DE1472860A1 - Heat developable copy paper - Google Patents

Description

Heat developable diazo type paper

The invention relates to a diazotype paper which can be developed by the action of heat _{or the like}

The already known papers of this type have numerous disadvantages, of which the following may be mentioned: Higher Price, short shelf life before using the paper, development too slow, pungent odor during development, too high development temperature, too low light sensitivity, Yellowing tendency too high during development, sticking of the paper during development, colored background, etc. "

The invention is based on the object of eliminating the aforementioned disadvantages «

The aim of the invention is to ^{create a heat-developable diazotype paper r} /, u , which can be used as a carrier and on Boinur a lent tem ρ find lic; not to mention

9 U 2 3 / I) 8 R 2

BATH ORIGINAL

the at least one Diaz overbung and one by an acid

has stabilized coupling component, which is thereby ■ j

It is characterized by the fact that it has at least one developer layer that at least one of the elements of a mixture of at least one salt of a first volatile or liquid base and one first acid and from at least one salt of an acid that is weaker than the first acid and a base that is stronger as the solid base, the development of paper contains

Jf occurs through the neutralization of the diazotype paper

bilizing acids with the help of a gaseous or liquid alkaline medium, the increase in pH ~ obtained in this way together with the action of temperature enables a rapid reaction between the coupling component and the diazonium salt, both of which are present in the tracing paper, and leads to Formation of the azo dye _e The formation of the alkaline substance (hereinafter referred to as developer for short) occurs during the heat treatment of the paper and proceeds according to a very simple principle that allows the use of a large number of chemical products

The process of development takes place through the double decomposition of a salt of an acid and a volatile or liquid base with a salt of a weaker acid and a stronger non-volatile base weak base, water and a weak acid ₀ The latter has no effect on the tracing paper. The weak

i'09 «23 / 08ß? BAD ORIGINS ~

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Base in connection with the water leads to the desired development

For a better illustration, the following schematic equation, according to which the reaction of developer formation takes place, is used:

Afo Afa + Afa Bfo> Afo Bfo + Afa Bfa AD + H ₂ O

In this equation:

Afo ss anion of a strong acid
Afa = anion of a weak acid
Bfo ss cation of a strong base
Bfa = weak base cation
Afa = weak acid

BfaAD = volatile or liquid at the development temperature weak base = developer

The terms "weak" and "strong" are to be related to each other and not to be understood in an absolute sense *

From a practical point of view, the following example may be given:

+ 2KHCO ₅ >> K ₂ SO ₄ + 2 CO ₂ + 2 NH ₃ ♦ 2 H ₂ O

(D (2)

909823/0662

The mixture of salts (1) and (2) is described below as a reaction pair designated

Once the principle of "generating the developer is established, It must be pointed out that all possible mixtures are suitable for the production of a heat-evolving tracing paper not suitable · Understandably, the paper is so more interesting, the lower the temperature for generating the developer is · A lower temperature limit should still be observed · This temperature minimum can be set to 80 ° C on the one hand, in order not to trigger self-development in fresh papers that are stored at higher temperatures and on the other hand, to prevent development in contact with the exposure drum of large printer-type printing machines Temperature is sometimes at 70 ° 0,

■ The reaction pairs or components must be chosen so / that the heat-sensitive tracing paper kfcinen the aforementioned Disadvantages have "Therefore, one must fall back on reaction pairs" which are as stable as possible at normal temperature but whose reaction rate is very high at the development temperature. It is important that the reaction pair reacts not only at a certain temperature and not at a temperature below that, but rather. that this reaction is also quick and as complete as possible. If these conditions are not met, receives one in the first pail a heat-sensitive tracing paper!

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that in the unexposed state, is not storage-stable, im second pail a paper whose development is too slow goes or of the reaction pair above-average properties, ten requested.

It must be pointed out that the components of the reaction pair, taken by themselves, are not developers, doh «, that they are unable to produce the dye, if they are used without a suitable second component.

The inheritance of the heat tip indigenous tracing paper can, on the other hand, be improved significantly if the components of the reaction pair are separated and only at the moment of development under the influence of the temperature unite.

The advantage of the paper according to the invention is the need to to have to unite two substances for development, and in the fact that these substances up to the moment of Development can be kept separate, since they are contained in two different layers «From these layers can one being a water-containing one and the first component of the reaction pair in the form of a solution or dispersion and possibly also contain a first binder, while the second layer comprises an organic liquid which the second Component of the reaction pair as well as a second binding agent contains »

9096.23 / 0862

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The contact between the two layers during development is caused by the melting of one or the other component of the Reaction pair caused or by the softening or melting of the binding agent.

Depending on the circumstances, it is appropriate, moreover an infusible one Add pigment to give the two layers some strength and thereby tearing or "sticking" of the To prevent paper.

The pouring of the reactant complex in a single Layer is still possible · In this pail it is preferable to turn the two components in finely dispersed form in an organic liquid containing one or more suitable Contains binding agent,

This type of production is more complicated than the previous «Es It is often advantageous to use two layers of paper. For reasons of reatability, these are preferably referred to as the back Layers are applied because then the first component of the reaction pair is simply in the anyway on the back of the light-tracing paper poured liquid - generally water to ensure the required flatness <- brought into solution will·

This layer can also contain a binder, its Main task is the penetration of the organic

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Layer that comes to lie on top of the water-containing layer, to regulate »It is important that the organic fluid of this the second layer penetrates very carefully into the first layer,

so that the fortification of the whole complex is guaranteed. ,.

The penetrating amount of organic liquid is only allowed to be very high be low in order to prevent premature contact between the components of the heaction pair «

The second component is preferably in the aforementioned pigment form, namely as a suspension in the organic liquid second layer is used.

to fix this constituent and make the To avoid organic layer, one uses one or more soluble binders, the task of which is the whole, before the To protect the effects of external moisture «These binders also serve to regulate the viscosity of the second layer and thus support the perfect adhesion of this second layer on the first,

The optimum "viscosity" depends on the coating process used away.

The binders of the organic layer can be used during development melt or become white and thus facilitate the reaction of developer formation.

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As a binder of the first layer that prevents the penetration of the The second regulate, gelatine, carboxymethyl cellulose, alginates, methyl celluloses and others. ··

The following are the binders of the organic layer called: epoxy resins, carbonated chalk, chloropolyethylene, butyl chewed, acrylic acid copolymers, styrene-butadiene copolymers, Chloropolyvinylidene copolymers, polystyrenes, Acrylic resinsβ

The following resins can be added to these substancesί Oumarone, indene and terpene resin, resins derived from styrene, Hard paraffin, butadiene styrene resin, microcrystalline paraffins, microcrystalline paraffins and butyl rubber.

The purpose of these substances is to ensure that water vapor is impervious to water to improve, a whitening of the layer in the warm to » stand to make it possible to improve the adhesion of the layer, to influence the flatness of the diazotype paper, among other things.

The use of dispersants, wetting agents or emulsifiers will be recommended in most cases to solve the dispersion problem to simplify and in the semolina process precipitation and To avoid lump formation

The substances were made to a degree of fineness of. Crushed 1 to -10, which is in a liquid medium or in solid form

90 9023/08 62; - 9 -

can happen * The 3? grain size is required to get the to favorably influence chemical conversion in the development of development and to avoid that the paper gets a rough surface »

. The use of lump-preventing or emptiness-absorbing agents in the course of the grinding process; will very often be indispensable in order to obtain a finely divided substance. It is pointed out that grinding can be avoided if finely precipitated precipitates W are used, which are obtained by adding a non-dissolving agent to their solution. ,

The list of binders mentioned above is by no means restrictive; the substances to be used may be, depending on the type of salt used in the first and second layers and, depending on the used organic liquid different, the latter being the local legislation may be subject "For example, when the salt of the first layer meltable λ bai ? is, then it is by no means necessary - and not even useful ·· that the salt of the second layer is also fusible o It is also of no use if the organic binder is fusible «In this case a second layer could be used, which _f aside of the second salt, a high melting point binder, or even a non-fusible; contains a binding agent that is dissolved in a suitable liquid

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If, on the other hand, the salt of the first layer is not meltable, - but that of the organic layer, the structure of this layer can be made more insoluble by using a certain amount Stabilize pigments, e.g. colloidal or non-colloidal silicas, talc, titanium oxide, etc.

Finally, if you want an organic layer that is in the Heat softens, ethyl celluloses or polyvinyl acetates with the addition of fusible substances can be referred to · Besonk Some plasticizers are of great interest in this regard »■

In some cases it is advantageous to have more of one salt per schioht or a component with a relatively low melting point * - point to lower the melting point of the whole complex and in this way obtain a paper that is a lower one Development temperature has »

The lowering of the developing temperature can finally be achieved

certain additions can be made, which in themselves affect the implementation have no effect on developer formation · Such an additive can be mannitol, for example.

The developer mixture can often be used as a top or top layer which is poured onto the light-sensitive soleplate »In this case the different salts are separated crushed and before pouring the top or top layer. agree.

909823/0802

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A variant of this manufacturing process is that a single component of the reaction pair is used in the top layer and the second component is mixed with the photosensitive solution causes “In this lall you can turn on the coupler . insert the pre-layer of the tracing paper.

Some coupling components can j | be used either as a pigment or diapered in the organic top layer »

Below is a list, which is in no way limiting in nature, of some of the salts that are used as constituents of the reaction pair can be used:

Substances of the type Afο Bfa. Substances from the gyp Afa Bfο

NH ₄ NO ₅ ; Na ₂ CO ₅

C ₂ H ₅ OCO-CH ₂ NH ₂ «HC1 X ₂ CO ₅ . ί

NaHCQ _-5

5 BaCO,

NH ₄ Cl KHCO ₅

3 NH.HSO, CaO

(NH ₄ J ₂ (SiF ₆ ) , ....... _{, CaBO 5}

NH ₄ SCN. _ν ,, -......... Ba (0H $ ₂ .8 H ₂ O

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Substances from ifarp Afc Bfa Substangea. of the! type Afa Bfο

(NH.) _O Ss> 0q MgBO,

MJgOI ₂ -HH ₊ Oi- _{6H 2} O NaOCO- ^

O-

NaOOO

10 H ₂ O

O ₂ H ₅ O _:. · ". ' NaOOO-CHg CH ₂ OOONa

-C - NHg.HCl 'N-OH ₂ -CH ₂ -N

_H0 5HOCO-OH ₂ CH ₂ OOOH

-4 H ₂ O

NaOCOCH ₅

The following non-restrictive ones serve for a better understanding Embodiments of the invention

Example 1 '

A erete schioht cast, which is composed as follows «

Ammonium ihiooyanate 15 kg

Water . 10 kg

1 # (jelatin solution 0.5 kg

■■■ · '■' -. . t

This layer is ge-troekoet ·· 'on with the usual means. 1m ²

Läfeeohiohtete area should be between 5 and 10 g, solid substance ;; omitted "

Then a second sauce is prepared, which is composed as follows:

Crushed calcium borate 15 kg

Toluene 60 kg

Polyvinyl acetate 5 kg

This sohioht is first poured in the usual way and dried for five seconds at 100 ° C.

After exposure, behind a translucent or translucent A blue copy is obtained from the original artwork by heating it to 130 ° C.

Example 2 ,

It is poured under the conditions of Example 1, the following first backing layer ι

Water 10 kg

Ammonium chlorate 4 »5 kg

Mannitol 2 kg

The second reverse side is poured onto this sole

Toluene J5 kg

Crushed sodium bicarbonate 15 kg

Butyryl polyvinyl acetal 4 kg

By heating to 135 ° C obtained * ton a blue Far.

Example 5 . _: ? *; ■ /

A first is poured under the conditions of Example 1 back layer:

Ammonium nitrate 10 kg

Water 10 kg

ITaoh dem! To dry, you pour the second back layer!

Benzene 30 kg

Polyvinylidene chloride '7 kg

(in solution) in acetone 14 kg

Crushed magnesium oxide 21 kg

Acetone 30 kg

2
The precipitate of solid substances should contain 5 to 15 g per m layer support. It is dried sehneil · at 80 to 100 ° C, by heating to 120 ° C we get a blue color ·

Example 4

Pour onto the back of a blueprint paper, which gives a blue color in the so-called dry or gas development one and then dried at 80 to 100 ° C. the following dispersion!

Xylene 15 kg ^ polyvinylidene chloride 3 kg in solution

in acetone 6 kg

Crushed borax 5 kg

Crushed ammonium fluorosilicate 10 kg

j _v acetone, 10 kg

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ο The precipitation of solid matter should be per m layer support

10 jjfis 20 g.

Warming up to 120 ° 0 results in a blue shade »

Example 5

It is poured under the conditions described for Example 1

the first back layer

Water 15 1 ^

Ammonium sulfamate. , 10 kg

1 $ igea Grlyko! Alginate in water 7000 enr

Compartment for drying is poured the second back layer ι

Comminuted disodium salt of ethylenediaminetetraacetic acid 1.8 kg

Acrylic resin 300 g

Ethyl cellulose 50 g

Toluene 4 kg

Colloidal silica - 100 g ■ *

Triphenyl phosphate ''"" ■■■ --- ■■ ioo g '

The development at 110 ° 0 gives a blue image.

Example 6 __ _; .

The following mixture is poured under the conditions described for Example 4: ... ,

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Crushed sodium borate 5 kg

Crushed benzylamine hydrochloride 10 kg

Ethyl cellulose 2 kg

Benzene 60 kg

The development at 130 ° C gives a blue hue.

Example 7

On the back of a blueprint paper, which is ϊ -

M development with ammonia gas yields a black color, then poured to a first backing layer, which is dried:

Warm water of 60 ° 0 100 kg

Ammonium bromide 50 ^: kg

Ammonium chloride. 30 kg

5 to 10 g of solid substance should be deposited on 1 m ^{2 of the substrate.}

It is dried and then the second back layer is poured

Benzene x 100 kg

Crushed titanium oxide 1 kg

Carbon polyethylene 8 kg

Crushed borax 30 kg

About 5 to 10 g of solid matter should be used in 1 m ^{2 »}

Untwioklung at 110 C results in a black, green

playing picture · _{ft ΛΑ A Ä} ;

909623/0802 -17-

Example 8

On the light-sensitive side of a tracing paper, which turns blue when dry or gas develops
results, you pour and trooknet at 60 to 70 ° 0 the following mixture

Crushed sodium bicarbonate 5 kg

Crushed ammonium sulfamate 20 kg

Chloropolyäthyleh 3 kg

0? Oluene 25 kg

2
One rubs between 5 and 10 g of "substance" on a 1 m layer support

Heating to 120 ° C gives a blue picture,

Example 9

On the back of a lioht tracing paper that was used during development If you add ammonia gas to a red color, you pour the first layer on the oil side and then dry it 1

Crushed potassium bicarbonate 12 kg

Water 8 kg

Polyvinylidene chloride 2 kg

There should be 5 to 10 g of solid substances on 1 m ^{2 of the substrate *}

One prepares the second, back-side souvenir

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· »18«

Toluene 60 kg

Polyvinyl acetate ¹ 4 kg

Solution a

Methanol 60 kg

Ammonium nitrate 10 kg) (40 ° 0}

B gründliohem Under stirring is poured, the I ^ sung7in the solution A _f which precipitation of the nitrate effected in very fine form * This dispersion is then gegos- via the first backing layer

Wk sen and dried for 5 seconds at 70 C «

The heating of the diazotype paper obtained in this way r results in a red! hue »

Example 10

In a so-called precaution, as is usually the case for the production of tracing papers is used, one brings 5 to 10% by weight of the blue coupler J.

2 _> 3 "-dihydroxynaphthol-> 6 - sodium sulfonate. Pour and dry as usual.

Then you pour the photosensitive solution}

water 100 1 ajhiooarbamide 4 kg Sulfamic acid 2 kg Zinkeala of 4-dimethylaminodiazobenzene 1 kg Zinc chloride 5 kg \ Ammonium sulfate 90 ^ 823/0862 , 30 kg - 19 -

The mohawk takes place in the usual way «

Sohließlioh the over "or" cover layer, as it is in Example 8 is described, but does not contain ammonium sulfamate contains «Auf / 1 gpr, layers should be 5" to 10 g solid substance not applicable. »One dries at 60 to 70 ° 0.

, Pie, heating to 120 ° C results in a blue shade »

Everything in the description belongs to the invention is included, including what deviates from the specific exemplary embodiments for a person skilled in the art

Claims t

Ra - 17 120

909623/0862

Claims (1)

PATENT LAWYERS PATENTANWALT D1PL.-ING.RICHARD MOLLER-BÖRNER PATENTANWALT DIPL.-ING. HANS-HEINRICH WEV BERLIN-DAHLEM · PODBIELSKIALLEE 68 UfI MUNICH SZ · WIDENMAYERSTRASSE 49 TELEPHONE: 76 ZS 07 · TELEGRAMS: PROPINDUS mSJ TELEPHONE: 22 65 85 ■ TELEGRAMS: PROPINDUS 120 Berlin, October 5, 1965 Dr. Expl. U72860 Establishments BAUCHET & öle », Rueil-Malmaison, Seine & Oise (France) Claims t 1 One-layer heat-developable diazotype paper support and on one of the sides of the support with a light-sensitive layer, the at least one Diaao compound and an acid-stabilized coupling component, characterized in that the diazo type paper . has at least one Intwioklersohioht that at least one of the elements of a mixture of at least one salt of a first volatile or liquid base and a first Acid and at least one salt of an acid which is weaker than the first acid and a base which is stronger is as the first base, contains " 2 «Process for the production of the DiazAtypie paper according to claim 1, daduroh characterized that one of the salts in the photosensitive Schioht and the other in an organic Over or * top layer is included » 909823/0862 TELEPHONE: O1I40S7 3β method according to claim 2, characterized in that the G-e complete complex of salts in a single, based a developer layer made of an organic liquid is contained v 4 «Method according to Claim 3», characterized in that the Developer layer is arranged so that it is the photosensitive Layer covered. 5 »Method according to claim 3, characterized in that the ^ Developer layer on top of the photosensitive layer arranged opposite rear side of the substrate 6 * heat developable diazo type paper according to claim 1, characterized in that some of the salts are in a first back water-containing layer and the other salts contained in a second rear organic layer are «(| 7 »A process for producing the paper according to claim 6, characterized in that _r the salts contained in the aqueous layer in solution," 8. Procedure nasch. Claim f, characterized in that the Salts in. The water-containing layer in the form of pigments. contain; whose particles are below icyt. 9 * Method according to claim 7 and. 8, characterized in that the water-containing layer contains a binding agent which regulates the penetration of the organic layer « 1Oe method according to claim 9 »characterized in that the Binder is a substance from the group consisting of gelatin, Alginates, carboxymethyl celluloses and methyl celluloses includes ο Ύ 11 · Process for producing the paper according to Claim 6 »characterized in that the organic layer contains a binder which is not solid at the developing temperature 12 »Process for producing the paper according to the claims 6 and 11, characterized in that the binder of the organic layer consists at least partially of a substance the group, the epoxy resins, chlorinated rubbers, butyl ^ rubbers, acrylic polymers, styrene-butadiene copolymers, I "polyvinylidene chloride copolymers, polystyrenes, chloropolyethylene, Coumarone, indene and terpene resin & that of styrene derived resin, abietoformophenolhazr, hard paraffin, Butadiene styrene resin, microcrystalline paraffins and microcrystalline paraffins in connection with butyl rubber includes. 9 0 9 823/0 S3 13 · The method according to spoke 12, characterized in that the organic layer contains a plasticizer that is on. has a beneficial effect on the contact between the salts, 14 - method for producing the paper according to claim 6, characterized in that the organic layer contains at least one salt which is in solution in a first organic liquid and by a second organic liquid is precipitated 15 »Novel industrial product, which is represented by a! Diazo with the reproduction of a line drawing u« ä · and prepared by a diazo according to claim 1 to 14 a projection image of the line drawing u _# ä _# exposed and the copy obtained is then entwikkelt, by exposing the blueprint paper to heat 16, Thermally Developable Blueprint Paper and Process to its manufacture, characterized by the features contained in the coating * Ra -17 120 9 98 237 086