DE1961974C - Heat-sensitive stencil paper - Google Patents

Description

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The invention relates to a waterproofing agent that is suitable as a binder that can be used according to the invention Lich stencil paper made of thin, porous backing - all previously common and known substances

paper with thermoplastic and especially those with vinyl acetate polymer or Synthetic resin film and in particular one for acrylic resin and the like as the main component. To belong to Diverse purposes, the coloring in the perforated area 9 for example various products, such as a able to present images, which during the perforation methanolic solution of a Vinylacetathomopolymerb

Process are observable. from the degree of polymerisation around 1100, only Vinyhden- The most common, known heat-sensitive schachloride-acrylonitrile copolymer in dissolved form or

Blonenblatt consisted of a thin, porous, an alcoholic acrylic resin solution and others.

7 to 15 g / m ¹ heavy paper from Mitsumata, 10 also as a paper and film part of the new one

Paper mulberry, Manila hemp, etc. - natural stencil paper are all suitable

fibers or made of viscose, polyvinyl alcohol, tere substances, but with film layers made of vinyl

phthalate polyester resin synthetic fibers, the surface of which is chloride-vinyl chloride copolymer as particularly suitable

have proven to have an approximately S to 10 μ thick film from a thermo.

plastic synthetic resin, such as polystyrene, polypropylene, 15 When stencils scroll of the invention type A uses polyethylene or vinylidene chloride-vinyl chloride, wore. a connection is made to the binding agent which, when such a stencil sheet is used, one can develop a color when heated. Since this is usually done in such a way that it is coated on the film side with binding agent, usually made of an alcoholic original that carries the image, and then consists of a synthetic resin solution, this color-bound original should also expediently irradiate alcohol rays through the original with light including infrared ao connection, with the film in the sections be soluble. Of course you can also work with alcohol perforations that work with the image area of the substance that is closely insoluble, provided that they correspond to the fine original. Distribution mixed into the binder, that is, in it

During this process, the amount of incident has been suspended. The compound should also be suitable for radiation, ie the extent of exposure, a noticeable influence in the temperature range from 120 ° to borrowed on the clarity of the 170 ⁰ C obtained thereby, by also the perforation image on the stencil sheet. If the process of film perforation is pressed by infrared radiation, the perforation is done when the temperature is too low. In other words, it should be too weak when irradiated, so that in the case of a later stencil sheet according to the invention after its use of the stencil for printing it provides a blurred coverage with the original image and in the case of infrared prints; Time on the other hand too excessive in comparison to the original image, the binder layer a colored image of the Oriso that likewise only blurred prints emerge. ginals and in the film layer a corresponding Since the well-known, heat-sensitive stencil perforation image is created. Therefore, this colored paper, both in the paper and in the film layer 35, should not only be evenly distributed in the extremely thin binder layer, but also determine with the naked eye whether the perforation coloration was within a temperature range If the image on the stencil was okay or not, you can wind which is similar to or close to the one and consequently the correct setting was also made by perforating the film. Exposure very difficult. Under these circumstances 40 The proportion of the color-developing substance in one has hitherto not required the correct amount of exposure in the binder layer to be empirically determined in such a way that stencils are made from the color-developing layer of a heat sheet, printed with them and then used to be sensitive copy material; it is sufficient to compare the prints with the original image. rather, at least 0.3 parts thereof per part by weight

The invention now aims to provide a binder, and if more than 4 parts by weight thereof

heat-sensitive stencil sheet, which is easy to perforate even the stencil sheet

Determining what is correct for stencil making affects. If one uses the aforementioned color-

Exposure extent enabled or used with a mere binder containing binder

The eye can judge whether the perforation achieved is thin, porous backing paper with a film

is useful. 50 at least 1.5 g of solid matter per square meter

Accordingly, the invention includes both a bring, so he not only provides a visible image and stencil sheet from a thin, porous support - a firm bond between film and paper, paper and a film of thermoplastic synthetic - but also facilitates the determination of a suitable resin, which on a paper surface with the aid of a binding degree of infrared radiation. It is important to note that it is attached to a heat-sensitive, 55 but that it is not advisable to use more than 10 g of binding visibly reactive component, as well as a medium per square meter for the above-mentioned order stencil sheet, also made of backing paper and the purpose, because otherwise the perforation of the stuck-on film, the outside of the film suffering from the performance of the stencil sheet.
Layer is covered, which the aforementioned, heat- The stencil sheet of the invention type B other sensitive, visibly reacting component on the other hand can be produced in two ways. Holds in both. Cases, a solution or dispersal is first

It should be noted that the present invention uses the aforementioned color-developing compound used and explained in more detail later, heat-sensitive in a suitable solvent, e.g. B. in alcohol borrowed and visibly reacting constituent from an alone or an alcohol-ether or alcohol compound or composition consists of 65 keto alcohol mixture and then carries it as generally for a so-called heat-sensitive top layer on a film, which can be either Copying material is used, which is thus attached to the backing paper by means of a binding agent alone Infrared exposure is capable of producing prints. had or subsequently on the non-coated side

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with the help of a binder with the backing paper phenylcarbinol, phenolic compounds such as resorcinol,

covered. Pyrogallol, 3-hydroxytoluene-4-sulfonsttMre, 4-nitro-

It is advisable to carry as much of this resorcinol as 4,6-dibromoresorcinol, aliphatic, more- Solution on the film that it is with 0.5 to 10 g / m ⁸ valent alcohols such as erythritol, sorbitol, galactose, Color developing agent is covered. If you soak 5, maltose, mannitol and sucrose;

from this area on, there is a risk that As inorganic metal salts and metallacelals

either assess the exposure or which are suitable compounds that deal with sulfur too

The perforation performance of the stencil suffers. Convert as Lö- colored sulphides, such as two

solvents for the heat-sensitive, visible for example the sulfates, nitrates, carbonates, and

reacting substance are alcohols, such as acetates of copper, lead, tin, molybdenum, cobalt,

Ethanol, n-propanol, n-butanol and 2-ethylbutyl-chromium, nickel, manganese, titanium, antimony, rhodium,

alcohol, ether, such as ethylene glycol monomethyl -, - ethyl mercury, iron, barium, bismuth, arsenic, magnesium

and butyl ether and diethylene glycol monoethyl ether si to, indium and iridium;

and keto alcohols such as diacetone alcohol. One can c) preparations, which mainly consist of a hydroxyl »

the solution also contains a small amount of the residual compound according to b) above, sulfur

for the film-paper association used binder and a complex compound according to the above

to add. Since the FiFm consist of substance or binding a). Such preparations are in Japanese

If the medium solvent is somewhat etched, an interpretation document 14 511/1966 (applicant: Kabushiki

the substance has a fairly firm bond with the film Kaisha Ricoh);

surface a. ao d) Preparations, which mainly consist of a coal

With stencil sheets of both types of invention hydrate and a drainage agent exist one needs to know about the color developer- Such preparations are in the Japanese amount of solvent, either written on the film surface 13 237/1967 and insisted as an example or added to the binder, on the one hand, sucrose, fructose, galactose not exactly on the aforementioned proportion range as or starch as carbohydrate and on the other hand to keep. However, if you fall below the minimum value, sulfuric acid, glacial acetic acid, anhydrous zinc chloride then you can not use the clarity of the perforated or p-ToluoIsulfonsäure as a dehydrating agent. Expect the image created in the district, which is sufficient, except for these aforementioned connections and around a suitable amount of exposure in the preparation preparations are than discoloration time due to the action of heat to capture the stencil. If more than 30 bare materials are exceeded, the following compounds on the other hand, the upper limit, namely 10 g, and preparations known:

amount of substance carried per square meter, so e) preparations containing an iron salt of a long-chain

Inadequate generation of fatty acid images such as iron (II) stearate or myristate, as well as

achieve which as a benchmark for the achievement of a phenol or a phenolic compound, such as tannin,

proper perforation can be used. 35 gallic acid and ammonium salicylate;

Suitable for carrying out the invention are f) preparations which mainly consist of a heat-sensitive, visibly reacting substances metal salt of an organic acid, such as nickel, numerous substances, as they are in the literature about heat, cobalt, lead, copper, iron, mercury or sensitive copying materials and the like are silver acetate, stearate or palmitate and a are written. Among them have in particular 40 alkaline earth metal sulfide, such as calcium, strontium or the following proved to be useful: barium sulfide, consist. Furthermore, also preparations,

a) Complex compounds that change their color between those mainly composed of an organic heavy metal - 50 and 12O ⁰ C. They are described in the Japanese salt of the aforementioned type and an organic chelate patent application 14 509/1966 (Applicant: Kabushiki compound, such as S-diphenylcarbazide or Diphenyl-Kaisha Ricoh) and include, for example, 45 carbazone;

Substances such as g) preparations that are mainly composed of a heavy

Hexamethylenetetramine ■ cobalt chloride (CoCl ₂ ■ metal oxalate such as silver, lead, mercury or

2 C H N 10 H o eelbrot) thorium oxalate, and a sulfur-containing compound

Hexamethylenetetramine cobalt iodide (light yellow-red), ^d " ⁿ 8- * ^ie _K sodium tetrathionate, sodium thiosulphate

Hexamethylenetetramine · cobalt bromide (light yellow-red), ⁵ ° ^od ^ thiourea consist;

Hexamethylenetetramine · Nickel chloride (light green), _c ⁿ > ^ »Parate, consisting mainly of a fatty acid

Hexamethylenetetramine nickel bromide (light green), iron (H) salt, such as E.sen (III) stearate, and an aro-

Hexamethylenetetramine ■ Cobalt nitrate or sulfate rustle polyhydroxyl compounds, such as 3.4-D.hydroxy-

j _e tetraphenylmethane, consist;

Hexamethylenetetramine · Nickel nitrate or sulphate. 55 0 Preparations, which mainly consist of a noble

metal salt of an organic acid, such as silver or

b) preparations which mainly consist of a ^{compound which melts between mercury oxalate and an organic polyhydroxyl 100 to 18O 0} C melting compound with a secondary compound, such as polyhydroxy alcohol, glycerine or alcoholic hydroxyl residues of this type, together with sulfur glycoi;

and an organic metal salt or metal acetate 60 j) Preparations, which are mainly made of a noble

exist. Many of these compounds are metallic salts of an organic acid such as silver beetate

in Japanese Auslegeschrift 14 510/1966 (An or -stearate, and a reducing, aromatic

meider: Kabushiki Kaisha Ricoh) described; Compound such as protocatechuic acid, spiroindane or

Among the compounds with secondary, alcoholic hydroquinone, consist;

Hydroxyl residues include, for example, Benzoinver- 65 k) preparations, which mainly consist of a fatty

bonds, such as benzoin itself, 2-methoxybenzoin, acidic iron (IIl) salt, such as iron! I) pelargonate or

4-chlorobenzoin, 4-dimethylaminobenzoin and laurate, and a thiosemicarbazide or isothio

2-chloro-4'-dimethylaminobenzoin, carbinols such as dicarbazide derivative exist;

I) Preparations which are mainly equivalent from a lead salt. S °, ^{mil ka} " ⁿ " enhehinnpnhiBtn.r an organic Sfture'wle lead capronate, pelargonate the disadvantage of the usual stenciled animal or bohonate, and a thiourea derivative, such as eliminating that the correct amount of infrared ethylene thiourea or N-dodecylthiourestolY, irradiation only through actual consumption; 8 templates and their printouts are assessed

m) Preparations, which can mainly from a difficult. _{,, nWara} " ,,"""""",

metal salt of a higher fatty acid, such as ferric iron - The following examples disclose preferred ones stearate, copper stearate and zinc dialkyldithiocarbamal embodiments of the invention without the need for existing; to restrict scope.

n) preparations such as B. a Resorcin-Nitriso- io

Compound combination to form an oxazine dye, Example 1

or preparations that provide an azo dye. .

In addition to these preparations, which are only mentioned as an example, a solution of 8 _{i are suitable for the purposes of the invention as heat-sucrose in 7 ml of water and a solution of 8 g of sensitive, visibly reacting substance seen-15 p-toluenesulfonic acid in 15 ml Methanol is also a solution for all those preparations that thermally release a thermally sensitive, visibly reactive metal cation and are generally ready.

can be applied to the thermal copying field. This solution was with the equivalent amount These include, for example, the aforementioned adhesive resin solution made from a 50% methanolic solution Heavy metal salts of an organic acid or the ao solution of a vinyl acetate homopolymer from the poly mixed preparation from organic reducing agent, degree of merization 1100 (commercial product »Gohsenyl Sulfur compound or amino compound and an M 50 Y-5 "from Nippon Synthetic Chemical such a visual salt of an organic acid or Industry Co., Ltd.), the viscosity of which is mixed all those one / .elsubstanzen par excellence, the thermal addition of methanol was adjusted to 10 cP, and thereby create a color. as a binder that has a heat-sensitive

When a stencil was manufactured by means of infrared borrowed, visibly reacting components contained, irradiation of a stencil according to the invention was then used with this binder

sheet occurs simultaneously with the perforation of the 7 μ strong, transparent film of vinylidene chloride original image areas corresponding film areas, a vinyl chloride copolymer as a main component with a discoloration of 30 30 μ thick and 10 g / m ^a heavy, thin porous preparation existing in the perforated film region, and the colored melt collects backing paper, mainly made of Manila hemp fibers, concentrically along the perforation edges, wherever.

through a clearly visible image with perforations. The binder was in a roller

existing, sharp outline arises. In addition, the amount corresponding to 2 g of solid per square meter The superfine particles of the colored 35 stick to the backing paper. That won Melt onto the backing paper fibers, whereby the stencil sheet was perforated with a pressure on the film side Area with the naked eye just as clearly documented original, namely a piece of newspaper, and occupied like a normal print, characters or then in a commercially available thermal copier Photo becomes viewable. The heat-sensitive, infrared-irradiated from the paper side to reduce the Visibly reacting substance thus forms during the 4 ° to effect film perforation. One received on this Melt and film perforating the colored way on the perforated stencil area Melt, and this collects, as I said, along a sharp, dark brown image and can: easily that the outline of the perforated image area and the original image create congruent perforations. This also adheres to the bare stencil through the perforation, even when used in one laid backing paper fibers, so that in the end a commercially available duplicator can cut a large number results in an image that is visible to the naked eye. As a result, to deliver sharp and faithful prints, In this case, the perforated area can never be The determination of the correct infrared radiation

affect the passage of ink. extent was done in a convenient way by

In the production of the schema according to the invention, the perforation image is also included during the irradiation The color developer-containing binding agent can be controlled by the naked eye and the irradiation medium either on the backing paper or on the repeated until it has become completely sharp Film applied and the eventual union of was. For example, it resulted for one on the stencil Paper and film carried out in the usual way. The film coating with the binder radiation duration of about 4 seconds, or the color developing agent itself, on the other hand, for the sake of comparison, four other stencils were made by roller application, spraying on or the like. leaves obtained by simply joining the aforementioned

When making a template from the invented film and backing paper were made, each with one appropriate stencil sheet occurs not only the DIN A4 large print image original occupied and in Advantage of having the correct infrared radiation 60 aforementioned heat copier 3, 4, 5 or 6 Sedosis can determine, but at the same time can announce long infrared irradiated. With all four samples if one also offered the perforated stencil easily, the perforated image was almost unrecognizable and one Observed with the naked eye and with the original image could not determine which one was correctly exposed compare and thus from the clarity of the visible was. When you get these four stencils in a commercial fab picture on the stencil also applied to that of the later 65 common proof printers, it turned out that Close stencil hoods. In addition, you only get the one gained from the 4 second exposure during the actual printing process - prints, their clear stencils true to the original prints, but all the rest The image visible on the stencil was only able to deliver blurred prints.

Example 2

_ In a mixture of 15 ml of methanol and 1 ml Ethylene glycol monomethyl ether was dissolved in 10 g of fructose and 1.5 ml of undiluted sulfuric acid. This solution was applied to a 7 μ thick, transparent film made of vinylidene chloride-vinyl chloride copolymer applied as the main component, which is then covered with a coating of a heat-sensitive, visibly reacting preparation was provided. Then the film was on the coating-free Same side as in Example 1 and using the same, but using methanol 8 cP adjusted, commercially available adhesive solution according to Example 1 with a thin, porous backing paper proven.

The stencil sheet obtained in this way provided a stencil after infrared irradiation as in Example 1 with a sharp, dark brown perforation image, which was suitable for the release print, and at Use in a commercially available peel-off printer a variety of prints with extraordinarily delivered a sharp picture. The production of perforations was just as easy as in Example 1.

Example 3

First it was made by dissolving 7 g primary cobalt acetate and 1.5 g thiourea in 80 ml methanol a solution of a heat-sensitive, visibly reacting preparation is made.

A certain amount of this solution was mixed with the equivalent amount of that previously described, commercial binding agent (»Super Dain FB-85«) based on polyacrylic resin (-), mixed, the the viscosity of 8 cP had previously been given by the addition of methanol. With the help of this color developer-containing Adhesive solution was a backing paper similar to that of Example 1 with a conventional method heat-perforable film connected and thereby obtained a stencil sheet according to the invention.

With it one could easily get the right amount of infrared radiation for obtaining a stencil, find a multitude of in the duplicator Able to deliver printing with images that are faithful to the original.

Example 4

A color developing agent-containing binder was obtained this time in such a way that, in a ball mill 25 g of a 50 ° / ₀ aqueous alcoholic polyvinyl acetate solution (commercial product "Gohsenyl M 50 Y-5"), 100 ml of methanol and of 3.0 g of lead acetate, 5.0 g of thiourea and 0.5 g of a vinylidene chloride-acrylonitrile polymer binder (commercial product Krehalon-SN) were mixed together. With the help of this binder solution, a 6 μ thick, transparent film made of vinylidene chloride-vinyl chloride copolymer as the main component was bonded to a carrier paper similar to that of Example 1, thereby creating a stencil sheet according to the invention. When it was converted into a stencil in the manner described in Example 1, a sharp, dark brown, recognizable perforation image was obtained, the perforation of which could easily be carried out. The stencil produced in this way was able to deliver a large number of prints with true-to-original image reproduction in a commercially available duplicator.

Example 5

Following the procedure of Examples 1 and 2 and using the binder formulations tabulated below a series of stencil sheets according to the invention was produced and checked for the appearance of the Examined perforation image.

Stencil sheet
Type Heat sensitive
visibly reacting substance binder solvent Hue of
Perforation image example 1 Hexamethylenetetramine and Polyvinyl acetate Methanol blue Cobalt chloride example 1 Benzoin lead acetate and sulfur Polyvinyl acetate Methanol Dark brown example 1 Iron (III) stcarate and gallic acid Polyvinyl acetate Methanol Dark brown example 1 Zinc carbonate and diphenyl carbazone Polyvinyl acetate Methanol Red example 1 Lead oxalate and thiourea Polyacrylic resin Methanol Dark brown example 1 Silver stearate and protocatechin Polyacrylic resin Methanol Dark brown acid example 1 nisen (Ul) -laurat and thiosemi- Polyvinyl acetate Methanol Dark brown carbazid example 1 Copper carbonate and dialkyl zinc Polyvinyl acetate Methanol Dark brown dithiocarbamal Example 2 Diphcnylnitrosoamin and Polyvinyl acetate Methanol Dark brown Protocateic acid c

Claims (7)

Patent claims: 1. Würniecm-sensitive stencil sheet, thereby g e k e η 11 7 c i c h η e 4. that it is out a thin, porous carrier paper and a Film that reveals a thermoplastic synthetic resin as a main component and on the one hand Carrier paper is attached with the help of a binder. that a worm-sensitive. visible contains a reactive preparation, or it consists of a thin, porous backing paper and a ViIm consists of a thermoplastic synthetic shark / Contains as the main component and on the one TrügcrpapuMM'iU · mi} HiIU 'of a Hindcmitlcls 209 627/234 is attached and has a coating on the film surface away from the paper, which has a heat-sensitive, contains visibly reacting preparation. 2. stencil sheet according to claim 1, characterized in that the preparation in the binder in an amount between 0.3 to 4 parts by weight per part by weight of binder and in the stencil sheet is contained in an amount between 1.0 to 10 g per square meter of sheet size. 3. stencil sheet according to claim 1 or 2, characterized in that the film consists of a 5 to 10 μ thick film made of vinylidene chloride-vinyl chloride copolymer consists. 4. stencil sheet according to one of the preceding claims, characterized in that there: Backing paper weighs 7 to 15 g per square meter 5. Template sheet following one of the preceding going claims, characterized in that the preparation consists of a preparation as it bi: is now being used for heat-sensitive copying material. 6. stencil sheet according to claim 1, dadurcl characterized in that the preparation in the coating in an amount between 0.5 to 10 g per square meter is included. 7. stencil sheet according to one of claims 1 or 6, characterized in that the coating contains binders in addition to the preparation. 2404