DE2039931A1 - Leuco printing ink containing chlorinated n-paraffins for matrix or stencil printing processes - Google Patents

Description

t RESPIRATORS

DR. E. WIEGAND DIPL-ING. W. NIEMANN 2039931

DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MDNCHEN HAMBURG

TELEPHONE = 555476 8000 MONCH EN 15, 1 1, All!?, 1970

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 400 10/70 - Ko / B

Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa / Japan

Leukodruok paint, which contains chlorinated η-paraffins, for die or template druok processes

The invention relates to a Leukodruok color for Stencil or matrix printing processes that use a Chlorinated η-paraffin as a solvent for a colorless one Contains dye precursors.

So far, known solvents in matrix or stencil or screen printing inks that have a color Contain loose dye precursors, for example chlorinated diphenyl, Rioinus oil, linseed oil, phthalic acid esters and the like ·, used »Ss is also known that the most effective solvent consists of chlorinated diphenyl.

This chlorinated diphenyl is used as a solvent for printing inks that are used in amateur printing processes, for example screen printing processes, because it penetrates the stencil or matrix sheet for the typewriter and also an intrusive Has odor and toxic properties * unfavorable.

In the context of the invention it has now been found, as a result of numerous experiments, that chlorinated n-paraffin very effective as a solvent as a carrier for one

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Are printing inks that contain · colorless · dye precursors.

In general, the Farbstoffrorläufer is colorless and forms a · color upon contact with an electron accepting material, so that the dye precursor-containing ink is colorless dyed or at most low * Therefore, "klargedruokte ψ images when a übliohes paper is printed with the ink not received However, when printing is carried out on paper coated or impregnated with an electron-accepting material, which is hereinafter referred to as

clay-coated paper is used (clear color images formed on it.

The leukodruok dye according to the invention contains η-paraffin in chlorinated, which is dissolved a colorless dye runner and an aid for giving a good print ability, for example a wax, fat or oil or a synthetic high molecular compound. The dye * τοrlaufer dissolved in these solvents gives a deep color in contact with one clay coated paper, however, gives one dispersed therein Dye freeze run no deep color, even in Touching a clay-coated paper. Therefore see the matrix or template print color, contains the dye precursor as a coloring component, against the commonly known print colors like pigment suspension type for stencil or matrix print With regard to the α · point sees that the dye is a goal runner must be dissolved in the carrier.

As examples of dye freezes in the context of Invention are leuco derivatives τοη dyes, such as leuco

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203SG31

crystal violet or Ieukomethylene blue, lactone derivatives ▼ on dyes such as crystal violet laoton, laotam derivatives of dyes such as rhodamin-3-lactam, and spiro compounds such as 3-methyl «2.2 ^l -epirobi (benzo / f / -chromene) listed ·

Preferred examples of solvents for these dye precursors include chlorinated n-paraffins, the more than 0.5 wt. $ 5, based on the solvent, des dye vorlaufera dissolve and a rough color formation speed develop on the clay-coated paper.

The balanced η-paraffins are generally colorless or yellowish and are known to be non-toxic. The solubility of the Farbefcoffvorlaufer in the chlorinated n-jrur & ffinen becomes high with an increase in the chlorination AuemaBses (wt _# -; 6 chlorine). Thus, for example, a chlorinated tea η-paraffin, since a n-.pa raffinate consists of 12 to 14 carbon atoms with a chlorination of 50%, can contain more than 6% by weight of the dye precursor, for example J- Hethyl-Z.i'-spiroibenzo / f. ^ Chromene ^ dissolve at ordinary temperature, Jadooh an identical paraffin which is eu 20% chlorinated can only dissolve 1.5% by weight of this dye precursor. Furthermore, chlorinated η-paraffins with more than 20, for example 20 or 24 carbon atoms, are of high viscosity and are at one; Chlorination degree of about 50 # very viscous oils and continue to solidify at a chlorination degree of over 70 *.

Chlorinated n-paraffins with a degree of chlorination from 30 to 60 pounds, however, have a high salinity for the dye precursors and are opposite to chlorinated

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Diphenyl in relation to the color formation process overlay on construction paper

On the other hand, chlorinated isoparaffins, which are obtained by chlorinating isoparaffins, are considerably yellowish oils not only with an obtrusive odor, but also have the disadvantages of a slight elimination of chlorine and a slight coloration of the dye precursor in the case of heating to 50 to 130T if the Dye precursor is to be dissolved therein.

That is why the use of chlorinated isoparaffins unfavorable as the main solvent in Leukodruok colors.

The typiecharweiae Preferred solvents for the Leukodruakfarben consisting of chlorinated n-Paraffintn with a viscosity of 0.2 to 25 poises at 25 ⁰ C with a Ghlorierungagrad of more than $ 30 to $ 60 less ale. If the viscosity is below 0.2 poise, solid-liquid separation is obtained in the production of leukodrux paints, so that the separation of the oil is no longer possible, and materials above 25 foises have too high a viscosity to produce good prints to achieve on the output sheets.

Furthermore, binds in chlorinated η-paraffins with a degree of chlorination below 30'X the dye precursor difficult to dissolve, and those with chlorination levels greater than $ 60 have high viscosity and result in an elimination of hydrogen chloride.

The chlorinated η-paraffins can usually in a portion of around 30 öew .- $, based on Leukodruek color be used. Particularly excellent

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drew print images with few spots in the screen print obtained on the phone paper when a leuco printing ink with a chlorinated η-paraffin with a viscosity Tone 1 poiee to 13 poises is used «

Furthermore, the Leukodruok colors show with the Chlorinated η-paraffin as a solvent for the pigment base an extremely low level of leverage on the die-printed sheets, which is caused by the ibislioh the resin sohioht on a stencil paper for Typewriter, as it is often used for stencil duplication printing, in comparison to the well-known Leukodruok inks, the chlorinated Contain diphenyl; For example, fog will form on the entire surface of the printed sheet from 400 "to 600, printed sheet in the former case and in the latter Case received from 100th to 150th sheet printed. Therefore, there is an extremely remarkable difference in the number of stencil paper to printing sheets * As mentioned above, the chlorinated η-paraffins show various superiorities as a solvent for dye precursors as described in Leukodruok colors are used, not only against ohlorinated isoparaffins, but also against ohlorier « tem diphenyl, which is an excellent solvent for the previously known Leukodruok colors, with regard to the lower fog formation caused by matrix paper caused by typewriters, lower ßeruoh, low toxicity and costs *

A typical example of the production of the Leukodruok color is given below.

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The following stages were used in combination: (1) a dye precursor old chlorinated paraffin as a solvent, (2) incorporation of auxiliaries such as waxes, fats or oils, natural high molecular compounds, thermoplastic synthetic polymers and the like, for the purpose of improving the printability as a printing ink and controlling the flowability and thixotropic properties, - ^ (3) heating the emisohes to dissolve the dye precursor in the solvent and at the same time to dissolve or melt the auxiliaries to form a uniform Solution, cooling with stirring to precipitate a part of the total amount of the auxiliaries in fine parts in the solution of the dye precursor in the chlorinated η-paraffin, in which case more than 1 # of at least one of the auxiliaries, which is one or in combination of two or more can be used without being dissolved in the chlorinated η-paraffin Bt and duroh Precipitation on cooling in fine Te 11 before nfor »is kept so that the chlorinated paraffin is held in nets or grids of the aid, and Wk (4)» if necessary, addition of finely divided cellulose powder, powdered gum arabic or curious fibers , for example made of acetate, polyamide or polyester for this purpose.

In practicing the process, it is possible to use two or more kinds of chlorinated n-paraffins with different viscosities and degrees of chlorination are used as the main solvent and also 1 to 20 £ of auxiliary solvents.

Particularly superior solvents for the Leukodruok colors According to the invention, a Qemisoh can be

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80 to 90 parts of chlorinated η-paraffin with a Degree of chlorination τοπ 50 pounds and 12 to 14 carbon atoms and 20 to 10 parts of a chlorinated n-paraffin with a degree of chlorination τοη 30 to 35 # and 12 to H. Carbon atoms.

All auxiliary solvents can within the scope of the invention for example liquid paraffin, silicone oil, alkylbenzenes and the like can be used. Auoh can less than $ 5 of chlorinated isoparaffin mixed in will"

The Leukodruok colors according to the invention become general Terpackt in a tube or can be used as printing ink for releasing small amounts • A rotary copier or duplicator is used are, however, taken into account in the form of τοη leukodruok color arcs used without leaving stains on the hand or towels at the pressure stage.

The Leukodruok color sheet is made by applying the Leukodruekcolorbt on a carrier, the opposite of the Leuko druok color is resistant, in a frame-shaped state obtain. Examples of carriers include cellophane, with Polymer films, bonded papers, synthetic polymer sheets and covered with different types of τοη polymers or coated polymers.

From Ieukodruokfarbenbttgen, who ait this printing ink coated in a thickness τοη 200 a on a carrier 200 to 300 printing sheets were obtained. In the Stage of matrix printing using the Leukodruok arches one is opened by means of optional, electrical, thermal or mechanical working methods Hatrice on the ink-coated surface of the

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Leukodruok color bow and, so that the clay-coated Paper in contact with the matric surface comes, by means of a roller for the transfer of the Leukodruok color ron the openings of the matrix on the clay-coated paper and for the formation of color images accordingly the openings of the die on the clay-covered Pressing paper and mass production of printing material becomes through the repetition of these operations a carried out easily and with great success

The following specific examples serve to further illustrate the invention without limiting it.

example 1

A Gemisoh of 95 g of chlorinated n-paraffin (chlorination degree 43 #, viscosity 2 poises at 25 ⁰ C) and 2.0 g Kristallviolettlaeton were heated at a temperature below 65 ⁰ C for dissolution. NaOH addition of clay 18 g of microcrystalline wax having a Sehmelzpunkt τοη 70 to 72 ⁰ C the resulting mixture was then heated to 75 ⁰ C, so that a uniform solution was obtained · This solution was cooled to room temperature with stirring, while still sohwaohgrünlioÄe pasty Leukodruokfarbe wherein precipitated microcrystalline wax was contained. When the Leukodruok paint was replicated on a construction paper through the stencil paper openings, clear blue images were obtained on the printing sheets. With this Leukodruok color it was possible to get more than all 500 sheets of print material without damaging the stencil paper? furthermore the material was deodorant.

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Example 2

A mixture of 95 g of chlorinated n-baraffin (degree of chlorination 50 to 52 #, viscosity 12 poise at 25 ⁰ G), 5 g of rhine oil and 1.5 g of rhodamine B-Iaetone was heated to dissolve. This is because 12 g of Speroaeetieum, 2 g of paraffin wax with a breaking point of 68% and 5.0 g of a low molecular weight polystyrene (designation Piccalaatic 0-100 from Ebso Standard Corp.) were added to this to form a uniform solution and then cooled to room temperature while charging , whereby a pale brown pmsten-like leuco printing ink was obtained, which contained precipitated very small particles of spermaceti and paraffin wax.

The Leukodruok paint was then applied to a heat sealable Cellophane applied «so there is a room in circumference a strength of 200 / u but division of the Leukodruok color sheet What was obtained was «Sin thermal drawing paper with openings (payment Riaοfax der Eiso Kagaku K.K.) was then gueammen with the Haykodruok bows and clay ~ Practical paper attached and lur transfer of the leukodruok color onto the tonUbenogent paper through the openings de «Matrlsenpapierea giprefit, and red The printed image was retained on the paper soaked in the phone. This operation was repeated, with a total of 900 sheets get the same print greaterials,

Supplement 3

Su a Qmiaah ron 90 g ·· a chlorinated n-paraffins (C5hlorierun "fgrad 5OJi, Viskoeltät 6 POLST at 25 ⁰ C) · ohlorierten η-paraffins old one" Chlorierungegrad of

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50 i (viscosity 0.2 poise at 25 ⁰ C) and 2.0 g of 3-methyl-2 _t 2 * spirobi (Benio / ~ f / ear ones), 12.0 g bleached bees guard (Seseiohnung Lunanelt HS-200 of the Dai Nippon Ink ft Chesiioale Inc.) sugigt.

The resulting mixture was was then heated to 110 ⁰ C but resolution heated and cooled to room temperature under stirring, thereby obtaining a lightly greenish paste-like leukodruckfarbe.

When the leuco printing ink through a wax matrix paper was applied with openings to a clay-coated paper, deep green reproductions were made on the clay-coated paper Papers formed.

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Claims (6)

Claims 1. Leuco printing ink for stencil or matrix printing processes, marked by the content of a chlorinated η-paraffin with a degree of chlorination tone 30 to 605 * and a viscosity τοη 0.2 to 25 poise at 25 ⁰ C, at least one colorless dye precursor, the βατ Formation of a distinctive color in Uoasetaung with an electron-accepting material is capable and is dissolved in the chlorinated n-baraffin, and feiten particles of at least one of the materials wax, pett or oil or synthetic high molecular compounds, with the chlorinated n-paraffin in the netaen or grids of these fine particles is held * 2. Leukodruek color according to claim 1, characterized in that that the fine particles consist of microcrystalline wax, whale wax, paraffin wax or beeswax. 3 * Leukodruok color according to claim 1, daduroh marked, that the fine particles of cellulose powder, Rubber larabi powder, acetate, polyamide or polyester exist. 4. leuco printing ink according to claim 1 to 3 »characterized in that the chlorinated n-baraffin 8 to 26 contains carbon atoms 5 · Seukodruok color according to claims 1 to 4, characterized marked, because the chlorinated η-paraffin bit is a the auxiliary liquid paraffins, siliconulene and / or Alkylbensoltn renn laughs. 6. Leukodruckfarbe NaOH claims 1 to 5 »gekennteiohnet daduroh that the colorless FärbstoffrorlHufer from Leuk (methyl blue, IristallTioltttIacton, rhodamine-B-Laotaa and / or 3-methyl-2 _t 2 ^f -> splro (BENEO / f / chroaen) beeteht « 109810/2139 BAD LOCATION