DE2050024A1 - Heat-sensitive stencil sheet - Google Patents

Description

Kftbuahlki Kaieha Rlooh 1 2nd OCT. 1970 Tokyo, Japan Heat-sensitive template sheet

The invention relates to a heat-sensitive stencil » sheet made of porous, thin backing paper and attached film made of thermoplastic synthetic resin and is concerned especially with the task of creating a suitable for transfer printing purposes To create a stencil sheet that is colored in its perforated area and observable during the perforation process Image can offer.

There are already heat sensitive stencil sheets made from

7 to 15 g / m heavy, porous thin carrier paper made of mitsumata, paper mulberry, manila hemp and the like natural fibers or rayon, polyvinyl alcohol, terephthal polyester resin. Acrylic resin or the like synthetic fibers and on one side of which, about 5 to lü / U thick film of thermoplastic synthetic resin, such as polystyrene, polypropylene, polyethylene or vinylidenechlorld-vinyl chloride copolymer exist. Order to produce a Umdruckschablon "If such a sheet is fllrnseitig closely anli ^ g ^ nci with the perforated to be duplicated original and exposed ^<a s then lnalbildbezirken from the opposite side with electromagnetic radiation, whereby the film layer to the Cri & appropriate places.

In this perforation process, the extent of radiation, i.e. in practical terms, the exposure tent, a noticeable impact on the clarity of the resulting perforation pattern

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In other words, if the irradiation is too short, the perforation will be defective in that it will produce unsharp prints during subsequent printing with such a stencil, and if the exposure is too strong it will be excessive compared to the original image, which in turn leads to blurred prints. Since, as already mentioned, the previous stencil sheets only had an extremely thin film on the backing paper, it was only with great difficulty that it was possible to determine with the naked eye whether a usable perforation image was created and, accordingly, to determine the correct amount of anti-radiation with great difficulty. Rather, they could only be determined by trial and error, by making several stencils with different exposures, re-printing them and comparing the various prints with the original.

The aim of the invention is to create a heat-sensitive stencil sheet which enables easy determination of the correct exposure level for stencil production or the estimation of the perforation quality with the naked eye.

Accordingly, the invention consists of a heat-sensitive stencil sheet of porous thin paper support and on one side thereof adhesively attached film consisting essentially of a thermoplastic resin of which, characterizing Specialties standardize consists in that

either A) the adhesive contains a visibly reactive, heat-sensitive component and a heat-fusible compound

or B) is provided which Filraoberfläche with a coating containing the above-mentioned under A) two additions.

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With the visibly reacting, heat-sensitive component used according to the invention, as will be explained in more detail later is explained, a compound or composition is meant which has hitherto been generally referred to as a so-called heat-sensitive Has used copier material that can be used to make copies by pure infrared radiation.

The heat-fusible compound used according to the invention is, as will also be explained in more detail later, a substance meant that when heated to 50 ° to 15ü ° C or a little above or below it becomes transparent through melting »

All previously known, customary adhesives are suitable for the Ezfinduiigsdurchführung, including, for example, those based on vinyl resin, which mainly consist of vinyl acetate as a homopolymer or of its copolymers with ethylene, maleic acid, methyl acrylate, acrylic acid, butyl methacrylate or 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. These include, for example, the commercial product "GOHSKNYL® M-50 Y-5" from Nippon Synthetic Chemical Industry Co., Ltd. in the form of a methanolic solution of a vinyl acetate homopolyra with a degree of polymerization of around 1100, the commercial ^{product M} KREHALON ^ -SN "from Kurcha Chemical Industry Co., Ltd. in the form of a solution of a vinylidene chloride-acrylonitrile copolymer, the commercial product" SUPER DAIN®FB -85 ^W of Nissetsu Industry Co., Ltd. in the form of an alcoholic acrylic resin solution and other adhesive products of this type.

All conventional materials of this type are suitable as porous, thin carrier paper and as thermoplastic film, and as as the main film substance, it is best to use a vinylidene chloride-vinyl chloride copolymer.

109883/1038

In the production of the stencil sheet according to the invention of type A, in which the two additives are contained in the adhesive layer, it is advantageous, in view of the fact that the paper-film binder is generally used in an alcoholic solution, that the additives also be mixed in Additional substances are alcohol-soluble, although they can of course also be used in alcohol-insoluble form and then suspended in finely divided form. The additives have on heating to the temperature range of 120 ° to 170 ⁰ C, in which the film perforation is effected by infrared radiation, to develop a color. In other words, after the original has been placed on the stencil sheet and exposed to infrared radiation, a transparent or opaque, visible color image of the original must be created at the same time as the film is perforated in the adhesive layer. Accordingly, it is desirable that the additives are not only evenly distributed in the adhesive layer, but also, as already mentioned above, are able to develop the color approximately or precisely in the temperature range in which the film perforation occurs.

The heat fusible link is required to have a clearer color image formed in the perforated stencil area and allows it to become more contrasted with respect to the background.

The additives are therefore added to the adhesive in an amount of 0.1 to 1.0 part by weight per part by weight of solid adhesive substance, i.e. resin.

Of all the glue that is too dumpy, one uses this time based on Qesamt solids content - about 0.5 to 5.0 g each Square meters of leaf area. If the applied adhesive mass contains more additional material than specified, the perforability of the stencil sheet suffers, and less additional material than is desired, the clarity of the perforation image suffers, and in both cases one can no longer use the

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Assess the extent of the infrared radiation with the naked eye.

If 3 finally the total solids content of the adhesive layer

2 is less than the minimum length of 0.5 g / m, suffers the cohesion of paper and film and on top of that the clarity of the perforated image, and if it is the upper limit of

2
5 * 0 g / ^ffl , as said, the perforability of the stencil sheet suffers.

In the preparation of the inventive stencil sheet type D one goes from either from a pre-made stencil sheet from the backing paper, Klebzwischenschicht and film and% coats it on the film side with a solution or dispersion of the additive materials in as alcohol, alcohol ether or alcohol-keto-alcohol to form a mainly layer consisting of these additional substances, or from the film which is first covered on one side with the additional layer and then connected to the backing paper on the opposite side by means of adhesive. Suitable solvents or dispersants for the additive substances are, for example, alcohols such as ethanol, n-propanol, n-butanol or 2-ethylbutyl alcohol, ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or dietary hy lenglykolrnonoine thy lethers, and keto alcohol monoethers and keto alcohols. If necessary, can be added to the additional substance solution or dispersion like something of said adhesive substance. With or without the addition of an adhesive, the solvent causes a certain degree of etching of the film surface and thus a fairly strong bond between the additional substances and the film.

The approach containing additional substances more expediently contains about 0.1 to 1.0 part by weight of heat-fusible compound per 1 part by weight visibly reactive, heat-sensitive component. The approach is brought to the filra surface in one Amount corresponding to 0.1 to 3.0 g / m of solid substance. as well as with type A stencil sheets suffer

^109883/1 ° 38

The correct exposure estimation and perforation capacity are based on these area limits.

With both types of stencil sheet it is basically not possible mandatory, the specified ranges for the additional substances which are either applied to the film surface or dissolved or dispersed in the adhesive. At a However, if the lower limit falls below the image clarity in the perforation area cannot be expected which is sufficient to to capture a usable amount of exposure in the production of the stencil. When exceeding the upper limit of On the other hand, 6.0 g / m 2 for the amount of additional substance is achieved no satisfactory image formation which can be used as a standard for achieving a correct perforation.

Regarding the visibly reacting heat-sensitive constituent which can be used according to the invention, there are in the literature there are numerous references to heat-sensitive copying material and the like. Of these known compounds, however, are the following are suitable for carrying out the invention:

a) complex compounds which are between 50 ° and 120 ⁰ G change their Färb ·. They are described in Japanese Patent Application Laid-Open 1 ^ 509/1966. They include, for example, Hexamethy 1 entetraralnkobal tchl or id (C OCI ₂ · ² ^ H ₁₂ N ₄ · yellow-red;

Hexaiethylenetetramine cobalt iodide (light yellow-red); Hexamethylenetetramine cobalt bromide (hot yellow bread); Hexamethylene tetraulin nickel chloride (light green); Hexamethylene tetramine nickel broinide (light green); Hexamethylenetetramine cobalt nitrate or sulfate as well as Hexamethylene tetracnine nickel nitrate or sulfate.

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/ ι

b) They consist mainly of three components, namely a compound melting between 100 ° and 180 ° C with a secondary alcoholic hydroxyl radical, an inorganic metal salt or metal acetate and sulfur. Some of them are described in Japanese Patent Application Laid-Open No. 14510/1966

The first-mentioned constituent includes, for example, bartzoin compounds such as benzoin, 2-methoxybenzoin, 4-chlorobenzoin, 4-dimethylaminebenzoin and 2-chloro-4'-dimethylaminobenzoin, carbinols such as diphenylcarbinol, ™

? ^v ericlv5ri3indungen such as resorcinol, pyrogallol, 3-hydroxy-4-sulfonic acid, 4-nitroresorcinol and 4,6-Dibromresoroin and henceforth polyhydric aliphatic alcohols such as erythritol, sorbitol, galactose, maltose, mannitol and sucrose;

The second-mentioned component includes, for example those compounds which 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.

0) Mixtures of mainly one compound with secondary alcoholic hydroxyl radical (corresponding to the first component of b) and a complex compound according to a). Such Mixtures are described in Japanese laid-open specification 14511/1966.

d) Mixtures of a carbohydrate and a dehydrating agent, as described in the Japanese patent application I3237 / I967 are described. There are two

109863/1038

for example as carbohydrates sucrose, fructose, oalactoea and starch and sulfuric acid as a detergent » Acetic anhydride, anhydrous zinc chloride and p-toluenesulfonic acid are listed.

In addition to these heat-discolored compounds or mixtures mentioned above, the following additional combinations of substances are also known:

e) a mixture of an iron salt of a long-chain fatty acid such as Elsen (III) stearate or myristate and phenol or a phenolic compound such as tannic acid, gallic acid or ammonium salicylate;

f) a mixture of mainly on the one hand a salt one Sword metals such as nickel, cobalt, lead, copper, iron, mercury or silver, and an organic acid such as Acetic, stearic or palmitic acid, and on the other hand an alkaline earth sulfide such as calcium or barium sulfide. Instead of of the alkaline earth sulfide can also be an organic chelate compound, such as 3-diphenyl « carbazid or diphenylcarbazone, may be present;

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

h) a mixture of mainly a fatty acid iron (III) salt, such as iron (III) stearate, and an aromatic polyhydroxy compound, such as 3,4-dihydroxytetraphenylmethane;

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1) a mixture of mainly one precious metal on the one hand an organic acid such as a.B. Silver oxalate or Queclin beroxalate, and on the other hand an organic polyhydroxy compound, such as a polyhydroxy alcohol, Glycerin or glycol;

j) a mixture of mainly on the one hand a noble metal salt an organic acid such as silver behenate or stearate, and on the other hand a reducing organic compound, such as protocatechuic acid, spiroindane or Hydroquinone;

k) a mixture of mainly a fatty acid iron (III) salt, such as iron (HI) pelargonate or laurate, and on the other hand Thlosernicarbazid or isothiosernicarbazide;

1) a Geraisch mainly on the one hand a lead salt of an organic acid, such as 3. Lead capronate, pelargonate or behenate, and on the other hand a; n thiourea derivative, such as ethylene thiourea or N-dodecylthioureaί

m) a device consisting mainly of a heavy metal on the one hand salt of a higher fatty acid, such as Elsen (III) - or Copper stearate, and on the other hand zinc dialkyldithiocarbarateJ

n) a mixture which, on the one hand, either, such as resorcinol plus nitroso compound, a dye or on the other hand forms an azo dye.

However, the invention is not necessarily based on the above with regard to the visibly reacting, heat-sensitive component Listed compounds or mixtures of compounds is limited, but can also be seen through

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109883/1038 bad

Use Anything customary in the field of thermocopying Perform components that thermally release a polyvalent metal cation. These include, for example, the aforementioned heavy metal salt of an organic acid or a mixture of on the one hand an organic reducing agent, sulfur compound or amino compound and on the other hand Heavy metal salt of an organic acid or any individual compound that can thermally develop a color. In addition, those compounds or mixtures can also be used which differ because of the insufficient intensity of the Thermally supplied dyeing is not suitable for the production of heat-sensitive copying material.

Suitable for ErfindungsdurchfUhrung thermofusible compounds include the metal salts of saturated or unsaturated higher, C, _Q means - Cp ₂ fatty acids with melting ranges between 70 ° una 150 ⁰ C. As an example of the acid component may be stearic, Palraitin-, lauric, myristic -, 01-, eruca and behenic acid, and the metal components - based on the table of periods - are metals from group II, such as calcium, zinc, cadmium, magnesium, etc., those from group IV, such as lead, those from group VII, such as manganese, those of group VIII, such as iron, cobalt, nickel, etc., and those of group I, such as copper. They can be used individually or in groups. Metal salts of fatty acids with fewer carbon atoms than capric acid (CgH, _Q C00H) fail because of their unpleasant odor in practice. It is true that lan can work with metal salts of fatty acids with more carbon atoms than the C ₂₂ visual acid; however, those salts of fatty acids with up to 22 carbon atoms are most suitable. For the combination of a heat-sensitive component and a heat-fusible compound, it is preferable to select substances that do not chemically react with one another.

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If "a stencil sheet with the invented, thermally discoloring additives is irradiated with infrared radiation for the purpose of stencil production, not only are the films corresponding to the original image thicknesses perforated" but at the same time the constituent present in these areas melts and discolors, giving them increased clarity, and the colored melt creeps together along the perforation edges, so that in the end a clearly observable image with sharp contours consisting of perforations is created. CABEI attach the allerfeinaten particles of gefärbjten-melting, zs to the fibers of the backing paper to, soctass to the _Λ th of perforated areas with the naked eye as clearly as a pressure ™ eir "T u 1 or ^r eir.e photography can consider normal fashion. in addition, results from the described outlet of the colored melt from the perforated G ^<J rivets the important advantage that the later üurchti'itt cer JDruoKfarbe learns through them no disturbance.

In the stencil sheet according to the invention of type A, the additional adhesive can first be applied either to the carrier paper or to the film and then both can be combined in any usual way. In the case of type B stencil sheets, on the other hand, rr.an can apply the additive solution to the filter surface by roller or spray application or by spraying. Λ

In summary, it should be noted again that the production a template from the inventive template sheet Associated with the advantages is that nan can not only determine the correct infrared exposure, inaeinaein the perforated "stencil area observed with the naked eye and with the Original image compares, but also from the clarity of the color image formed on the template to the clarity of the later can close prints made with the template because

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Color image and print are equivalent in terms of clarity . The invention therefore eliminates the inadequacy of previous stencil sheets, that the correct exposure can only be assessed after the stencil made with them has been completed and used.

In the following, the invention will be made more preferred by way of some Execution examples explained in more detail without being limited to them »

example 1

Here the visibly reacting, heat-sensitive one existed Ingredient au3 zinc stearate and diphenylcarbazone and the heat fusible Compound of calciurostearate, both in the Adhesive approach were introduced.

This approach was prepared in such a way that 10 g of zinc stearate and lü g of calcium stearate were added to 150 ml of a 4.5% methanolic polyvinyl acetate solution, the Oernisch obtained was worked through well in a ball mill for 3 hours and finally 2.0 g of diphenylcarbazone were added.

With this adhesive approach, a 7 / U was then thicker, more transparent Filii, made mainly of vinylidene chloride-vinyl chloride copolymer with a 9 g / in heavy and J5ü> u strong, porous thin paper made mainly of Manila hemp fiber. Of the Glue was applied to the paper by means of a roller

2
Quantity applied corresponding to about 2, "d g / iu solid.

The stencil sheet obtained in this way was i'il; ns <; itlg with one Original, namely a newspaper clipping, documented and then from the paper side into a device of the 3-M Co., Ltd. infrared irradiated. So you got on the stencil

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a perforation image and a red image that was congruent with it, which was clearly and sharply set off from the pink background. This made it easy to achieve perforations true to the original. The stencil produced in this way delivered a large number of sharply-razed and true-to-original prints in a commercially available duplicating machine.

The correct exposure in stencil production was determined in such a way that one of the colored Perforation image observed with the naked eye and at first repeated the exposure correspondingly often if there was still a lack of clarity, for example in the present case of the DIN-4 large original a 4 seconds long exposure than the right one.

For comparison, the same materials were used, but with additive-free polyvinyl acetate solution as an adhesive, four stencil sheets produced, which again under a DIN A4 original la Thermofax machine exposed for about 5 seconds, 4 seconds, 5 seconds, or 6 seconds became. In all four cases, the resulting perforation image was barely recognizable and it was not possible to determine » which stencil sheet was correctly exposed. Of the so obtained four templates could only be used with 4 seconds lichtung produced in the duplicator to deliver true-to-original prints, while the rest of the prints resulted in blurred prints «

Example 2

Example 1 was repeated with the modification that the adhesive formulation 30 g lead acetate, 5 g benzoin and 3 g sulfur as heat-sensitive ingredient and manganese stearate as the heat-earring ingredient Compound were added.

109883/1036 _ß AD ORKäNAU

Daa Sohablonenblatt provides · a sharp, dark brown ·, good "Flathable perforation" picture on a white background, and old A large number of sharply engraved prints were made from the finished template.

Example 3

According to the procedure described in Example 1, six types of stencil sheet were produced in which the adhesive formulation of polyvinyl acetate solution contained the additives according to the invention indicated in the table below, which gave the perforation image the color indicated as well.

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Template heat receiver nenblatt component

Heat melting · Mixture coloring of the connection ratio Perfor.Bildee

b a / b in

Parts by weight

Hexamethylene lead palmitate t et r aiainkoba 11 chloride blue

Iron (III) stearate and

GaIl u-s-s sura (3: 1)

Manganese stearate 2: 1

blackish brown

Lead oxalate

and
Thiourea (1: 1)

Potassium palatine blackish brown

Silver behenate and

Protocatechuic acid (6: 1)

Zinc stearate

2.3! 1 blackish

Brown

Iron (III) laurate
and
Thiosemicarbazide

Magnesium myristate

2.8: 1 blackish

Brown

Cu (II) stearate and

Zinc dialkyld ithioc arbatnat

Cobalt-

.! iyristat

, t>! 1 blackish

Brown

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109883/1038 ORIGINAL BATHROOM

Example 4

The additives according to the invention were incorporated into a top layer brought in.

In 8OO ml of a 4.5 '/' methanol laugh polyvinyl acetate solution became 5 g of pyrocatechuic acid as a heat-sensitive ingredient and 20 g of diphenylnitrosamine and as a water-soluble compound 10 g beta-indispersed nickel laurate

The dispersion obtained in this way was applied to a 7 u thick, transparent Mainly vinyl chloride-vinyl chloride copolymer film applied and dried.

The film coated in this way was on its free 3 side with
With the help of an adhesive consisting only of polyvinyl acetate solution
combined with the backing paper according to Example 1 to form a stencil sheet.

This resulted in further processing according to Example 1 in
again with a stencil in an easily controllable manner
a sharp, blackish-brown, clearly visible perforation image, with which a large number of
received sharp prints.

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10 98 83/1038

** 0 OR1GI _Na

Claims (1)

Kabushiki Kaisha Ricoh
Tokyo, Japan Claims 1. Heat-sensitive stencil sheet made of porous », aünnem Backing paper and on one iJeite by means of adhesive attached film of mainly thermoplastic resin, characterized in that the adhesive has a t;: tohtbar reacting, with heating a color !; developing, would be a primary component as well as a hot melt Connection aua., At least one ln-caxlsaia of a higher one iu'H iiiit Iu fciu 2ΰ Kohleriütoffato..ien contains. üohablonenblatt according to claim 1, characterized gekennzelchaet, daso ha adhesive contained to 1 part by weight of dry matter of two additional types depending üewiohtsteile 0.1 to 1.0 and to ^ atzhaltlge adhesive as a whole in an amount corresponding to (J, 5 to 5 * 0 β / υ · * "of its dry matter! is contained in üchablonenblatt. | ochaolonenbiatt according to claim 1 or k: characterized by, that the Filui is 5 to lu / U üiuk and mainly Hch consists of vinylidene chloride-vinyl chloride copolymers 4. üchaolonenblatt according to one of the preceding claims, characterized in that the Trägex'papier 7 to lfj g / 2
eat hard intm - 18 -109883/1038 5. stencil sheet according to one of the preceding claims, characterized in that the visibly reacting, heat sensitive component made from such components exists as it has been for heat-sensitive copying material up to now to be used. 6. Heat-sensitive stencil sheet made of porous, thin Backing paper and on one side of which an adhesive film made mainly of thermoplastic resin, characterized in that the film has a coating; having, the one visibly reacting, with,;: '' gibberish one Color-developing, heat-absorbing component as well as a heat fusible compound of ii.inriest ^ r ..; a metal U, aiz a higher fatty acid iüit li; to d> Contains carbon atoms. 7. stencil sheet according to claim 6, characterized in that that the cover warms up to 1 weight point Ingredient l, 1 to l, o (weight parts wäi-iii Connection contains and to the. sheet in a length accordingly 0.1 to 3, o g / n. FiJstsubstnti ^ is present. H. iJchablonenblatt according to claim 6 ocirr '(, ciaciurc'n marked that the coating consists of the adhesive containing the two additional types. y, stencil sheet according to one of claims 6 to 8, characterized in that the film ^f j to lü.u is nicked and consists mainly of vinylidene chloride-vinyl chloride copolymer. 109883/1038 ßAD lü. Template sheet according to one of Claims b to <y, characterized in that it is heavy. characterized in that the backing paper is 7 to 15 g / m 11. stencil sheet according to one of claims 6 to lü, characterized in that the visibly reacting, heat-sensitive component is made up of such components exists as it was previously for heat-sensitive copying material to be used. 109883/1038, "; BATH ORIGINAL