DE2050024C - Heat sensitive stencil sheet - Google Patents

Description

Partly dry matter from both additional types of each standing perforation image.

^{0.1 to 1.0 parts by} weight are included and, in other words, the pertora "" ⁿ . ^M ' ^Z "

additional adhesive total in a lot of short irradiation insofar. defective ^^ they ° e.m

corresponding to 0.5 to 5.0 g / m «of his dry later transfer printing with e.ner: '? ^lc h ™ template

substance is contained in the stencil sheet. * o supplies fuzzy prints, and beι zu ™ ^e _ J ^

3. stencil sheet according to one of claims i radiation compared to the original image μ excessively and 2, characterized in that the becomes visible, which in turn has to be purchased ^A ° ^z ,% ⁿ '"* £ .."*; reactive, heat-sensitive components from as already mentioned, the previous Schablonenblat he is such ingredients as used previously for only an extremely thin film on the Tragerpapier heat-sensitive copy material advertising * 5 had, you could only nut utmost ^ Jwengke _"to determine with the naked eye whether a useful

4. "Heat-sensitive stencil sheet made from perforated image, and accordingly

porous, thin backing paper and a hard-to-find way to determine the correct amount of irradiation.

one side of which is attached by means of adhesive film. Rather, they could only be found on the ^ν ™ η5-

mainly made of thermoplastic resin, determine the 3 ° paths by using several templates

characterized in that the film made a differential exposure overlay with them

has, the one with a visible overprint when heated and the various prints with the

Coloring developing component as well as an original compared.

heat-fusing connection of at least it has already been proposed (German

a metal salt of a higher fatty acid with 10 to 35 Offenlegungsschrift 1961974) with heat-sensitive

Contains 22 carbon atoms. lent stencil sheets the thermographic color

5. stencil sheet according to claim 4, characterized by the reaction of a binder additive for the recognition of the fact that the coating is to be used to 1 degree of perforation by weight of the stencil, partly heat-sensitive component 0.1 to 1.0 Ge Finally, it has already been proposed (German parts by weight heat-melting compound contains 4 ° Offenlegungsschrift 2,043,342), the recognizability, and is present on the sheet of in an amount corresponding Perforieruhgsgrades of the film with the naked eye from 0.1 to 3, ⁸ OgZm solid. improve by adding the binder or the

6. stencil sheet according to one of claims 4 adhesive layer a metal salt of a higher fatty acid and 5, characterized in that the coating is incorporated and uses its ability to pass into a transparent form containing the two additional types when heated.
Adhesive exists. On the other hand, the object of the invention was

7. Stencil sheet according to one of claims 4, another embodiment of a warm-up 6, characterized in that the visibly sensitive stencil sheet to create the Reactive, heat-sensitive constituent from the determination of the stencil production Components consists of how they were previously made easier and just as easy for exposure times so borrowed When using heat-sensitive copying material, the degree of perforation of the stencil can be seen with the naked eye designed to be recognized.

The subject of the invention is thus a heat

sensitive stencil sheet made of porous, thin

55 backing paper and a film of mainly thermal

The invention relates to a heat-sensitive plastic resin, which is characterized by a stencil sheet made of porous, thin carrier paper, that the adhesive has a component that develops a visible film of thermoplastic color that is attached to it when heated, as well as a heat-synthetic resin and is particularly concerned with the melting connection of at least one METAU-task .r a nick ^J purposes for ¹ L stencils suitable salt of a higher fatty acid having 10 to 22 to provide Konlenstoffnenblatt containing atoms in its perforated region or that the film a coating a colored and during the Perforationsvorganges which is able to present a visible, observable image when heated. Color-developing component as well as a warm

There are already heat-sensitive stencils ^{- 6} 5 melting compounds made of at least one metal sheet, which consists of 7 to 15g / m ^a heavy, porous salt of a higher fatty acid with 10 to 22 carbon-thin carrier paper made from Mitsumata, paper mouth atoms,
Berry tree, Manila hemp and the like natural fibers or with those used according to the invention, visible

The reactive thermosensitive component, as will be explained later, means a compound or composition which has heretofore been generally used for a so-called thermosensitive copying material capable of making copies by infrared radiation alone. As will also be explained in more detail later, the heat-fusible compound used according to the invention has one substance in common, which is 0.5 g / m As mentioned, if it exceeds the upper limit of 5.0 g / m ² , the perforability of the stencil sheet suffers. In the production of the stencil sheet according to the invention of type B, one starts either from a prefabricated stencil sheet made of carrier paper, adhesive interlayer and film and covers it

yy, y, yylt oe consist of crotonic acid, or those based on acrylic resin, such as polyacrylic acid, polymethacrylate, polyethyl acrylate, Polypropyl acrylate, polybutyl acrylate, butyl acrylate-vinyl acetate copolymer or acrylonitrile-methacrylic acid copolymer.

All common materials are suitable as porous, thin backing paper and as a thermoplastic film i

Heating at 50 to 150 ⁰ C or slightly above or on the film side with a solution or dispersion which is transparent including by melting io. Additional substances in z. B. alcohol, alcohol-ether or

For the implementation of the invention, all alcohol-keto alcohol are suitable with the formation of a mainly hitherto known, customary adhesives, including borrowed from this. Additional substances existing layer, for example those based on vinyl resin, that is, or from the film that is first placed on the mainly of vinyl acetate as homopolymer or 15 one side covered with the additional layer and then from its copolymers with ethylene, maleic acid, on the opposite side by means of adhesive with the carrier methyl acrylate, Acrylic acid, butyl methacrylate or paper connects. As a solvent or dispersant

alcohols such as ethanol, n-propanol, n-butanol or, for example, are suitable for the additional substances 2-ethyl butyl alcohol, ethers such as ethylene glycol monomethyl ether, Ethylene glycol monobutyl ether or diethylene glycol monomethyl ether and keto alcohols such as diacetone alcohol. If necessary, you can use the

g additional substance solution or dispersion something else

of this type, and add substance as the main film substance 25 of the aforementioned adhesive. With it is best to take a vinylidene chloride-vinyl or without the addition of adhesive effects the solvent chloride copolymer.

In the production of the stencil sheet according to the invention of type A, that is to say in which the two additives
are contained in the adhesive layer, it is with regard to 3 «
that the paper-film binder is generally used in alcoholic solution, from
The advantage that the additional substances to be mixed in are alcohol-soluble, although they are natural
also used in alcohol-insoluble form and then 35 corresponding to 0.1 to 3.0 g / m ^{2 of} solid substance. can be suspended in finely divided form. As with the type A stencil sheet, the additives have to suffer when heated on the
Temperature range from 120 to 170 ° C in which the
Film perforation caused by the infrared radiation
will develop a color. In other words, 40 must be
after the original is placed on the stencil sheet and when it is infrared irradiated at the same time
with the film perforation in the adhesive layer
transparent or opaque, visible color image of the

Originals are created. Accordingly, it is desirable that 45 th of the lower limit but not the image Additions not only in the adhesive layer expect uniform clarity in the perforation area, which is sufficient

in order to capture a usable amount of exposure in the production of stencils. On the other hand, if the upper limit of 6.0 g / m ² for the amount of additional substance is exceeded, no satisfactory image formation which can be used as a yardstick for achieving correct perforation is achieved.

With regard to the applicable according to the invention, visible

The additives are therefore added to the adhesive in a heat-sensitive component that reacts at 55 bar Amounts of 0.1 to 1.0 part by weight per 1 part by weight are available in the literature on heat-sensitive materials

a certain etching of the film surface and thereby a fairly strong bond between additional substances and film.

The batch containing additive substances expediently contains about 0.1 to 1.0 parts by weight of heat-meltable substances Compound per 1 part by weight of visibly reacting, heat-sensitive component. One brings the approach to the film surface in a lot

bsi going out of these range limits correct exposure estimation and perforability.

For both types of stencil sheets, it is generally not necessary to use the specified areas pause for the additional substances that are either applied to the film surface or in the adhesive be dissolved or dispersed. If the

are distributed, but also, as already mentioned above, the color approximately or exactly in the temperature range able to develop in which the film perforation occurs.

The heat fusible link is required to be that in the perforated stencil area The color image formed can be clearer and more contrasted with respect to the background.

part adhesive solid substance, d. H. Resin too.

The total of the additional adhesive is used this time based on the total solids content - about 0.5 to 5.0 g per square meter of leaf area, if * the applied adhesive compound is more Contains additional material as specified, she kneels! 'He Forgeability of the stencil sheet, and if there is less / iisut / material than desired, the stencil suffers Clarity of the perforation image, and in both cases one can no longer see the extent with the naked eye assess the infrared radiation. When finally the total solids content of the adhesive layer less copying material and the like multiple references. Of these known compounds, however, the following are suitable for carrying out the application:

a) Complex compounds that change between M) and 120 C, / u They include, for example, hexamethylene _{tetramine cobalt iodide (C (KI 2} · 2 C ₆ H ₁₂ N ₁ · 10 H ₈ O). yellow-red; hexamethylene tetramine cobalt iodide (light yellow-brown), Hexamethylene tetramine cobalt bromide (light yellow-red), hexamethylene tetramine nickel chloride (light green), hexamethylene tetramine nickel chloride (light green).

Hexamethylene tetramine cobalt nitrate or sulfate and hexamethylene tetramine nickel nitrate or -sulfate.

b) mixtures of three main components, namely a between 100 and 18O ⁰ C melting compound with secondary alcoholic hydroxyl radical, an inorganic metal salt or metal acetate, and sulfur.

The first-mentioned component includes, for example, benzoin compounds such as benzoin, 2-methoxybenzoin, 4-chlorobenzoin, 4-dimethylaminebenzoin and 2-chloro-4'-dimethylarainobenzoin, carbinols such as diphenylcarbinol, phenol compounds such as resorcinol, pyrogallol, 3-hydroxytoluene-4-sulfonic acid, 4-nitroresorcinol and 4,6-dibromoresorcinol and also polyhydric aliphatic alcohols such as erythritol, sorbitol, galactose, maltose, mannitol and sucrose;
The second component includes, for example, compounds that react with sulfur to form colored sulfides, such as sulfates, nitrates, carbonates and acetates of copper, lead, tin, molybdenum, cobalt, chromium, nickel, manganese, titanium, antimony, rhodium, mercury, Iron, barium, bismuth, arsenic, magnesium, indium and iridium.

c) Mixtures of mainly one compound with a secondary alcoholic hydroxyl radical (corresponding to the first component of b) and a complex compound according to a).

d) Mixtures of a carbohydrate and a dehydrating agent, e.g. B. as carbohydrates Sucrose, fructose, galactose and starch and, as a dehydrating agent, sulfuric acid, Acetic anhydride, anhydrous zinc chloride and p-toluene sulfonic acid.

In addition to these aforementioned, heat-discoloring compounds or mixtures are also known the following further combinations of substances:

e) a mixture of. an iron salt of a long chain Fatty acids, such as iron (III) stearate or myristate and phenol or a phenol compound, such as tannic acid, gallic acid or ammonium salicylate;

f) a mixture of mainly on the one hand a salt of a heavy metal such as nickel, cobalt, lead, copper, iron, mercury or silver, and an organic acid such as acetic, stearic or palmilic acid, and on the other hand an alkaline earth sulphide such as calcium or barium sulphide . Instead of the alkaline earth metal sulfide, an organic chelate compound, such as SI) phenylcarbazide or diphenylcarbazone, can also be present as a second component;

g) a mixture of mainly on the one hand a heavy metal oxalate, such as silver, lead, mercury or thorium oxalate, and on the other hand one sulfur-containing compound such as sodium tetrthionate, sodium thiosulfate or thiourea;

h) a mixture of mainly on the one hand a fatty acid iron (III) salt, such as 7. B. fisen (III) stearate. and on the other hand an aromatic polyhydroxyl compound, such as. B. 3,4-dihydroxyte uaphenyl methane;

i) a mixture of mainly on the one hand a noble metal salt of an organic acid, such as. B. Silver or mercury oxalate, and on the other hand an organic polyhydroxyl compound such as z. B. a polyhydroxy alcohol, glycerin or glycol;

ίο J) a mixture of mainly on the one hand one Noble metal salt of an organic acid, such as. B. silver behenate or stearate, and on the other hand a reducing organic compound, such as. B. Protocatechuic acid, spiroindane or hydro

X ₅ quinone;

k) «in a mixture of mainly a fatty acid iron (III) salt, such as. B. iron (III) pelargonate or laurate, and on the other hand thiosemicarbazide or isothiosemicarbazide;

I) a mixture of mainly on the one hand a lead salt of an organic acid, such as. B. lead capronate, pelargonate or behenate, and on the other hand a thiourea derivative, such as. B. ethylene thiourea or N-dodecylthiourea;

m) a mixture of mainly on the one hand a heavy metal salt of a higher fatty acid, such as z. B. iron (III) - or copper stearate, and on the other hand Zinc dialkyl dithiocarbamate;

n) a mixture that either, on the one hand, such. B. resorcinol plus nitroso compound, an oxazine dye or alternatively forms an azo dye.

However, the invention is not related to the visually reactive, thermosensitive component restricted to the above listed connections or connection mixes, special can also be seen to be using any of the conventional ones in the thermal copying field Perform components that thermally release a polyvalent metal cation. For this include, for example, the aforementioned heavy metal salt of an organic acid or a mixture on the one hand organic reducing agent, sulfur compound or amino compound and on the other hand Heavy metal salt of an organic acid or any single compound that thermally has a color able to develop. Furthermore, those compounds or mixtures can also be used which not for production because of the insufficient intensity of the color they provide thermally of heat-sensitive copying material.

The heat-fusible compounds suitable for carrying out the invention include the metal salts of saturated or unsaturated higher, i.e. Ii . C ₁₀ - to Cjjj fatty acids with melting ranges between 70 and 150 C. Examples of the acid component are stearic, palmitic, lauric, myristic, oleic, erucic and behenic acids, and the metal components are on the table of periods - Group Π metals such as calcium, zinc, cadmium, magnesium, etc., group JV such as lead, group VH such as manganese, group VIII such as iron, cobalt, pimples, etc. and such of group I, like copper, in Bs; ra <in.

te

They can be used individually or in groups. This approach was made in such a way that

other | be used. Metallsake of fatty acids can ml to 1500 a 4 _t 5 ° / _o by weight methanolic Polymit less carbon atoms as capric acid vinylacetatlösung 10 g of zinc stearate and 10 g of calcium (C _B H _U COOH) fall due to their normal odor stearate hinzugab, the resulting mixture 3 hours for practice. It is true that you can work well with metal salts for 5 long in a ball mill and of fatty acids with more carbon atoms than the last added 2.0 g of diphenylcarbazone.
C, _2- behenic acid work; those salts of fatty acids. With this adhesive approach, a 7 μ with up to 22 carbon atoms was however suitable on a thick, transparent film made mainly from vinyl best. For the combination of thermal chloride-vinyl chloride copolymer with a 9 g / m ^a sensitive component and a heat-fusible 10 heavy and 30 μ thick, porous thin paper compound, it is preferable to choose substances made from mainly manila hemp fibers. The ones that don't chemically react with each other. Glue was applied to the paper by means of a roller

If you apply a stencil sheet with the thermally discolored additives according to the invention in an amount corresponding to about 2.2 g / m ^{2 for the purpose of substance.}

Stencil production infrared irradiated, are not 15 The stencil sheet obtained in this way became film-sided only those corresponding to the original picture districts with an original, namely a newspaper clipping, Film areas perforated, but at the same time melts occupied and then from the paper side in one and the color of the thermal copier available in these areas is also colored by infrared radiation. . These constituents, thereby increasing their clarity. A perforation image was thus obtained on the stencil there, and the colored melt creeps along the ao and a congruent red image that becomes clear Perforation edges together so that in the end it stood out sharply from the pink background, a clearly observable image with perforations. sharp contours are created. Achieve rations in the process. The template produced in this way delivered The very finest particles of the colored ones stick together in a commercially available duplicator Melt onto the fibers of the backing paper, so that the multitude of sharper and more accurate images one prints the perforated areas with the naked eye.

just as clearly as a print, a symbol or an

Normal photography. About this position was determined in such a way that one that In addition, the emergence of the described exit results in the forming, colored perforation image with the bare colored melt from the perforated areas of the eye was observed and at first even less important advantage that the later passage of clarity repeated the exposure correspondingly often. They do not adversely affect printing ink. This was found, for example, in the present case learns. of the DIN A4-sized original a 4 seconds long

In the case of the A-type stencil sheet according to the invention, exposure as the correct one.

one can first use the additional adhesive 35. For comparison, the same Mavcrialien, either on the backing paper or on the film, however, with an additive-free polyvinyl acetate solution apply and then both on somehow usual glue, four stencil sheets made that again Unite kind. In the case of type B stencil sheet other - under a DIN A4 original in one on the commercial side you can add the additive solution by means of roller-conventional thermal copier about 3 or 4 or 5 or spray application or otherwise exposed on the film for 40 or 6 seconds. In all apply area. In four cases, the resulting perforation pattern was hardly any

In summary, it can again be stated that it was recognizable and it was not possible to determine which of the stencils made from the stencil sheet according to the invention was correctly exposed. Of the thus proper stencil sheet with the advantages obtained four templates linked could only is that it not only the right infrared exposure "5 4 generated seconds exposure in the reproduction determining, by making one gets the perforated stencils to provide original image faithful prints while nengcbiet with observed with the naked eye and produced blurred prints with the rest,
compares to the original image, but also to the

Clarity of the color image bathed on the stencil example 2

on the clarity of the later raft of the template

can close, if the color picture and example 1 was repeated with the exception, Deduction are equivalent for clarity. Therefore, 30 g of lead acetate and S g of benzoin were added to the adhesive The invention eliminates the inadequacy of 3 g of sulfur as a heat sensitive component previous stencil sheets that the correct and manganese stearate as a heat-melting connection exposure were only added after completion and use.

would assess the stencil made with them. The stencil sheet provided a sharp, dark-

can. brown, clearly visible perforation image on white

In the following, the invention is based on some subsurface, and achieved with the finished template preferred examples are explained in more detail, one has a large number of sharp prints, without being restricted to them. «·»

Example 3 Example I. According to the procedure described in Example I.

In this case, the visibly reacting, heat-producing six stencil sheet types were used Sensitive constituents of zinc stearate and EH- «5 to which the adhesive is made from Pdyvmyiaceutlösung phenylcarbazon and the heat-fusible compounds given in the table below, binding to the calcium steroid, both of which contained in the adhesive additives according to the invention that were introduced into the perfume batch. rationsbild also gave the species-specific coloring.

309619/85

9 Heat fusible 10 Coloring of the Shabions More sensitive to heat Connection b Mix
ratio a / b perforated image leaf Component a Lead pal mitat in weight
divide blue 1 Hexamethylenetetramine cobalt 3: 1 chloride Manganese stearate Blackish brown 2 Iron (IIl) stearate and 2: 1 Gallic acid (3: 1) Potassium palmitate Blackish brown 3 Lead oxalate and 3: 1 Thiourea (1: 1) Zinc stearate Blackish brown 4th Silver behenate and 2.3: 1 Protocatechuic acid (6: 1) Magnesium myristate Blackish brown 5 Iron (lll) laurate and 2.8: 1 Thiosemicarbazide (1: 1.8) Cobalt myristate Blackish brown 6th Cu (II) -stearal and 2.5: 1 Zinc dialkyl dithiocarbamate

Example 4

Here, the additives according to the invention were introduced into a top layer.

In 800 ml of a 4.5% methanolic polyvinyl acetate solution As a heat-sensitive ingredient, 5 g of pyrocatechuic acid and 20 g of diphenylnitrosamine were found and 10 g of nickel laurate dispersed in as a heat-fusible compound.

The dispersion thus obtained was applied to a 7μ thick, transparent film mainly made of vinyliao The chloride-vinyl chloride copolymer applied and dried.

The film coated in this way was made on its free side with the help of a polyvinyl acetate solution only existing adhesive with the backing paper according to

as example 1 combined to form a stencil sheet.

This resulted in further processing according to Example 1, again in an easily controllable manner a stencil with a sharp, blackish-brown, clearly visible perforation image with which you can Received a multitude of sharp prints in the duplicator.

Claims (2)

* 2 Rayon, polyvinyl alcohol, terephthalic polyester resin patent claims: acrylic resin or similar synthetic fibers and applied to one side, about 5 ms ΐυ_μ 1. Heat-sensitive stencil sheet made of thick film made of ^ tm ^^ Ε
porous, thin backing paper and one on S polystyrene, polypropylene. one side of which is attached by adhesive cWorid vinyl chloride copolymer ^ ^ Produce film mainly of thermoplastic resin, a Umdruckschablone Jbelegt be characterized in a that such sheet filmseiüg closely "&& ** and to glue a visible multiplying Ongirnü upon heating ^ and exposes it then of coloring developing part and eme io the opposite side forth imtelektromagnemcherbrahlung, heat-melting connection made of at least whereby the film layer to the original naloüd a metal salt of a higher fatty acid with 10 to district corresponding places P ^ert ° "f ^Γ _ς ^w '™ _u
Contains 22 carbon atoms. In this Perfonervorgang £ / £ S ™ "ff _t ^h ' 2. stencil sheet according to claim 1, characterized in that the extent, that is, seen from the table, the Behchtungszeit, characterized in that in the adhesive per 1 weight i ₅ a noticeable influence on the Marheii