DE2323357A1 - DIE AND METHOD OF MANUFACTURING A WRITTEN OR PRINTED DIE - Google Patents

Description

Applicant: Weber Marking Systems Inc., Arlington Heigths, Illinois, V.St.A.

Die and process for producing an inscribed or printed die

The invention relates to a die which is provided with a layer of a hot-flow compound and it relates to a method for producing a peelable, printed or labeled matrix by the Image or print areas are subjected to heat generated by infrared rays.

British Patent 1,229,016 describes a thermographic Die, which has a color-permeable base sheet with a color-impermeable layer of a warm-flowable Having connection. This compound consists of a film-forming organic cellulose ester and a plasticizer, which is partially but incompletely compatible with the film former. This die is currently widely used in Commercially available. It is preferably placed in a die

OWGINAL INSPECTED

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used, on one side with an absorbent contact sheet and on the other side with a more rigid one Underlay is provided on which the absorbent sheet and the die are arranged. In use, an original, such as a written or printed sheet, is placed between the The die sheet and the die pad are used. The side with the absorbent sheet is printed in a thermal copier, like a "Weber Thermal Imager" or a Biermo-Fax device (3M Company) exposed to infrared rays. Heat is generated in the radiation-absorbing graphic areas of the original, whereby the connection of the matrix begins to fHessen in the corresponding areas and thereby corresponding image openings arise in the die. Part of the flowing connection is through the absorbent sheet and / or the adjacent Areas of the matrix absorbed. The original and the absorbent sheet are separated from the imaged stencil separated. The template and the pad are placed in a duplicating machine, the pad removed and Prints made.

It has been found that "oil" is released from the die when in use the original is transmitted in the image areas. This oil often causes widening and blurring of the copy on the typed original (smearing) and the presence of oil on the original is not desirable. Lubricating the Originals affects the copy speed in subsequent exposures because of the flattening of the image character or the transfer from the original to the die. Further work will be affected if the original is repeated is removed from the tray for further prints or, if so, the optimal exposure when producing the image the first die did not take place.

It is desirable to reduce oil carryover during the advantageous properties of the matrices mentioned are retained.

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In US Pat. No. 5,704,155 there is an improved thermographic Discloses a die in which oil transfer is reduced. This known die has a warm flowable one Compound that forms a cooled melt with a limited pourable liquid volume. The plasticizer in the joint has a limited glue and aniline point. This die has significantly better oil transfer properties and in many cases gives better copies. Nevertheless, there are still disadvantages, the improvements require. Accordingly, the various embodiments of this known die do not show optimal results for all essential work characteristics, such as copying speed, the image quality, in terms of oil smear, as well as oil transfer and durability. Often unwanted occurs Stick on when oil lubrication is reduced to a minimum. In some cases the oiling may not be the preferred one low levels are reduced. At the moment the copy speed or the image quality is far less than optimal.

The dies are with improved oil transfer properties less durable, especially when using the preferred compositions for the coating compound will. Changes in the coating connection, which increase the durability and cause a low oil transfer, affect other properties, especially the copying speed.

The object of the invention is to create a die in which the oil transmission is reduced and, preferably, the durability the die is increased while its other properties are maintained or improved to the working characteristics to optimize a thermographic matrix to a large extent.

The die according to the invention is based on the embodiment according to the above-mentioned British patent, in which each

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However, the oil transfer is reduced and the rest of the known Properties are retained or in some cases improved. In the preferred embodiments of the invention, the durability of the die is also increased.

The matrix according to the invention has a color-impermeable one Layer made of a hot-flow compound of a film former which consists of an organic cellulose ester and a plasticizer, this plasticizer partially but is incompletely compatible with the film former and in a ratio of 3-60 Vol- #, based on the total volume of the film former and plasticizer, a thermoplastic polymeric hydrocarbon resin containing a total content polymerized indenes (indenes) and coumarones of at least jX) by weight.

The hydrocarbon resin serves in the compound both as a plasticizer for the cellulose ester and as a film former, which, however, has a much lower film-forming power than the cellulose ester. Hence the hydrocarbon resin treated as a plasticizer, while its film-forming properties in the composition of a coating connection should be considered.

In a preferred embodiment of the invention, an alkylene oxide adduct, in particular an alkylene oxide ester or -ether of a long-chain fatty acid or a long-chain fatty alcohol with an HLB value of 1.5 - 8, incorporated and forms part of the hot-flow coating compound the die. The alkylene oxide adduct serves as a component of the plasticizer in the coating composition.

The invention also relates to a method for producing a negative matrix, the matrix with a graphic Original is brought into contact. The image areas of the template are generated by infrared ray absorption Exposed to heat in the original in order to make the connection flow in the image areas of the matrix. This will

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has the effect that the connection flows away from the image areas and the corresponding color-permeable openings in the matrix develop. Preferred embodiments according to the invention can also, or alternatively, mechanically with the image be provided.

According to the invention, a die can be created in which the oil transfer is reduced to a previously unattained minimum. It is only a very small proportion of the oil transfer by the preferred embodiments according to of the aforementioned British patent could be achieved. Furthermore, the preferred embodiments of the molds according to the invention have a significantly better durability if they multiply after the production of the image or transfer printing can be used. The addition of the alkylene oxide adduct increases those with various coating compounds reached durability. So can a die with extraordinary Durability up to 50 # greater than that known Matrices, if desired. In addition, a die with other favorable properties, For example, sensitivity in the mechanical production of the image or the negative, which affects the durability of the die affect, can be made more durable with the measures according to the invention than is otherwise the case. Simultaneously the quality of the copies does not suffer and the copying speed is maintained and sometimes increased.

The matrix according to the invention has a matrix base which consists of any suitable fibers, such as abaca fibers, abaca and wood fibers, kozo fibers or polyester fibers, which are loosely arranged in order to form a porous, highly permeable fabric. The weight of this fabric can be about 2.04 to 5.44 kg / 278.71 m ² (24 "by 36" per 500 sheets). A layer of a hot-flow compound that is solid at room temperature is applied to this base. The amount of the applied layer

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carries about 6.35 to 9 * 52 kg / 278.71 m ² (dry basis is),

preferably about 9.52 kg / 278.71 m.

The hot flow coating composition melts
preferably at least about 65 C. A
Melting range of about 65-180 ° C., preferably about 90 160 ° C. The melting point, as it is meant here, denotes the temperature at which the compound is on a die

visibly melts or becomes liquid.

The hot-flow compound consists of an organic cellulose ester, which is suitable as a film-forming agent and is therefore able to form a continuous, cohesive, tough, flexible, color-impermeable film. The cellulose ester melts or is platifiable in the range from about 65-180 ° C. Lower alkanoic acid esters of cellulose are preferred, with 2-5 carbon acid esters being particularly preferred.
This subheading includes cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate valerate, cellulose propionate butyrate, cellulose propionate valerate, cellulose butyrate valerate,
Cellulose propionate, cellulose butyrate and cellulose valerate.
The amount of cellulose ester used is preferably about 5-45% by volume (6-52% by weight), in particular about 14-30% by volume (16-36% by weight) of the coating compound, including but excluding the film-forming and plasticizing substances of the additives added. In practice it has been found, in agreement with the theoretical calculations, that "parts by volume are more sensible than parts by weight when it turns out that one component is to be replaced by another. For this reason, the constituents of the coating compound are in most cases in The preferred cellulose esters indicate a total content
Butyryl and valeryl of at least about 35% by weight and a hydroxyl content of at most about 4.7% by weight. The most beneficial results will be when using higher
Total proportions of butyryl and valeryl, at least about 44 parts

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weight ^, and low Em hydroxyl content, at most about 2% by weight, achieved. A total butyryl and valeryl content of at least about 48 weight percent and a hydroxyl content are optimal less than about 0.7% by weight.

Cellulose acetate butyrate is currently the preferred cellulose ester because it provides a very high quality product and is also readily available commercially. Of the available grades of cellulose acetate butyrate, preference is given to using those which have a butyryl content in the range of about 35-55 & preferably at least about 44-48 #. In the advantageous grades, the average acetyl content is in the range of about 1.5-1.5.5 # and the hydroxyl content in the range of about 0.1-4.7 $, both on a weight basis. As mentioned above, the better products are obtained with the lower hydroxyl contents, below 2 #, preferably below 0.7 #. The preferred grades have viscosities of about 0.07-6 seconds as measured by ASTM Method D-1J43-54T in Formula A, ASTM Method D-871-54T, and melting or softening points in the range of about 125-185 ° C, preferably at least about I50 ⁰ C, determined at the time at which a sample is first appears wet.

The film-forming cellulose ester is combined with a plasticizer, which is partially but incompletely with the ester ■ is compatible. This plasticizer is a substance that, when heated with the film former in the proportions used is, forms a substantially homogeneous, single melt phase, and after the melt has cooled to the ambient or room temperature forms a two-phase mixture, wherein at least one phase of the mixture contains substantial proportions of both the film former and the plasticizer.

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The preferred embodiments of the coating composition of film former and plasticizer show a transition between a single-phase mixture and a two-phase Gemifth at a temperature generally in the range of about 50 - is I3O ⁰ C. This transition temperature is referred to herein as the compatibility temperature and is determined as the cloud point when cooling the single phase mixture. Accordingly, the first appearance of turbidity indicates the transition from the single phase to two phases. In general, there is a transition from a clear liquid to a cloudy liquid, but a masking substance can be present without, however, the effect being impaired.

After cooling below the tolerance temperature, the separation proceeds into two phases. The mixture remains liquid above a temperature range and then the mass containing the main part of the film-forming agent begins at Cool to room temperature gradually harden to a solid mass. The remaining phase can be at room temperature solidify or remain fluid. In the preferred embodiments the remaining phase is liquid at room temperature, so that a solid-liquid two-phase mixture is formed. the Liquid phase can be enclosed by the gel structure of the solid phase or it can appear as a separate liquid component secrete.

As described in the referenced British patent, the plasticizer of the coating composition can be any be a single compound or consist of several plasticizers. Plasticizers are essentially non-volatile substances that serve to modify the physical properties of the film-forming cellulose ester, for example the To change the melting or softening point, the compatibility and / or the flow properties. You can either use liquid

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or be solid, from room temperature to Working temperature. But at least they have to be liquid at work. This applies to 'the total salary the plasticizer in the coating composition.

With regard to the compatibility with the film former, the plasticizers are essentially divided into three groups, and partially but incompletely compatible, incompatible and compatible substances. Certain of the partially compatible plasticizers can be used individually. On the other hand, two or more plasticizers with their own compatibility properties can also be used, it being possible for these degrees of tolerance to range from complete tolerance to complete incompatibility. It is only important that the plasticizers are matched to one another in such a way that they together achieve the appropriate balance the most compatible with the film former. When a variety of plasticizers are used, it is extreme it is desirable that they are compatible with each other at room temperature and form a single phase mixture when used for Mix together to be heated and cooled.

The plasticizer or the finished plasticizer mixture of the preferred Coating composition is oily or oily, i.e. it contains one or more oily plasticizers. As can be seen from the UK patent cited above, Numerous oily plasticizers can be used, such as mineral oil, castor oil, hexadecyl alcohol, polypropylene glycol monobutyl ether, Polyoxyethylene ethers of lanolin alcohols, pentaerythritol tetraester aliphatic acids with 5 to 10 carbon atoms, trimethylolpropane triesters of aliphatic acids with 5 to 10 carbon atoms, resin oil, polyoxyethylene polyol fatty acid esters and various other natural and synthetic oleaginous substances. According to the invention

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The hydrocarbon resin used may contain oil, while the alkylene oxide adduct used according to the invention contains oil. Numerous other plasticizers such as those mentioned in the above Can also be incorporated into the coating composition.

It has been found that a plasticizer or a finished plasticizer mixture with certain additional properties are particularly suitable. For example, an "amorphous plasticizer" with an optimal viscosity of about 40-110 Saybold seconds at 99 ° C is preferred for producing the negative separable liquid phase, which remains in a cooled melt of the coating compound, to be kept to at least about 10 cp at 20 C. For good aging or post-curing properties, it is advantageous if the plasticizer has a maximum vapor pressure of about 0.1 mm Hg and is essentially not hygroscopic For the stability of the emulsion of duplicating inks it is important that the water solubility of the plasticizer is at most about 1% at 30 ° C.

For the mold of the present invention, it is generally most advantageous to use a mineral oil with the hydrocarbon resin for performance, availability and economy. If the alkylene oxide adduct is added to the plasticizer or plasticizer mixture, it should have the properties mentioned above, although other of the mentioned additionally oil-containing plasticizers can also be used. Mineral oil and / or another of the oil-containing plasticizers can preferably be present in a proportion in the range of about 10-70 % by volume, in particular 15-65 % by volume, based on the total volume of the film former and plasticizer.

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The preferred mineral oils, especially petroleum oils, have a viscosity below about 10,000 Saybolt Seconds (SUS) at 38 ° C, preferably about 30 Saybolt seconds at 38 C. mineral oils with an aniline point in the range of about I5 ⁰ C (mixed aniline point ) up to about 115 ^° C. (straight aniline point) have proven to be useful. In general, oils with a lower aniline point are preferred with less tolerant. borrowed cellulose esters are used, ie those esters whose acyl groups to be esterified have a lower average molecular weight, and vice versa.

The aniline points reported herein were generally determined by A.S.T.M Test D-1012-62, unless otherwise stated is. The mixed aniline point is the minimum equilibrium solution temperature a mixture of 2 volumes of aniline, 1 volume of sample and 1 volume of n-heptane of a certain purity. Straighter Aniline point is the minimum equilibrium solution temperature of a mixture of 1 volume of aniline and 1 volume of sample. if If the aniline point of a sample is too high or too low for a direct measurement, a Substance with a known aniline point of the opposite size can be mixed. Then first the aniline point of the mixture determined and the unknown aniline point using the formula

. ^A m - Vk

u N determines, where A is the unknown aniline purict,

A is the aniline point of the mixture, A. the known aniline point in ic

and N, and N are the volumetric fractions of the substances with the ic χι

mean known or the unknown aniline point. The theoretical aniline points reported herein were thus obtained certainly. Likewise, the aniline points of plasticizer mixtures calculated as the average of the aniline points of the individual plasticizers, based on their relative volume fractions. The aniline points given in the examples are in this way, has been determined.

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The plasticizer is a polymeric hydrocarbon resin in Quantities of about 3 - 60 volume - $>, preferably 10 - 30 volume- ^, based on the total volume of the film former and plasticizer including the resin. The preferred resins are synthetic Thermoplastics are derived from coal tar or petroleum and they can more precisely be referred to as polyindenes (poyindenes) will. They contain a minimum amount of about 30, preferably 40 weight- ^ polymerized indenes and coumarones, in particular polymeric indene, coumarone and their mono- and di-methyl derivatives, as they are found in the hydrocarbon resin mixtures, the indenes and coumarones are called bicyclic Called monomers.

Further suitable hydrocarbon resins are polymers with a monomer content essentially based on indenes, coumarones and Styrenes is limited and they can include aliphatic unsaturated monomers, especially cyclopentadienes. The ones meant here Styrenes are also referred to as aromatic vinyls or monocyclic monomers and include styrene and its Derivatives such as those mono- and dimethyl-substituted in the ring and in side chains Derivatives of styrene, * ethyl styr oil, divinylbenzene and the like, as found in hydrocarbon resin mixtures., Divinylbenzene is contained in some resins, but is an undesirable monomer and is preferably limited to a maximum of about 8% by weight of the monomer content a resin limited. The cyclopentadiene includes in particular mono- and dicyclopentadiene and their mono- and dimethyl derivatives, as they can also be found in the carbon resin mixtures. The cyclopentadienes are expedient to a maximum amount of about 20% by weight, preferably about 10% by weight, of the monomer content a resin limited.

It is also a hydrocarbon resin preferred that at least about 40% by weight polymerized indenes and coumarones; and at least about 80% by weight polymerized aromatic contains "unsaturated" or aromatic "olefinic" monomers,

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in particular the indenes, coumarones and styrenes described above are included. Any remaining monomer content of the Resins can essentially polymerize from, aliphatic (including cycloaliphatic), unsaturated or olefinic Monomers, in particular the above-mentioned cyclopentadienes. It is also preferred that the monomer content of the resin at least about 8θ; 2> polymerized indenes and coumarones, the remainder consisting essentially of (a or more) polymerized styrenes. The latter resins are referred to as coumarone-indene resins, the usually from the crude heavy oil solution fraction of the coal tar light oil as well as certain carburized water gas oils.

The hydrocarbon resins suitable according to the invention can be liquid or solid at room temperature and softening points (Ring and Ball, A.S.T.M. E-2J5-42T) preferably in the range from about 5 - 175 ° C. The preferred resins longer shelf life are solid at room temperature and have softening points above about 50 C, preferably above about 90 ° C.

Corresponding hydrocarbon resins have a specific weight (25 ° C, A.S.T.M. D-71) in the range of about 0.969 - 1.15, preferably about 1.016-1.145, and most preferably about 1.132-1.145. The suitable hydrocarbon resins have one Refractive index (n, ^) in the range of about 1.53-1.65, preferably about 1.56-1.64, especially about 1.62-1.64. Your iodine numbers (Wijs, A.S.T.M. D-I959) seem generally lower than about 100, the viscosity (Brookfield) is 1 poise at about 70-270 ° C and 10 poise at about 40 220 C. It is appropriate that the color has a maximum of about Gardner 14 (Neville 5), preferably Gardner 9 (Neville 2).

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The preferred coal tar resins are through.Polymerization made of monomers from crude low-solution naphtha, which boil in the range of about 150 - 200 ° C. The existing The main monomers are indene, methylindenes, coumarone, styrene, Vinyl toluenes and alpha methyl styrene. The resins can through Polymerization of the monomers in the presence of a catalyst such as acid, clay and Friedel-Craft catalysts will. Examples of such methods are described in U.S. Patents 1,990,21.5 and 2,565,222. Preferred coal tar resins include the coumarone-indene resins known as coumarins (Neville Chemical Co.), which grades R-I, R-J5, R-5, R-6. LX-509, R-7, R-9, R-IO, R-H, R-12 and R12A. The next in the series of preferred coumarins include grades R-IJ, R-10, R-15, R-16, R-17, RH-17 and R-19. The coumarins R-21, R-27, R-28, R-29, P-IO and P-25 can also be used be used.

The preferred petroleum hydrocarbon resins are made by the polymerization of by-product monomers produced by Cracking at high temperature and low pressure of petroleum naphthas, natural gas or gas oil in the production of ethylene, Propylene, butene and / or isoprene can be obtained. The monomers preferably boil within a range of about 100-300 C, contain indene, methylindenes, styrene and vinyltoluenes as the main polymerizable component and can also contain certain cyclopentadiene compounds. the Resins can be produced by Priedel-Craft polymerization of the monomers as described in US Pat. No. 3,422,053 is. A preferred resin made by this process is that known as Neville LX-15I7 (Neville Chemical Co.)

Further suitable hydrocarbon resins are those under the name Nevex 100 and Nevex 110 (Neville Chemical Co.), Resin EC-70 and Resin XL-30 (Velsicol Chemical Corp.), and piccoumarone 410-HL and Ficcoumaron 410-L (Pennsylvania Industrial Chemical Corp.) well-known products. The suitable hydrocarbon resins are low molecular weight polymers, which are preferably

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an average molecular weight of less than about 2000, preferably in the range of about 290-1600, especially in the range of about 400-1200, the determination by means of a vapor phase osmometer (osmotic pressure meter).

The plasticizer is an alkylene oxide adduct, ie alkylene oxide esters or ether of a long chain fatty acid or a fatty alcohol, incorporated, in a preferred amount of about 5-60 VoIum-%, in particular about 10-55% by volume of _s based on the Total volume of the film former and the plasticizers including the adduct. Preferred adducts are ethylene oxide and propylene oxide esters and ethers of fatty acids and alcohols having 12 to 20 carbon atoms. Particularly preferred are adducts which contain 1-3 * 5 mol of ethylene oxide or about 1/10 mol of propylene oxide reacted with a fatty acid or alcohol.

The alkylene oxide adduct is a nonionic compound which is preferably used in the amounts added at room temperature in the remaining components is completely soluble or miscible with this. The preferred adducts have an HLB value in the range of about 1.5-8, preferably about 4-7 x the "HLB" value is an index of the "hydrophile-lipophile balance" as it is in "The Atlas HLB System" of Atlas Chemical Industries, Inc. (1963). The HLB value is an indication of the percent by weight of the hydrophilic component of a nonionic Molecular and is about 1/5 of such a percentage or it is an experimentally determined apparent value in the case of Polypropylene oxide and certain other compounds.

Preferred alkylene oxide adducts are those under the following designations known fabrics: Brij 92, Brij 72 and Brij 52 (ICI America); Volpo 3 and Provol 30 (Croda, Inc.); Arosurf

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66-E2 and Arosurf 90-E2 (Ashland Chemical Co.) ■; Neodol 25-3 (Shell Chemical Co.) and Emery 3926-D (Emery Industries).

If desired, one or more additional plasticizers can be added to the coating composition when one or more properties of the die are to be set. So are for example other plasticizers are described in the aforementioned British Patent and U.S. Patent 3,704,155. It can also be beneficial be, the coating composition finely divided Add silica gel (U.S. Patent 3,694,244). Together with the inventive Composition, silica gel prevents unwanted sticking, also reduces oil transfer where it is less than is optimal and can additionally improve the durability.

It appears advantageous that the mixed aniline point is the total plasticizer or the plasticizer mixture in the range of about 4-54 0 when it is used as film-forming agents cellulose acetate butyrate. With the preferred grades of cellulose acetate butyrate, the preferred range is between 21 and 54 ° C. In general, the compatibility of the cellulose ester film former increases with the ratio of acyl substitution and the preferred aniline point of the plasticizer increases with increased film former compatibility and vice versa. For example, the preferred mixed aniline point of the plasticizer when cellulose acetate valerate is used is about 20 ° C. higher than for cellulose acetate butyrate. The hydrocarbon resin used according to the invention preferably has a mixed aniline point in the range of about 30-65 ° C, in particular 45-60 ° C. The alkylene oxide adduct used according to the invention has a mixed aniline point in the range of about -5 to 40 ° C., preferably -5 to 10 ° C. One or more plasticizers can be mixed with the hydrocarbon resin, or with the hydrocarbon resin and the adduct to obtain the desired aniline point for the finished plasticizer.

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The specific film formers and plasticizers as well as their proportions are selected based on the properties defined here. The film formers and plasticizers are volatile Solvent soluble and are also selected and mixed in proportions that they are essentially one form a homogeneous, continuous, continuous coating when they are applied from a solution. In addition, the The base should be essentially clear, which means only the active or basic film-forming and plasticizing substances and the effect of the additives is not taken into account. Additives are silica gel, pigments, fillers and substances be added for other purposes. The reference to the clarity also excludes the clouding effects of fabrics, which have covering and opacifying properties, such as waxy substances, and which at room temperature are solid and are incorporated at temperatures which are above their solubility limits at room temperature. Film-forming agents and plasticizers are also selected and mixed in proportions so that they form a matrix coating, which melts in the range of about 65 - 180 ° C.

If the ingredients used are the basic or preferred If conditions are met, the proportions of the individual components can be adjusted within limits in order to to maintain the optimal properties.

The film former and plasticizer composition is in a volatile solvent at a temperature below about 60 C, preferably at room temperature, expediently completely soluble. The advantageous compositions are in organic solvent mixtures of an aromatic hydrocarbon and an aliphatic ester and / or aliphatic Soluble in alcohol. The dissolved composition is applied to the support and the solvent is evaporated. The matrix covering produced in this way is a uniform gel. The gel structure is changed so that the matrix

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layer is physically irreversibly converted when it to its melting point and sometimes when it is heated to the tolerable temperature, even if it is below the melting point. As a result, the coated die pad will be at a temperature below the melting point and the compatibility temperature, preferably at least 5 ° C. below the two temperatures.

To a die according to the invention with the optimal properties the following evaluation processes can be observed will:

Pur a selected amount of cellulose ester becomes a mixture of Plasticizers are made with different aniline points and their relative proportions are adjusted to the aniline point of the plasticizer mixture. until an optimum for the desired results are ensured. In general, the higher aniline points, the better the quality of the aniline Copy, slower copy speed, more oil transfer, lower durability, better pressure sensitivity and less result in unwanted sticking. The reverse is true for lower aniline points. The proportion of the cellulose ester is then also adjusted for optimal properties. In general, the higher the ester content for the same aniline point Decrease the quality of the copy, slow down the copying speed, decrease the oil transfer, increase the durability, reduce pressure sensitivity and reduce unwanted sticking. The reverse is true for low ester contents. the Adjustment of the plasticizers for an optimal aniline point can then be repeated with the optimal cellulose ester content.

Then a hydrocarbon resin is selected and examined in various proportions, whereby -the ^ ptimal men-

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ge cellulose ester is used with the plasticizer mixture at the optimal aniline point. The aniline point and / or the The proportion of the cellulose ester can - if desired - be adjusted again in order to achieve a better "balance" to achieve the properties with the existing hydrocarbon resin. In the same way, an alkylene oxide adduct in the composition can be evaluated along with the hydrocarbon resin. If desired, the one with the Hydrocarbon resin and the adduct used plasticizers or the plasticizers are replaced by other plasticizers, and / or the proportion of hydrocarbon resin or adduct can be varied by introducing or removing other plasticizers. This way the product can be in a or more of its properties improved, or made more economically attractive, or existing facilities or available materials. These variations can be continued indefinitely. It was also found that changes to the product for certain types of final use and / or reproduction facilities can be useful.

The die can be used in a conventional thermograph, such as a roller copier from Weber Thermal Imager or a Tape copier, such as the thermal fax model 45CG "Secretary", be provided with the negative image. A tungsten filament lamp or another suitable infrared radiation source is used for this purpose. A printed or written original is brought into contact with the die and immediately exposed to the rays exposed, i.e. within 0.03-0.1 seconds. The temperature in the image or print areas is reduced to room temperature sufficiently increased, i.e. to around 65 - 180 ° C.

The coating composition in the die is down to their melting point is heated and almost immediately in a flowing

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able state brought. Part of that composition is absorbed equally by the absorbent sheet or in the adjacent areas of the matrix, so that color permeable Image areas remain in the matrix. The openings are bridged by the fibers of the matrix pad. This base is color permeable and its pasers are used to position letter centers and the like to keep. It was also found that part of the coating hardens in the image openings after melting and remains here in finely divided particles. If the stencil is used for transfer printing duplicating, the Color flow around these particles. After the die has been provided with the negative image, it becomes the original and the absorbent sheet separately to serve as a duplicating template.

In the following examples the coating compositions were prepared in a solvent mixture, which consists of (partly in amounts by weight) 50 parts of toluene, 35.8 parts Ethyl acetate, 14.2 parts ethyl alcohol (95 # denatured, U.S. Formula C). It is indicated where this composition has not been used. In the solvent mixture was first the cellulose ester and then the alkylene oxide adduct - if one was added - dissolved. This was followed by the loosening of the Hydrocarbon resin and any other plasticizer except mineral oil. If mineral oil was added, this was finally mixed in with stirring. Silica gel was dispersed in part of the solvent mixture, if at all, in the solution of the film former and the plasticizer are added and mixed well. In this order, each coating composition was made at a concentration of about 30-35 weight- ^ in given the solvent mixture.

A stencil pad made of abaca fiber was coated with a coating composition and impregnated.

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The fabric of the die pad weighed 3 * 04 kg / 278.71 m. For coating, the underside of the support was brought into contact with the composition in a bowl and excess liquid was removed with a doctor wand. The pad was then hung and air dried at room temperature. The total layer weight was between 11.79 - 13.6:
wa 0.056 mm.

11.79 - 13.61 kg / 278.71 m ² . The thickness of the die was about

In addition to the specified ingredients (every coating composition 0.17g of dilauryl thiodipropionate antioxidant per 100g of active substance.

Each template was assembled with an absorbent sheet and. used for thermal tests where the negative copy speed and the quality of the copies

became. The absorbent sheet consisted of a 4.54 kg / 267.55 m heavy weave of mixed abaca and wood pulp fibers (grade 55 weave, Dexter Corporation). The oil smearing of the original was with a paper (bond paper) written on with a carbon copier tape and the oil transfer on an offset print certainly. Adverse sticking was identified by storing unassembled matrices at room temperature that were mutually exclusive were not touched and were wrapped in foil. Undesirable sticking was also identified in many cases by evaluating Fine holes examined after exposure with an unprinted sheet of the coated sheet in a thermal copier. The durability was determined on a Weber Model 50 (Weber Marking Systems) label pen of a copier.

Examples of substances that can be used according to the invention are described in more detail below:

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Cellulose ester

CAB 500-1 is a cellulose acetate butyrate of grade EAB 500-1 (Eastman Chemical Products) with an average Butyryl content of 49.6 #, an average acetyl content of 5.5 #, a hydroxyl content of 0.1-0.7 #, a viscosity from 0.8 - 1.2 seconds, measured according to the ASTM method, and a melting range of around 165 - 175 ° C.

CAB 500-5 is a cellulose acetate butyrate of grade EAB 500-5 (Eastman Chemical Products) with a medium butyryl content of 48 #, an average acetyl content of 6 #, one Hydroxyl content of $ 0.6-1.1 with a viscosity of 4-6 seconds (ASTM) and a melting point range of about I65 - I75 C,

CAB 381-2 is a cellulose acetate butyrate grade EAB 381-2 (Eastman Chemical Products) with an average butyryl content of yi%, an average acetyl content of Ij5.5 #, an average hydroxyl content of 2 #, a viscosity of 1-3.5 seconds (ASTM) and a melting point of I7I - 184 ° C.

Half-second butyrate (Eastman Chemical Products) has an average butyryl content of $ 37, an average acetyl content of Ij5.5 #, an average hydroxyl content of 2.%, a viscosity of 0.3-0.5 seconds (ASTM) and a Melting point range from I55-I65 ⁰ C.

Tenth of a second butyrate (Eastman Chemical Products) has an average butyryl content of 37 #, an average acetyl content of 13.5 #, an average hydroxyl content of 2 #, a viscosity of 0.07-0.16 seconds (ASTM) and a melting range from about I55 - I65 ⁰ C.

CAB 45I-I is a cellulose acetate butyrate grade EAB 451-1 (Eastman Chemical Products) with an average butyryl content of 44 #, an average acetyl content of 8.5 #, an average

309849/0412

Hydroxyl content of about 1.3 & a viscosity of 1-2 seconds (ASTM) and a melting range of 150-155 ° C.

butyrate
CBV is Celluloseate "^" Ltvalerat (Eastman Chemical Products) with an average valeryl content of about $ 46, an average butyryl content of about 6% _}, a viscosity of 0.9 seconds (ASTM) and a melting point of about 120 ° C.

Silica gel

That under the name Syloid 255 (Davison Division, W. R. Grace Company) is a silica gel with an oil absorption of about 142.88 kg / 45.36 kg, a particle size in the range of 0.8-12 microns (90 #) and an average particle size of about 3-4 microns.

Plasticizers

The known under the name Mobilsol L (Socony Mobil Oil Co.) product is a refined naphthenic petroleum oil having a viscosity of olSaybolt Seconds (SUS) at 38 ⁰ C, a straight aniline point of 74 °, an API gravity of 25.7 °, and a distillation range of 254-370 ° C (100 ^).

That known under the name Hercolube A (Hercules ,, Inc.) The product is the monopentaerythrl-tetra-ester of caproic acid, and has an acid number of 0.1, a saponification number of 420 and a specific gravity of 1.002 at 25 ° C. Its mixed aniline point is 17 ° C.

The under the name Si ^ belite Ester 5 (Hercules, Inc.) known product is a hydrogenated resin purified by steam distillation, the typical softening point of which (Hercules drop method) is at 81 ° C. Its acid number is 5, the specific gravity at 25 ° C is 1.06 and the mixed aniline point is 24.4 ° C.

Under the name Benol (Witco Chemical Company)

309849/0412

known product is a white mineral oil that is commonly used a viscosity of 100 Saybolt seconds at 38 ° C, a theoretical aniline point of 182 ° C, an API gravity of 34 °, a distillation range of 347 * 75 - 438.85 ° C ($ 100), an ASTM cloud point of -10 ° C, an ASTM Has a pour point of -12 ° C and a flash point of 199 C.

The under the name Conoco DBCL (Continental Oil Company) well-known product is dodecylbenzyl chloride ($ 94.5) with a viscosity of 101 Saybolt seconds at 38 C and a mixed aniline point of 18 ° C.

The product known as Texanol Isobutyral (Eastman Chemical Co.) is a 2,2,4-trimethylpentanediol diisobutyrate having a viscosity
a mixed aniline point of 8 ° C.

diisobutyrate with a viscosity of 9 cp at 25 C and

Under the name Flexol Plasticizer PEP (Union Carbide and Cabon Corp.) known product is di- (isodecyl) 4,5-epoxy-tetrahydrophthalate with a viscosity of 184 cp at 20 ° C and a mixed aniline point of 7 ° C.

A bis-alpha-methylbenzyl ether from Union Carbide and Carbon Corporation has a viscosity of 16.7 cp at 20 ° C and a Mixed aniline point of 22 ° C.

The product known as Atraul 122 (ICI America) is a solid that melts at around 52 C, made of mono- and diglycerides of edible fats and oils and a minimum amount of $ 54 contains monoglyeeride (alpha form) and one has a theoretical mixed aniline point of -1 ° C.

The products known under the name Conoco-Paraffins (Continental Oil Co.) are normal C-, j. to C-, r paraffins, the 97 3 weight $ n-paraffins and at most 2.2 weight -) ^ aromatic

309849 / CH12

Connections included. The product has a specific gravity of 0.78 at 16 ° C, a melting point of 8 C, a Viscosity of 2.7 centistokes at 38 ° C, and a mixed aniline point from 82 C.

The under the name Terpex Rosin Oil (SCM Glidden-Durkee) known product is a terpene hydrocarbon oil with a specific gravity of 0.945 at 15.5 ° C, a Gardner-Holdt Viscosity of H-K at 25 ° C and a mixed aniline point of 54 ° C.

Coal water first off-resin

Coumar Coumarone-indene resins (Neville Chemical Co.) characterized by the quality indications R-I, R-3, R-5, R-9, LX-509, R-7, R-9, .R-IO, R-Il, R-12, R-12Ä, R-I3, R-14, R-15, R-16, R-I7, RH-17, R-I9, R-21, R-27, R-28, R-29, P-IO and E25 have im essentially the following compositions:

Monomer proportions in

Weight- ^

Inden 41.7 - 90.2

Methylindenes 0-6.3

Coumarone 0-10.0

Styrene 0-14.8

Vinyl toluenes 3.2-37.0

Alpha methyl styrene 0-6.5

The preferred resin grades R-I, R-3, R-5, R-6, LX-509, R-7 R-9, R-IO, R-II, R-12 and R-12A have the following more precise monomer additions Administration:

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Proportions
Weight- ^ - 90.2 2323357 Monomer 79.8 - ■ 6.3 ■ Medium quantities
shares,
Weight- ^ In the 0 - 10.0 85.0 Methylindenes , 1.9 - 2.0 Coumaron 0 ■ 11.5 5.1 Styrene 3.2 - - 1.7 0 Vinyl toluene 0 7.7 Alpha methyl styrene 0.2

The above-mentioned preferred resin grades R-I to R-12A become collectively referred to as Type I resins. The resin grades R-13, R-.14, R-15, R-16, R-17, RH-17 and R-19 are classified as Type II Resins and the resin grades R-21, R-27, R-28, R-29, P-IO and P-25 referred to as type ΠΙ resins. The resins of the various Species generally have the following physical characteristics:

Type I Type II Type III

1st softening point, ⁰ C 98 - I65 56 - I05 7-48

2. Specific gravity, 25 ° C 1.132-1.145 1.016-1.127 0.969-1.099

3. Iodine number 51-65 48-76 46-84

4. Mixed aniline point, ⁰ C 46-56 32-62 33-64

5. Molecular weight 5 ² K) - 1150 40Q - 8OO 290 - 530

6. Temperature at 1 poise

Viscosity, ⁰ C 186-267 127-216 71-138

7. Temperature at 10 poise

Viscosity, ⁰ C I5I - 220 102 - I7I 44 - 98

8. Calculation number, 25 ° C 1.622-1.634 1.561-1.631 1.533 - 1.611

The individual coumarins used in the examples had the following physical properties:

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⁰ C R ^ RH-17 1.6241 2323357 1.5607 LX-509 ° C 111.5 71.5 R-19 I6O-I85 1. softening point, 1.141 1.123 56 1.134 2. Specific weight, 25 , ° c 51.2 63.1 1.016 58 3 iodine number 46.8 42.0 53.5 55.8 4. Mixed aniline point Poise 613 445 58 1090-1148 5 · molecular weight 591 6. Temperature at 1 Poise 195 - 167 Viscosity, ⁰ C - - 7. Temperature at 10 ⁰ C 159 - 220 Viscosity, ⁰ C 1.632 - 1.634 8. refractive index, 25

The analysis methods for the properties of the Coumarins were as follows:

1. ASTM D-28

2. ASTM D-71 for solid resins, pycnometer for low melt

ASTM D-70

3. Neville N I2.09-56T (modified Wijs)

4. ASTM D-611 modified (5g resin, 5ml n-heptane, 10ml aniline) 5 · Vapor phase osmometer, number average, Mechrolab Model 30IA 6th and 7th Brookfield Viscometers, Model LTV

8. Extrapolation of 70% resin by weight in toluene above 25 ° C Melting point determined on $ 100 resin with a softening point of 25 ° C or below.

The product known as Neville LX-I5I7 (Neville Chemical Co.) known product is a petroleum hydrocarbon resin, produced by polymerizing petroleum naphtha fractions which boil in the range of 100-3OO C and the following typical monomer compositions and physical properties exhibit:

309849/04

Monomer In the Proportions 103 1.593 Methylindenes Weight- ^ 1,062 Styrene 24 I9-27 Vinyl toluene 19th • 39.9 Alpha methyl styrene 19th 840 Divinylbenzene 23 6. Temperature at 1 poise visc., 205 ° C other Cp styrenes 3 7. Temperature at 10 poise visc., ⁰ C 16l Physical 2-3 8. Refractive index, 25 ° C 1. Softening point, ° C 9-10 2. Specific gravity, 25 ^° C properties 3 iodine number 4. Mixed aniline point, ⁰ C 5. Molecular weight

Products known under the names Nevex 100 and 110 (Neville Chemical Co.) are primarily aromatic hydrocarbons resins with the following typical properties:

1st softening point, ⁰ C 102-109

2. Specific gravity, 25 ° C 1.112-1.116

3. Iodine number 5 ^ -60

4. Mixed aniline point, ⁰ C 44.1-45.2

5. Molecular weight 602-699

6. Temperature at 1 poise visc., ⁰ C 184-192

7. Temperature at 10 poise visc., ⁰ C 147-154

8. Refractive index, 25 ° C 1.621-1.622

309849/0 ^ 12

The under the name Piccoumaron 41O-HL (Pennsylvania ' Industrial Chemical Corp.) well-known 'product is a hydrocarbon Material resin mixed polymer made mainly of indene and aromatic vinylene (especially styrene) in a weight ratio of 2.2-2.3 parts of indene per 1 part of aromatic Vinylene. They have a softening point of 110 - 115 C, a specific gravity of 1.10, a refractive index of 1.63 164, a theoretical mixed aniline point of 46 C, one Iodine value of 36, and a viscosity (Brookfield) of 1 poise at I95 - 200 ° C and 10 poise at I65 - 170 ° C

The product known under the name Resin EC-70 (Velsicol Chemical Corp.) is a hydrocarbon copolymer of 60 # indenes, 10 # coumarones and 30 $ styrene (estimated parts by weight), with a softening point (ring and ball) of 112-118 ⁰ C, a specific gravity of 1.08 - 1.11 (16 ° C), a theoretical mixed aniline point of 48 ° C and an iodine number of at most 80.

The product known under the name Resin XL-30 (Velsicol Chemical Corp.) is a hydrocarbon resin copolymer of indene and styrene, with a softening point (ring and Ball) from 102 - 107 ° C, a specific gravity of 1.04 1.07 (16 C), a refractive index of 1.6, a theoretical one Mixed aniline point of 40 ° C, a saponification number of 0-2 and an acid number of 0-2.

Alkylene oxide adducts

The product known under the name Brij 92 (ICI Amsrica) is a 2 mol of ethylene oxide ether of oleyl alcohol or polyoxyethylene ether, with an HLB value of 4.9, an acid number of at most 1.0, and a hydroxy number of I60 - I80. His typical viscosity is about 30 cp at 25 ° C (ASTM No. D445-53T) and its theoretical mixed aniline point is included -2.8 ° C.

309349/0412

The product known as BrIJ 72 (ICI America) Is a 2MoI ethylene oxide ether of stearyl alcohol with an HLB value of 4.9 * an acid number of at most 1.0, and a hydroxyl number of 150-170. It has a pour point (ASTM-D-97-47) of 43 C and a mixed aniline point of 23 ° C..

The product known as Brij 52 (ICI America) is a 2MoI ethylene oxide ether of cetyl alcohol with an HLB value of 5.3, an acid number of at most .1.0 and one Hydroxyl number from 160 - 180. Its pour point is around 33 ° C and its mixed aniline point is 12 ° C.

The product known under the name Volpo 3 (Croda, Inc.) is a 3MoI ethylene oxide ether of oleyl alcohol (polyoxyethylene ether) with an HLB value of 6.6, an acid number of at most 2 and a theoretical mixed aniline point of 8 ° C.

The product known under the name Provol 30 (Croda Inc.) is a 3OM0I propylene oxide ether of oleyl alcohol (polyoxyethylene ether) with a mixed aniline point of 34 ° C.

The under the name Arosurf 66-E2 (Ashland Chemical Co.) known product is a 2MoI ethylene oxide ether of isostearyl alcohol with an HLB value of 4.6-5.0, a hydroxyl number of 142-152, a melting point of about -5 C and a theoretical Mixed aniline point of -5 ° C.

The product known as Arosurf 90-E2 (Ashland Chemical Co.) is a 2 mol ethylene oxide ether of oleyl alcohol (Polyoxyethylene ether) with an HLB value of 5.1 and a theoretical mixed aniline point of -4 ° C.

The product known under the name Neodol 25-3 (Shell Chemical Co.) is a 3M0I ethylene oxide ether from C ₁₂ , C ^. ,, .C ₁ ^,

309849/0412

and C, (- linear primary alcohols, with an HLB value of 7.8, an acid number less than 0.001, a hydroxyl number of 166, a pour point of 4 ° C and a theoretical mixed aniline point of 6 ° C.

The product known under the name Emery 3926-D (Emery Industries) is a 3.5Mol ethylene oxide ether of the Stearing ⁷ acid, with an HLB value of 7 (cal.), A melting range of 31-34 ° C and a theoretical mixed aniline point of 15 C.

Various examples are provided according to the invention with the aid of the following examples coated matrices explained in more detail.

The aniline points relate to measurements of the mixture of plasticizers, without the cellulose ester, silica gel, or the pigments and solvents. The volumetric relationships are important only for the film former and the plasticizers and for them which are referred to herein as the "actives".

Example 1 -

Three coating compositions, referred to herein as A, B and C, were applied to a backing fabric of the die applied so that a total weight of the coating with A and

B of about 11.79 kg / 278 _Jl 7lm, and a total weight of the loading

stratification with C of 12.47kg-278.71m was obtained. The compositions A and B varied by the quality of the cellulose acetate butyrate and compositions A and C differed by the fact that C contained silica gel. The compositions were as follows:

3Ö9849 / CU12

example 1

A. link '16.85 C. 48 48 Alles B. 8:00 pm Volume % I27-I3O I30 Quantitative proportion,
Parts by weight material Quantitative proportion, 41.70 I6.85 128-135 116-127 19.9 CAB 500-1 16.85 21.45 19.9 CAB 500-5 8:00 pm 22.4 Coumar R-9 8:00 pm 41.70 38.I Mobilsol L 41.70 21.45 I9.6
4.0
(only connection C) ■ Brij 92
| Syloid 255 21.45 Temperature, ⁰ C Mixed aniline point
of the plasticizer 48 'Compatibility
temperature 130 Melting point of
Matri zenbe s chi ch-
tion 116-127

309849/0412

Under several test conditions, the three matrices showed thermal copying speed was generally good and the quality of copies was generally good.

Composition A had very good oil lubrication performance and good oil transfer. The oil lubrication and oil transfer composition B was good. Composition C containing silica gel had better properties than that Composition A because oil smear was excellent and oil transfer was very good. None of the matrices showed undesirable Glue and they were judged to be excellent in this respect.

Each die was very durable. The matrices made from compositions A and C showed the desired sensitivity while typing, while this sensitivity was low in the composition B die. The die with Composition C showed excellent aging properties, which were determined after 6 months of storage at 49 ° C.

The Coumar R-9 hydrocarbon resin used in the present invention In this and the following examples, a preferred resin is that of the composition and composition described Has properties. It was made by the PB sulfur method made, essentially as described in US Pat. No. 1,990,215, from crude low-solution naphtha the following typical properties (ASTM D-850): Specific gravity 16.6 / 15.6 ° C 0.965

Distillation, ⁰ C

First drop 164

172 174 178 182

I85 decomposition 194

309849 / CU12

232335?

Example 2

The following compositions A and B according to the invention and the composition C according to US Pat. No. 3,704,155 were compared ^{after application to a matrix fabric in total layer weights of about 12.25-12.70 kg / 278.71m 2:}

A. link 00 18.00 C '. · B. 20th material
I. 20th 46.30 18.00 CAB 500-1 Volume fraction, volume # 60 14.50 Coumar R-IO 18th 21.20 41.30 Mobilsol L 21 - Brij 92 38. 21.20 Staybelite Ester 5 22nd I9.50 Hercolube A. C. 48 Mixed aniline point
öes plasticizer
measure before s 45 Temperature ° 48

309849/0412

The main difference between composition B and composition C was that in B instead of the Plasticizer Hercolube A the plasticizer Brij 92 was used. The durability of the die was matched with the composition B increased by about $ 50. The other working characteristics the matrices from Compositions B and C were essentially the same.

The composition A differed from the composition B in particular in that instead of the Name Staybelite Ester No. 5 known plasticizer in composition B, the preferred according to the invention Hydrocarbon resin plasticizer known as R-IO was used in Composition A. the Negative copy speed increased from generally reasonable for Composition B to good and very good good with the die coated with composition A. The quality of the copies was good in both cases.

For compositions B and C, oil smear was good and the oil transfer adequate, oil lubrication as well as oil transfer were awarded the composition A. The undesirable sticking or the slipperiness was excellent in all cases. The durability was high for compositions A and B, lower for C. The typing sensitivity was similar and removable for all compositions.

Example 3

The following coating composition was applied to a Matrix pad applied from the fabric, a total layer weight of about 13 * 61 kg / 278.71 m was obtained.

309849/0412

Substance volume %

CAB 500-1 16.0

Coumar R-9 '4.0

Mobilsol L 38.9

Brij 92 37.8

Titanium dioxide abrasion
(70 weight- ^ in
Castor oil) 2.5

Chrome yellow abrasion

(65 weight- ^ in

Castor oil) 0.8

Syloid 255 1.36 kg / 45.36 kg the

remaining substances

The titanium dioxide and chrome gel pigments were used to contrast the image. This is with the mechanical Display and peel off important.

The thermal copying speed was adequate and the quality of the copies was good. The oil smear showed up as very good and the oil transfer as excellent. The undesirable Adhesion or slidability was excellent. the Typing sensitivity was relatively high. The durability of the die was mediocre.

Example 4

The following coating compositions applied on a matrix fabric to achieve a total layer weight of 12.02 -

Obtaining 12.93 kg-278.7 lm provided improved according to the invention Matrices.

309849/0412

material A. B. link D. 18.00 18th E. 16. P. 85 G 00 Half seconds
Butyrate or
Tenths of a second
Butyrate Proportions. , Volume-2 CAB 38I-2 18.00 C. 20th 20th CAB 45I-I 18th .00 8:00 pm 00 CBV 00 CAB 5OO-I 00 43 « 00 " 30th Coumar R-9 47. 16. 18th Coumar RH-I7 8:00 pm 20th 00 30.20 14th 00 19th 15th 70 Neville LX I517 Resin XL-30 3I.8O ° c 48 20th 48 Mobilsol L temperature 20th Benol 18.30 18th 20th 20th 35. 43. Brij 92 38 80 f Mi s ch-aniline point
of the plasticizer
mixed 43.7O 43. 80 28. 18th 27 27 74 38 85 00 75 40

309349/0412

" ³⁸ " 232335?

The solvent for the coating composition existed from 80 # toluene, 20 $ ethanol (95 #) (^ by weight).

Except for Composition C, the matrices had very high durability and low sensitivity. They did for writing on with the typewriter as well as for thermographic copying.

Example 5

The following coating compositions failed the application on a matrix fabric a total layer

weight from 12.02 - 12.93 kg / 278.71m. The ones made with it Matrices had improved properties and were suitable for both thermographic and for writing with the Typewriter.

309849/0412

link A. B. C. D. E. 16.85 31 I6.85 F. G material Volume fraction, volume # CAB 500-1 16.85 18.00 15.70 18.00 18.00 Coumar LX-509
Nevex 100 8:00 pm 8:00 pm 8:00 pm Piccoumaron 410-HL 8:00 pm 8:00 pm Coumar R-19 Coumar R-21 Coumar R-27 2I.7O 20.40 8:00 pm Coumar P-IO 41.45 42.75 8:00 pm Mobilsol L 37.60 43.40 42.30 temperature 34.70 25.6O Brij 92 19.70 18.60 22.00 48 31 27.30 36.40 Mixed aniline point
of the plasticizer
mix 48 48 37 31 Compatibility
temperature 127

309849/0412

- 4ο -

232335?

Example 6

The following coating compositions gave after Apply a total layer weight to the matrix fabric

11.79 to 12.70 kg / 278,7Im ^second Improved matrices were obtained.

material A. 70 B. link 85 16.85 48 D. E. , Volume % C. 48 I6.85 i 15.45 CAB 500-1 00 00 8:00 pm I6.85 8:00 pm Coumar R-9. 15- 30th C. 20th 38.20 25.OO 47-20 53- Mobilsol L 20th 00 Proportion 29.OO Conoco DBCL 34. 16. 95 Texanol
Isobutyrate 30th 20th 24.35 Plexol soft
maker PEP 38. Bis-alpha-methyl
benzyl ether 29.15 Atmul 122 24. temperature 4c " Mixed aniline point
of the plasticizer
misehes "48

309849/041 2

232335?

Example 7

The following coating compositions resulted in applied to a matrix fabric with a total layer weight of 11.79-12.93 kg / 278.71 m improved according to the invention Matrices.

A. B. ( 16 48 46 85 ■ E. 85 material link 20th 00 Volume # 00 CAB 5OO-I 15.70 25th 16. Coumar R-9 10.00 20th 20th Mobilsol L 49.OO 36. D. 56. 60 Conoco
Paraffins Quantitative proportion, 6th 55 15th Terpex resin
oil 15th Temperature, ° C. Brij 92
* Polyoxyethy-
len polyol
Fatty acid est 25.30 18th 20th 48 63. Mixed aniline
point of
Plasticizers
mixed 48 38. 40 Compatible
tempera
door 93 26th .00 .70 00 00 30th 30th 70 00

309849/0412

232335?

* Polyoxyethylene (40) sorbitol heptaoleate with an HLB value of 9, an acid number of 8-12, a hydroxyl number of 22-38, a saponification number of 100-110, a typical viscosity of 175 cp at 25 ° C and a mixed aniline point from 37 ° C.

Example 8

The following coating compositions, applied to a Matrizenunter.rlage in a total layer weight of about 12.25-12.70 kg / 278.71 m, resulted in improved inventions Matrices.

link A. B. C. D. E. Quantity share, volume % I6.85
8:00 pm
21.40
41.75 16.85
8:00 pm
38.IO
25.O5 15.70
8:00 pm
39.60
24.70 I5.7O
8:00 pm
4O.5O
23.8O I5.7O
8:00 pm
42.70
21.60 Temperature, ⁰ C 48 48 48 46 48 material CAB 5OO-1
Coumar R-9
Mobilsol L
Provol 30
Volpo 3
Neodol 25-3
Arosurf 66-E2
Arosurf 90-E2 Mixed aniline point
of the plasticizer
mix

309849/0412

Claims (15)

Claims 1. Die with a color permeable coating of a hot-flow composition of a thermoplastic film former, consisting of an organic cellulose ester and plasticizers, some of which are incomplete with the film former is tolerable, characterized in that the plasticizer 5 - 60 VoliB · ^, based on the total volume of the film former and plasticizer, a thermoplastic polymeric hydrocarbon resin containing a total of polymerized Indenes and coumarones of at least 30% by weight having. 2. Die according to claim 1, characterized in that the monomer content of the resin is essentially based on indenes, coumarones, Styrenes and aliphatic, unsaturated monomers are restricted and the resin has a total content of polymerized indenes and coumarones of at least 40% by weight and the Total content of polymerized indenes, coumarones and styrenes is at least 80% by weight. 3 · die according to claim 1 or 2, characterized in that the softening point of the resin is in the range of 5-175 ° C. 4. Die according to claim 1, characterized in that the resin is a coal tar-coumarone-indene resin and has a total content of polymerized indenes and coumarones of at least 80% by weight and the remainder essentially of polymerized Styrenes. 5. Die according to claim 4, characterized in that the er- 3098 43/0412 ■ - 44 - The softening point of the resin is in the range of 90-175 ° C. 6. Die according to one of claims 1 to 5> characterized in that the plasticizer also contains a mineral oil. 7. Die according to claim 6, characterized in that the proportions are 5-45 volume # cellulose ester, Z> - 60 volume # polymeric hydrocarbon resin and 10-70 volume # mineral oil, based on the total volume of the film former and the plasticizer . 8. A die according to one or more of claims 1 to 7 » characterized in that the cellulose ester is a cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate valerate, cellulose propionate butyrate, cellulose propionate valerate, cellulose butyrate valerate, cellulose butyrate or cellulose propionate. 9. Die according to claim 8, characterized in that the Cellulose ester consists of, a butyrate or valerate, with total
a minimum content of 35% by weight ^ butyryl and valeryl and a total hydroxyl content of no more than 4.7% by weight. 10. A die according to claim 9, characterized in that it contains 14 - ~ $ 0% cellulose acetate butyrate with a butyryl content of at least about 44 weight -; * »and · a hydroxyl content of at most about 2 weight- ^, 10-30 # of a thermoplastic coal tar coumarone-indene resin with a total content of polymerized indenes and coumarones of at least about 80 weight- ^ the remainder consists essentially of polymerized styrenes and whose softening point is in the range of about 90 - 175 ° C and contains 15 - 65% mineral oil. 11. Die according to one or more of claims 1 to 10, characterized characterized in that the plasticizer is also an alkylene 309849/0412 copy oxide ester or ether of a long chain fatty acid or one contains long-chain fatty alcohols that contain esters or ethers HLB white in the range from 1.5 - 8 and in a proportion of 5-65 volume, based on the total volume of the Film former and the plasticizer is present. 12. Die according to claim 11, characterized in that the Alkylene oxide is ethylene oxide or propylene oxide. 13. Die according to claim 12, characterized in that the Plasticizer contains a 1 to 3.5 mol ethylene oxide ether of a fatty alcohol having 12 to 20 carbon atoms. 14. Die according to Anapruah 12, characterized in that the Plasticizer a 3OM0I propylene oxide ether of a 12-20 carbon contains fatty alcohol containing atoms. 15. Use of the die according to one or more of the preceding claims for the production of an inscribed die by heating the image or print areas ¹¹ by means of infrared radiation absorption. 301841/0411