of the diazotype paper and in most cases also the possibility of a visual one Finding the end point of the exposure is considerably less. If it's made up of more than 95% of the If there is a component mentioned above, the image will not be visible quickly enough. The limits given above as are of course not sharp, but show approximately the appropriate proportion of the components.

Some of the phenyl mercaptobenzene and biphenyl diazo compounds are known, for example from Dutch patent specification 47 899, German patent specification 896 591 and British patent specification 759 045.

Many mixtures of diazo compounds can be used in the diazo paper according to the invention will. A list of a number of suitable mixtures is given below (the percentages refer to the number of molecules):

65% 4-diazo-2-phenoxy-5-chloro-dimethylaniline +

35% 4-diazo-2,5-dimethoxy-biphenyl,

75% 4-diazo-2-phenoxy-5-chloro-N-methyl-N-cyclohexylaniline +

25% 4-diazo-2,5-diethoxy 4'-ethoxy-biphenyl,
85% 4-diazo-2- (2 ', 4'-dichlorophenoxy) -5-chloro-

diethylaniline +

15% 4-diazo-2,5-di-n-propoxy-4'-methoxybiphenyl, 90 % 4-diazo-2- (2 ', 4'-dimethoxyphenoxy) -5-chloro-

dimethylaniline +

10% 4-diazo-2,2 ', 5,5'-tetramethoxy-biphenyl,
i> 5% 4-diazo-2- (3'-chlorophenoxy) -5-chloro-

diethylaniline + ^5C

5% A-Diazo ^^ - di-isopropoxy ^ '- acetamino-

biphenyl,
¹ SO% 4-diazo-2- (2'-chlorophenoxy) -5-chloro-

N-methyl-N-ethylaniline +
10% 4-diazo-2,5-dimethoxy- (4'-methoxyphenyl) -

mercaptobenzene,
70% 4-diazo-2- (4'-methylphenoxy) -5-chloro-

diethylaniline +
30% 4-diazo-2,5-dimethoxy- (2'-methylphenyl) -

mercitptobenzene,
90% 4-diazc-2- (4'-bromophenoxy) -5-chloro-

dimethylaniline +
10% 4-diazo-2,5-di-n-propoxy- (4'-chlorophenyl) -

mercaptobenzene.

⁶ 5

Of course, mixtures of more than two diazo compounds can also be used, such as Mixtures of

40 y 4-diazo-2-pbenoxy »5H! BJQr-diethyJ & JiUin +
40% 4-diazo-2- (4'-chloropbenoxy) -5-chloro-

dimethyJanilin, which together form the main

poneate form, with
20% 4-diazo-2,5-di-methoxy-4'-pbenoxydipbenyl

or a mixture of

70% 4-diazo-2- (3'-methoxypbenoxy) -5-cblor-

dimetbylanUin +
15% 4-diazo-2,5-diraethoxy- (4'-phenylphenyl>

mercaptobenzene and
15% 4-diazo-2,5-diethoxy (2 ', 4'-dimethylphenyl) -

mercaptobenzene,

the latter two compounds together forming the other component.
Of some of the diazo compounds, ^ those in the

One-component diazotype paper according to the invention form the other component of the mixture, it is known that they are attached to one-component diazotype material in mixture. other diazo compounds can be used. In this regard, reference is made to the article "Couches heliographiques" in Science et Industries Photographiques, vol. 26, no. 8, August 1955, and to Dutch patent 80603, column 6, line 39.

The purpose of their use is to change the tone of the azo dye »in the developed copy.

Their use in one-component diazotype paper according to the invention and the one achieved thereby Effects are not known.

Regarding the preparation of the diazo compounds which are the main component in the one-component diazo printing paper according to the invention, reference is made to the main patent. With regard to the Preparation of the diazo compounds, which form the other component, is referred to riat report 813, Pp. 1301 bis, 1306 and 1311-1314, to the German See U.S. Patent 896,591 and UK Patent 759,045.

The one-component diazotype papers according to the invention can contain the usual auxiliaries.

In the following examples, the diazo compounds are generally in the form of their zinc chloride double salts used. However, it is also possible to use other salts, such as the chloride, Nitrate, boron fluoride and the cadmium chloride double salts.

example 1

White base paper for dns diazotype processes of 80 g / in ² is supplied with a solubility of

16.8 g double salt of 4-dimethylamino-3- (4'-chlorophenoxy) -6-chlorobenzene-diazonium chloride and zinc chloride,

4.3 g double salt of 4- (4'-methylphenyl> mercapto-2,5-diethoxybenzene-diazonium chloride and zinc chloride,

5 g tartaric acid,
30 cm ^{3 of} a polyvinyl acetate dispersion

sensitized in 1000 cm of water and dried.

The sensitized surface contains approximately 0.44 millimoles of diazo compound per square meter; about 80% of it consists of the main component.

The photosensitive side of a sheet of diazotype paper is covered with a sheet of tracing paper a pencil drawing is made, covered and

7 8

with an actinic fluorescent low pressure ^ q thiourea

exposed to mercury vapor lamp. The exposure ₄ j | phloroelucin '

is continued until the empty with, ° _sul f _oni e _rt he succinic acid di iso butvlester

Parts of the drawing parts in contact { | ^ »On '^ di-iso-butyl succinate,

only a small amount of diazo compound 5 ₂ 5 e sodium benzoate

lagged behind. The point in time at which the be _m J _{tertiary sodium citrate (5} >

must be terminated, can very well by _{m 1} qJ _{K) cm3 water} ^vn '
visual observation (for example from the direction

the light source) which during the exposure in the The pH of the developer liquid is about 6.3.

Photosensitive layer changes color io The developed copy has a black image

to be established. on an evenly veiled surface.

The latent diazotype copy thus obtained is de- The image is visible considerably more quickly than when

by placing a layer of one on its face instead of the above-mentioned mixture of

about 9 g / m * of a developing liquid of the following diazo compounds excluding 20.6 g of the main

the composition applies: 15 components in the sensitizing liquid

4 ε phloroelucine would have turned. The azo dye in the veiled one

1 ε Acetoacetani'lid underground has the same color as that in the

llg ^ Ethylhexvlschwefelsaufemonoester in the black parts of the picture. The black azo dye is

Form of the sodium salt, ^ KändT ^ ™haben pH value extremely

15e ⁸ Nl "rhmibenzoate ^{If the G} .rundpapier has ^a 8 ^latte surface

1501 Sodium formate ^{1 and d} | f _t developer liquid with a roller.

in inoorm3 Wneeer is brought into one of the movement of the copy

in luw cm of water. rotates in the opposite direction, this can

The pH of the developer liquid is about 5.8. The wrapped picture bleed a little. As a result of this

The azo dye image on the copy will bleed quickly and the azo dye parts will be blurred

visible. The developed copy has a black border in the form of a band of clearly

Image on a uniformly veiled background of visible »fibers«, the length of which is between

The azo dye in the veiled lower part of a few tenths of a millimeter and a few millimeters

Grund has the same shade as the one in the black 30. This edge is nonexistent or there is a lot

zen image parts. The black azo dye is visually narrower or much less visible when the phen

' ^i! A drop in the pH value is extremely stable in the main component of the mixture

_Ί ^Ιι0: dig. The image is sharp and shows no traces of the diazo compound forming a chlorine atom as a substitute

'' ^c: bleeding on. tuenten wears or even if in place of the other

^!; '■''-' If, in place of the above-mentioned mixture of 35 component-forming diazo compounds, a much

^H ; '; ^! Diazo compounds only 21 g of the diazo compound, larger amount of the corresponding 2,5-diethoxyver-

^s V which forms its main component, is used, bond is used.

"/ - '" also produces a black image. This will

'but much more slowly visible. *

40 B e i s ρ i e 1 3

^L example 2

'' White base paper for the diazotype process

^{n ;;} of 80 g / m ² is sensitized with a solution of

White base paper for the diazotype process 45 n _g double salt of 4-N-methyl-N-cyclohexyl-

of 80 g / m * is mixed with a solution of amino-S - ^ '- chlorphenoxyVo-cbiorbenzol-

17 g double salt of 4-dimethylamino-3-phenoxydiazonium chloride and zinc chloride,

6-chlorberizol-diazonium chloride and zinc 3.3 g 4- (4'-methoxyphenyl> 2,5-diethoxybenzene-

chloride, diazonium chloride,

1.8 g double salt of 4- {4'-methylphenyl> mercapto- ⁵ ° 5 g tartaric acid,

2,5-di-n-propoxybenzene-diazonium chloride and 50 g particles of uncooked rice starch,

Zinc chloride, 30 cm ⁸ polyvinyl acetate dispersion

3.5 g of tartaric acid, _in ^ ^ ₃ water and dried

, i ' ^g » ^B ? ^rsätlre ; -, j · · 55 The sensitized surface contains about

30 _CT i * _e mer polyvinyl acetate dispersion 0.45 millimole diazo compound per square meter;

sensitized in 1000 cm ^{3 of} water and dried, 70% of which consists of the main component.

The sensitized surface contains about one sheet of the diazotype paper, as in

0.46 millimoles of diazo compound per square meter; Example 1 described, imagewise exposed

about 92% of it consists of the main component. 60 The end point of the exposure can easily be determined;

A sheet of the diazotype paper is soon reached, as in the case

game 1 described, imagewise exposed The end point The latent diazotype copy thus obtained is de-

the exposure can be determined very well and wrapped by placing a layer of on its image side

is soon reached ^about * · ⁵ % f ^m * ^ ^{051 developer liquid of} the following

The latent diazotype copy thus obtained is applied:
wraps by putting a layer on their bottom side

from about 8 g / m * of a developer liquid the following 10 g thiourea ^

the composition applies: 6.5 g PMörogracin,

4 g resorcinol,

2 g sodium salt of dibutylnaphthalenesulfonic acid, 1.5 g citric acid,
25 g sodium benzoate,
85 g disodium succinate (6 aq.)
in 1000 cm ^{3 of} water.

The pH of the developer liquid is about 6.2.

The developed copy shows a black image on an evenly veiled background. After applying the developer liquid, the

Image visible very quickly. The azo dye in the veiled background is the same color as that in the black parts of the picture. The black azo dye is extremely resistant to a drop in pH resistant. The image is sharp and has no traces of bleeding.

If, instead of the above mixture of diazo compounds, only 16 g of the main component in the If sensitizing liquid are used, a black image is also obtained. This will however much more slowly visible.

Claims (1)

i 284 292 1 2 contains, in which X is an anion, R ¹ an ^ AJkylrest with claims: 1 to 3 carbon atoms an alkyl radical with 1 to I, one-component piaxotype material that contains a benzyl residue or the Cyjbwytotwd,
Diazo compound according to main patent 1174612 5 stoffatoro, a halogenated
the general formula & Ä li ^ ÄTutai sub ^ ulm ^ _n