DE2151034B2 - USE OF LEUCAURAMINE COMPOUNDS FOR HECTOGRAPHIC COLOR SHEETS - Google Patents

Description

Hectographic color sheets for the spirit transfer printing process, which :; clean handling allow, consist of a fabric or other suitable film or sheet material on which there is a coating that is a colorless derivative of a basic dye, such as. B. Crystal Violet Lactone, contains. During the production of the stencil, this ink sheet is applied with its coated surface against the Surface of a stencil sheet placed, on which the other side is described. This creates a practically colorless inverted image on the first-mentioned surface of the stencil sheet at those Points where the color sheet and metric sheet are pressed together. The die; is then with multiple copy .-- scroll brought into contact with the with a solvent, such as. B. Ethanol, which one

to use, wherein each symbol R, R ', R "and R'" is independently hydrogen or an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical or forms part of an optionally substituted hydrocarbon chain which together with the adjacent nitrogen atom creates a heterocyclic ring; X represents hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical or an alkyl chain with 2 or 3 carbon atoms which is bonded directly to a carbon atom in the 2- or 6-position of the ring C; each symbol Ri, R ₂ and R ₃ independently represents an optionally substituted alkyl, cycloylkyl or aralkyl radical or forms part of an optionally substituted hydrocarbon chain which, together with the adjacent nitrogen atom, forms a heterocyclic ring; the rings A, B and C can optionally be further substituted; and Z- stands for an anion, for the production of hectographic color sheets.

Examples of optionally substituted alkyl radicals, which are represented by R, R ', R ", R'", X, R, Ri, R ₂ and R ₃ are: optionally substituted lower alkyl radicals, such as. B. ethyl, propyl, butyl, j3-hydroxylethyl, 0-chloroethyl and especially methyl.

Examples of optionally substituted cycloalkyl radicals represented by R, R ', R ", R'", X, R, R ₁ , R ₂ and R) are: 2-methylcyclohexyl, 4-methylcyclohexyl, cyclopentyl and especially cyclohexyl .

Examples of optionally substituted aralkyl radicals which are represented by R, R ', R ", R'" X, R ₁ , R 2 and Rj are: 4-methoxybenzyl, 2-methylbenzyl and, in particular, benzyl.

Examples of optionally substituted aryl radicals, which are represented by R, R ', R ", R'" and X are: 2-methylphenyl, 4-methylphenyl, 3-chlorophenyl, Naphth-2-yl and especially phenyl.

When R and R 'form part of an optionally substituted hydrocarbon chain, they together creates a heterocyclic ring with the neighboring nitrogen atom, then R and R '

be connected to one another, or at least one of the groups R and R 'can be connected to the ring A. be. The substituents R "and R '" can be parts of heterocyclic rings in the same way form. When R and R 'or R "and R'" are linked together, then are examples of heterocyclic ones Rings: 5- or 6-membered rings, such as B. piperidine, N-methylpiperazine and morpholine rings. When R and / or R 'are bonded to the aromatic ring A, then examples of heterocyclic rings are: Juiolidin-8-yl-, N-methyltetrahydroquinolin-6-yl and 1,2-dimethylindolin-5-yl rings.

X is preferably a hydrogen atom.

If one of the groups R ₁ , R ₂ and R ₃ forms part of an optionally substituted hydrocarbon chain which, together with the adjacent nitrogen atom, forms a heterocyclic ring, then at least two of the groups Ri, Ri and R ₃ can be bonded to one another or fused to one another, so that a heterocyclic ring or heterocyclic rings are formed with the nitrogen atom, the nitrogen atom being bonded to carbon atoms present in said heterocyclic ring or in said heterocyclic rings either by single bonds or by a single bond and a double bond, or it can be one or two of the substituents Ri, R2 and R _{3 may be} bonded to the ring C.

As examples of heterocyclic rings which are formed by combining at least two of the groups R ₁ , R2 and R ₃ and the nitrogen atom, so that the nitrogen atom is bonded to carbon atoms of the heterocyclic rings through single bonds, the following should be mentioned: pyrrolidine, pyrroline , Piperidine, morpholine, piperazine and pyrrole rings, as well as rings in which R ₁ , R2 and R ₃ are connected to one another so that they form a polycyclic ^ heterocyclic ring structure with the nitrogen atom in which the nitrogen atom has at least two rings which are present in the heterocyclic ring structure. Examples of such polycyclic heterocyclic ring structures are: pyrrolizidine, 1-azabicyclo- (2: 2: 2) -heptane, quinuclidine, l-azabicyclo- (3: 2: 1) -octane, l-azabicyclo- (3: 2: 2) -nonane, 1-isogranatanine, conidine, l, 5-diazabicyclo- (3: 3: l) -nonane, 3,7-diazabicyclo- (3: 3: l) -nonane, julolidine, hexahydrojulolidine, LiIoIidin and the 1,4-Diazabicydo (2: 2: 2) octane ring structure.

As examples of heterocyclic rings formed by combining or condensing at least two of the substituents R ₁ , R ₂ and R ₃ so that the nitrogen atom is bonded to carbon atoms of the heterocyclic rings through a single compound and a double bond, there should be mentioned: unsaturated 6-membered heterocyclic rings which can contain substituents or which can form part of a condensed ring system. Examples of such heterocyclic rings are: isoquiniline and preferably pyridine rings, which can be substituted, for example by alkyl radicals, in particular the methyl radical, or halogen atoms.

Any substituents that may be present on rings A, B and C are: alkyl, Alkoxy and halogen substituents.

Examples of anions represented by Z are: chloride, bromide, iodide and methosulfate ions.

Under the general class of compounds of formula I, the leucauramine compounds are intended to be formula

R '"Z

may be mentioned in which each of the symbols R, R ', R "and R'", which can be the same or different, stands for an alkyl radical, R _{1 stands} for an alkyl, cycloalkyl or aralkyl radical, R2 and R3, which are the same or can be different, represent alkyl radicals, X represents a hydrogen atom or an alkyl, aryl or aralkyl radical, the rings A and B can optionally be substituted by alkyl radicals, the ring C can optionally be substituted and Z ~ represents an anion .

The leucauramine compound of formula I can be prepared by making a compound the general formula

R '
/ (H) CH-
I. YQ \
R '

wherein R, R ', R ", R'" and the rings A and B have the meanings already given, Y for sulfur or is preferably oxygen and Q is alkyl or, preferably, hydrogen, with an amine formula

NHX

(111)

wherein X and the ring C have the meaning given above and D is a quaternary group the formula

/ ■

-NR ₂ Z "

is in which R ₁ , R2, R ₃ and Z- have the meaning given above or in which D is a group which can be converted into the stated quaternary group by known methods, reacts, and optionally carries out the conversion into the stated quaternary group .

Examples of groups which are represented by D and which can be converted into quaternary ammonium groups are: tert-amino groups of the formula --NRiR ₂ , which can be qualified by reaction with compounds of the formula R _{3 Z in the usual way.}

Examples of compounds of the formula II are:

Michlers-Hydrol, bis- (4-diethylaminophenyl) -methanol, Bis- (2-methoxy-4-dimethylaminophenyl) -methanol, bis- (4-piperidinophenyl) -methanol, Bis- (2-methyl-4-dimethylaminophenyl) -methanol and bis- (M-methyl-6-tetrahydroquinolinyl) -methanol, Bis (4-dimethylaminophenyl) methyl mercaptan and the alkyl ethers thereof.

The process for the preparation of the leucauramine compounds is conveniently carried out in a solvent such as, for. B. water, alcohols or toluene, using reaction ^{temperatures of 20 to 150 0} C, preferably 60 to 100 ° C, performed. In the case where D is a quaternary ammonium group, the solvent is preferably a mixture of water and a water-miscible organic solvent such as. B. Ethanol.

Leucauramine compounds of Formula 1 can also be prepared by adding a compound the formula

R '

R "

/ aVc

(IV)

R '"

wherein R, R ', R ", R'", Y and the rings A and B have the meanings given above, including neutral ones or reduced alkaline conditions in the presence of an amine of the formula III.

Suitable compounds of the formula IV are Michler's ketone and derivatives thereof.

Leucauramine compounds of the formula I in which X is hydrogen can also be prepared thereby that one is an auramine derivative of the formula

R '"

wherein R, R ', R ", R'", D and the rings A, B and C have the meanings given above, including neutral ones or alkaline conditions.

Useful reducing agents are sodium in ethanol, sodium borohydride or hydrogen gas in combination with palladium or platinum catalysts.

In the production of hectographic color sheets, a coating that contains the leucauramine compound is used contains, on a suitable carrier material, such as. B. a polyester film applied. The topping can also contain the following: a wax, such as. B. Carnauba wax, Ouricuri wax, sugar cane wax, Beeswax, Chinese insect wax and candelil-Ia wax, ozokerite wax and raw montan wax, and mixtures of the above waxes, petroleum jelly, such as. B. Vaseline, polymeric materials such. B. Copolymers of polyvinyl acetate and polyvinyl chloride, polystyrene, ethyl cellulose and cellulose acetate, mineral oils, Lanolin, tallow and animal and vegetable oils, neat fat and blown castor oil.

The amount of the leucauramine compound present in the coating can be 15 to 5% and preferably 35 to 55%, based on the total covering weight.

The covering can be produced in an expedient manner by conventional methods, such as ι. B. Working through the ingredients at a suitable temperature in a mill or other mixing device, such as e.g. B. in a Dreiwalzmühlc, a heated ball mill or an attritor mill.

The covering can then be applied to the carrier material, such as. Onto a fabric, film or other sheet material, using any suitable device, such as a roller, doctor blade or the like, to obtain a covering weight between 10 and 15 g / m ² and preferably between 15 and 25 g / m ² to create. If the base material consists of paper, it should be provided with a suitable barrier coating before the coating containing the leucauramine derivative is applied. A suitable barrier layer consists of ethyl cellulose or a mixed polymer of polyvinyl chloride and polyvinyl acetate. A barrier pavement weight of approximately 6 g / m ² is suitable.

The die obtained in this way is substantial colorless. Adding a small amount of titanium dioxide can improve their appearance.

When the coated surface of the die comes into contact with a surface of a die sheet is brought and when the other surface of the stencil sheet is written on, then an im produces a substantially colorless inverted image on the first-mentioned surface of the stencil sheet, which surface then successively with several copy sheets, which with a copying liquid are moistened, can be brought into contact in the presence of an acidic substance, so that a visible Reproduction of the original writing on the stencil is produced on the copy sheets. It can any conventional transfer printing machine can be used.

A suitable copying liquid for the matrices according to the invention consists of methylated fuel, the 0 to 70% by weight, preferably 10 to 40% by weight, of water contains. It is desirable that a higher boiling polar solvent such as. B. benzyl alcohol, too is present, otherwise the first copies will only show a faint image.

The acidic substance can be present in the copying liquid or on the copying sheets. So can the Copying liquid an organic acid, such as. B. tannic acid, tartaric acid, salicylic acid, anthranilic acid or benzoic acid, or an inorganic acid, such as. B. hydrochloric acid. To prevent corrosion in the To reduce the transfer printing machine, it is preferred that the acidic substance be present on the copy sheets. If the acidic substance is present on the copy sheets, then it can be something called an acidic mineral be, such as B. attapulgite, kaolin, pyrophyllite, talc, bentonite, halloysite, calcium sulfate, calcium citrate, magnesium trisilicate, Calcium phosphate or barium sulfate. In this case, the copy sheets can also have one Have acid-treated coating, such as him, for example is obtained with topping composition, the acids such as tannic acid, oleic acid, gallic acid, lauric - "= Ä.ure, Phosphotungstic acid and phosphomolybdic acid, possibly in conjunction with precipitated Contains calcium carbonate or blanc-fix.

50 to 100 copies can be obtained from a single stencil.

The invention is illustrated by the following examples, all parts and percentages

Weight are expressed. Parts by volume refer to the ratio of milliliters to grams.

Example i

106 parts of Michlers-Hydrol and 53.5 parts of trimethyl- (m-aminophenyl / ammonium bromide hydrochloride are dissolved in 500 parts of 96% aqueous ethanol, and 27.6 parts of potassium carbonate are added. The mixture is heated to the boiling point for 4 hours and then cooled and filtered. 1,500 parts water and 900 parts of ether are added to the filtrate, and the resulting aqueous layer was separated from the ether and evaporated to half its volume under reduced pressure and cooled. the Leucauraminverbindung in which R, R ^1, R ^2, and R ^{3 are} methyl groups, X is hydrogen and A is bromide anion, is precipitated and obtained by filtration as a gray solid melting at 146 ° C.

Michler's thiohydrol behaves similarly to Michler's hydrol under the above reaction conditions.

100 parts of m- [bis- (dimethylaminophenyl) -methyl] -aminophenyl-trimethylammonium bromide, which has been prepared as above, are mixed with a mixture of 30 parts of fatty, gray carnauba wax and 70 parts of medium viscosity mineral oil. The mixture is then passed through a heated three roll mill until the dispersion gives a value of 6 on a Hegman scale. The dispersion is then applied to a polyester film so that a covering weight of 18.0 g / m ² results. The flow behavior of the covering is good.

The covering is completely hardened after 3 days. The stencil sheet is used to make an inverted Create image on a copy sheet. Clear writing will be obtained. The topping is at the points completely transferred to the die sheet that the types hit.

The die obtained is used in a transfer printing machine to make copies with copy sheets, that with a mixture of 86 parts of 94% ethanol, 10 parts of benzyl alcohol and 4 parts Tannic acid are impregnated. Greenish-blue copies are obtained from the first copy. The color is ι (i fully developed after about 10 min.

Example 2

32 parts of bis (4-diethylaminophenyl) methanol, 26.8 parts of trimethyl (m-aminophenyl) ammonium bromide

Ii hydrochloride and 13.8 parts of potassium carbonate are in Suspended 150 parts of acetone and heated to reflux for 4 hours and then cooled. The departed gray Solid is filtered off and dried, 40 parts of bis (4-diethylaminophenyl) methane - «- trimethyl- (m-

2 (i aminophenyl) ammonium bromide can be obtained.

An ethanol solution of this leucauramine results in contact with one impregnated with benzoic acid Paper an intense blue color. The compound can be used to produce a hectographic ink sheet

2), which is suitable for use in a transfer printing process as in Example 1 is suitable.

The following table gives further examples of leucauramine compounds of the formula I which according to the procedure of Example 1

so can. When they are applied to a polyester film as described in Example 1, hectographic color sheets are obtained which can be used as in Example 1 for the production of copies .

Ex. R&R " R '& R "' A. B. X R2 & R3 Ri I. Substitucnl on ring C 3 ethyl ethyl Phenyl Phenyl H methyl ethyl Br p-oMe 4th jß-chloro- methyl Phenyl Phenyl H methyl methyl Br H ethyl 5 / f-mechoxy- methyl Phenyl Phenyl Il methyl methyl Br H ethyl 6th methyl methyl 2-methoxy 2-methoxy H methyl methyl Br H phenyl phenyl 7th methyl methyl Phenyl Phenyl H Piperidino methyl Br H 8th II ethyl Phenyl Phenyl H methyl methyl Br H 9 methyl methyl Phenyl Phenyl Tetra methyl methyl Br II hydro quinolinyl 10 Benzyl methyl Phenyl Phenyl H methyl methyl Br H 11th 4-methoxy methyl Phenyl Phenyl II methyl methyl J II phcnyl 12th Piperidino Phenyl Phenyl II methyl methyl Br H 13th Cyclohexyl methyl Phenyl Phenyl Il methyl ethyl J Il 14th methyl methyl Phenyl Phenyl methyl methyl methyl Br II 15th methyl methyl Phenyl Phenyl Benzyl methyl methyl McSO ₄ Il 16 methyl methyl Phenyl Phenyl Il methyl Benzyl J Il 17th methyl methyl Phenyl Phenyl Il methyl methyl Br p-methyl 18th methyl methyl Phenyl Phenyl II methyl methyl Cl p-methyl 19th - JuIoIi- JuIoIi- II methyl methyl Br Il din-8-yl din-8-yl

Example 20

13.4 parts Michler's ketone, 7.76 parts phosphorus oxychloride and 50 parts by volume of ethylene dichloride are ■ -, heated to 60 ° C for 1 hour with stirring. The solution is quenched in ice, the blue solid is filtered off, washed with ether and dried. Encore this solid to a solution of 16.5 parts of aniline-m-trimethylammonium bromide in isopropanol to results in an intense orange solution. Then 30 parts by volume of caustic soda solution are added, with a pale yellow solid is formed which is filtered off and washed with water.

The yellow solid is dissolved in ethanol, and ι ^r, sodium was added until the solution is colorless. Quenching in ice gives the desired leucauramine (2 parts), which has a melting point of 147 ° C. and can be used in the transfer printing process.

Example 21

5.9 parts of Michler's ketone and 4 parts of zinc accumulation are converted into a solution of 5.6 parts of potassium hydroxide added in 300 parts by volume of methylated fuel, unc the mixture is refluxed for 10 hours 200 parts by volume of methylated fuel are removed by distillation, and the reaction mixture is wire filtered and then poured into 200 parts by volume of water. The precipitated product is filtered through collected, washed alkali-free with cold water and dissolved in ethanol. 7.18 parts of aniline-m-trimethylam monium bromide and 10.5 parts acetic acid are added, and the solution is refluxed for 2 hours, heated. 4 parts of product are isolated as in Example 1.

Michler's thioketone behaves under the above reaction conditions in a similar way to the oxygen supply binding.

Claims (3)

Patent claims: 1. The use of leucauramine compounds the formula wherein each symbol R, R ', R "and R'" independently represents hydrogen or an optionally substituted alkyl, Cycloalkyl, aralkyl or aryl radicals) or part of an optionally substituted hydrocarbon chain forms, which together with the neighboring nitrogen atom forms a heterocyclic Ring generated; X stands for hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical or an alkylene chain with 2 or 3 carbon atoms which is directly attached to a carbon atom in the 2- or 6-position of the ring C is bonded; each symbol Ri, R2 and R3 independently for a possible substituted alkyl, cycloalkyl or aralkyl radical or part of an optionally substituted Hydrocarbon chain forms which together with the adjacent nitrogen atom form a heterocyclic Ring generated; the rings A, B and C can optionally be further substituted; and Z- for an anion stands for the production of hectographic color sheets. 2. Usage according to claim 1, characterized in that each symbol R, R ', R "and R'" stands for an alkyl radical, Ri stands for an alkyl, cycloalkyl or aralkyl radical, R2 and R3 stand for Are alkyl radicals, X is a hydrogen atom or an alkyl, aryl or aralkyl radical and the rings A and B can optionally be substituted by alkyl radicals. 3. Use according to claim 2, characterized in that each of the symbols R, R ', R ", R'", R ₂ and R ₃ stands for methyl and X stands for hydrogen. contains acidic substance, are moistened. The solvent dissolves part of the basic dye derivative and transfers it to the copy sheets, where it combines with the acidic substance, creating a visible Color is created which corresponds to the original lettering on the die. The basic dye derivatives used hitherto in this process have the disadvantage that They like to give sticky deposits that do not easily get onto the fabric or the film or sheet satisfactorily Sheet material can be applied. They can also cause unclear copies or too copies with give rise to poor lightfastness. To overcome these disadvantages, the invention proposes hectographic color sheets Leucauramine compounds of the form!