DE2039848A1 - Rhodamine-like lactones as color-forming substances in pressure-sensitive recording and reproduction material - Google Patents

Description

FARBWERKE HOECHST AG., Formerly Master Lucius & Brüning

< File number: Dr. Ot / We

* HOE 70 / F

Date: 1Ö. / LujfnU

Rhodamine-like lactones as color-forming substances in pressure-sensitive recording and duplication material "

From the French patent specification 1 507 389 it is known that one produces pressure-sensitive recording and duplicating material using color-forming substances that can be the backbone of the formula

(Alkyl) _F "As ~ o

(1)

A carrier material, such as paper, is coated on one side with a solution, suspension or emulsion a compound of formula (1) and on the other hand with a layer containing a weakly acidic clay mineral. Two Sheets coated like a dex produce a copy paper if one layer with egg color-forming substance of one lätttjs with the clay mineral containing layer of the second

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_ 2 -

Brings sheet into contact. When pressure is applied, for example when writing, the two layers react with one another in such a way that the weakly acidic clay mineral, the lactone ring of the color-forming substance, is split up and the strongly colored quinoid form is formed. The color-forming substances of the above-mentioned French patent specification, which are obtained by condensation of 2- (k 'dialkylamino-2'-oxybenzoyl) benzoic acids with various phenols, merely provide red shades, which also do not have good light fastness.

It has now been found that rhodamine-like compounds of the general formula ^s

C = O

as color-forming substances in pressure-sensitive recording and May use reproduction material. In the above formula (2), A denotes a substituted or unsubstituted radical the naphthalene series, which can also be partially hydrogenated, R is a hydrogen atom, a normal alkyl, hydroxyalkyl, Aralkyl or an optionally substituted aryl group, X is Hydrogen or halogen or a lower alkyl group, Y oin hydrogen or halogen atom, a lower alkyl, halo

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genalkyl, hydroxy, alkoxy, carbalkoxy, trifluoromethyl or NitxOgruppe, an optionally substituted amino, carbonamido or sulfamido group or Y and Z together represent the remainder of the general formula

(3)

form, where R has the meaning given above, η the numbers 0-2 and m the numbers 0 - h.

Similar compounds and their use as dyes for wool and calico are already from the German patents 115 991 and 118 077 known. The connections of the general Formula (2) can be prepared by the process described there be, namely by condensation of a corresponding, r f substituted 2 - ('4'-Amino-2' -oxybenzoyl) -benzoic acid with a Napthol, naphthol ether or naphthol ester in the o-position for this sour t of ff unkticn must be unsubstituted. Examples of naphthalene compounds are those in Question that are substituted once or twice by halogen atoms, alkyl, alkoxy groups or hydroxyl groups.

If connections are to be obtained in which Y and Z come together mean the remainder of the general formula (3), one takes

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instead of phthulic anhydride ■ · - i d l'yr - .. ·; ioin.it ¹ : ■ üurucii rubydride. One arrives at Verb; i lulunficn, Oi u zvoi contain lactone group in the molecule.

As a substituent for the ?. - ('' (^ Amiiio- 2. '-oxyljoii, .oy 1) -bonzoic acids come, for example, oil gum! «-.- in 1 ·: γ," ^ ο. R can mean alkyl groups with 1 -' t C Atoms, hydroxytic alkyl groups with 1 - h carbon atoms, aralkyl groups, voiv.ugsiinisi? 13enzyl and aryl groups, preferably phenyl, which are substituted by substituents such as alkyl, halogen or alkoxy groups X, Y and Z can mean halogen atoms, preferably chlorine or bromine atoms. X and Z can also mean alkyl groups with 1-4 C atoms and Z also represents, for example, haloalkyl groups, preferably chloro- and brominekyl, alkoxy- or carbalkoxy groups each having 1 - k carbon atoms and for amino, carbonainido or sulfamido groups, which may also be substituted by alkyl radicals having 1 - k carbon atoms.

The coating of a carrier material than with compounds of the general formula (2) for making a pressure-sensitive Recorded ejinaterials can be used for example Woise indicated in French patent 1 5 ^ 7 3 ^ 9 take place. For example, the color-forming lactones can be used in a high-boiling solvent or a low-melting solvent Solids can be dissolved or dispersed and then thinner Slips onto a carrier material such as Pnp'ier. But you can also use the color-forming lactones in a solvent dissolve and then ri.lend a mixture, such as Gum arabicuin, cfif- ('in, tragacanth or fliiatine add, being

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An emulsion is formed in which the color-forming lactones are enclosed in so-called microcapsules. Such an Eimilion is also well suited for coating a Carrier material. It is also possible to have a mixture of two or several color-forming lactones on the carrier material to apply .. The weakly necessary for color development acidic compounds, such as clay minerals (attapulgite, bentonite, Kaolin) or calcium phosphate or aluminum oxide can be applied to the with the help of a binding agent such as starch or casein Carrier material are applied.

To produce a carbonless paper, for example, a sheet of paper is coated in such a way that the layer on one side a color-forming lactone according to formula (2) and the layer on the other hand contains a weakly acidic substance. Two sheets coated in this way, when placed one on top of the other in such a way that the color-forming lactone-containing layer with the layer containing the weakly acidic reacting substance in contact represents, a carbonless paper. During the writing process, i. by Pressure, both compounds react with each other, whereby the lactone ring opens and the colored one at the pressure points forms the quinoid form of lactone. You can do the two layers do not apply separately on each side of the carrier material, but also on one side one above the other, if necessary with the help of a separating layer.

The rhodamine-like compounds of the general formula (2) are particularly suitable as color-forming substances in pressure-sensitive substances Record ^ - and VorviolfMl tig-ungsma fco rial, da

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_: . . . BATH

they have a noticeable cigen color in their laclon form koi.no. In their clij.noiclon form gobon them brilliant hues. In comparison to the rhodaminähnli chon Vc rb i .ndungen of the French patent specification I 507 3 ^ 9 »which one by condensation with various substituted phenols, the colors stand out, obtained from the lactones of the general formula (2) by a better Lichtechthoit.

Example 1;

a) 02.6 g (0.2 mol) of 2- ( h '-Diethylamino-2'-oxybenzoyl) -benzoic acid and 28.9 g (0.2 mol) of c (-naphthol) are mixed and in the lead of 15 minutes . introduced into 250 ml of concentrated sulfuric acid the mixture is h - heated for 90 ° C After cooling to room temperature, the peak ion mixture is slowly incorporated slowly into excess 10 'pige sul- phuric left the precipitated product is filtered off with suction, washed and dried - 5 hours at 80... This gives 75 g of a gray substance which is boiled with about 500 ml of methanol for a further 2 hours to purify the product (about 70 g) of the following formula

BAD ORiQiNAL 209808/1592

instantly splits into one in the presence of acidic agents blue-rustic red dye.

b) 5 S of the compounds prepared above are dissolved in a 90 vat mixture of 100 g of carnauba wax and 50 g of dibutyl phthalate with stirring. The resulting solution is applied to a suitable base paper in the usual way and dried. A transfer sheet produced in this way produces, on a sheet placed underneath and coated with a suitable acid or an acidic substance, a bluish-tinged red writing when applied pressure right column.

2- (4'-Diethylamino-2'-oxybenzoyl) -benzoene acid

4-methoxy-i ~ naphthol

2-naphthol

1-methyl-2-naphthol

6-chloro-2-naphthol

5,6,7,8-tetralydro-1 -naphthol

5,6,7,8-tetrahydro- 2- naphthol

2,6-dihydroxynaphthalene

Red

red purple red

bluish red

red-brown

dunlcelro tbrown

violet

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2- (k '-Diäthylamino-2'-oxybenzoyl) benzoic acid

2- {h '-ethylamino-

5 · -methyl-2'-oxyben-

zoyl) benzoic acid

2- (h '-amino-5'-methyl-2'oxybenzoyl) -benzoe acid

2- ('ί · -Dimethylamino-2'-oxybenzoyl) benzoic acid

2-methoxy-1-naplithylarain

6- (N, N-diethyl) sulfamido-2-naphthol

6- N, N-di (B-hydroxy) ethyl Sulfamido-2-naphthol

6-13rom-2-naphthiol

1-methyl-2-naphthol

red-violet

Red

bluish pink

Red

bluish red

6-bromine ~ 2-naphthol bluish red

2-Oxy-3-naphthoe- bluish red acid methyl ester

Example 2 ;

3 ¹ »3 β (θ, 1 mol) Z- (h '-dimethylamino-2'-oxybenzoyl! -Benzoic acid and 17 | 8 g (0.1 mol) 6-chloro-2-naphthol are in 250 ml 80 $ sulfuric acid was heated for 6 hours at 150 C. After completion of reaction the mixture is poured onto ice, neutralized with sodium hydroxide or ^r.:. slightly alkaline and extraktiert with chloroform the chloroform phase is separated, dried, purified with animal charcoal, and to a volume of ca 200 ml concentrated.On addition of an excess of petroleum ether, the compound of the formula is precipitated from this solution

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■ - 9 -

off, which is vacuumed and dried. Yield 37 g · In counter wart of acidic reacting agents is immediately imagined intensely so dye.

The coating of a paper with this dye can be used in the in the same manner as indicated in Example 1-b.

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Claims (2)

Patent claims? : 1). Use of rhodamine-like compounds of the general formula A / = O in which A is a substituted or unsubstituted radical of Naphthalene series, R is a hydrogen atom, a lower alkyl, hydroxyalkyl, aralkyl or a possibly substituted one Aryl group, X a hydrogen or halogen atom or a lower alkyl group, Y a hydrogen or Ilalogen atom, Z a Hydrogen or halogen atom a lower alkyl, haloalkyl, hydroxy, alkoxy, carbalkoxy, trifluoromethyl or nitro group, an optionally substituted amino, carbonamido or sulfamido group or Y and Z together represent the remainder of the general formula form, whereby R has the meaning given above, η the numbers 0-2 and m means the numbers 0 - k , as color-forming substances 209808/1592 BATH ORIGINAL zen in pressure-sensitive recording and copying material. 2.) Pressure-sensitive recording and duplication material which, as a color-forming substance, is a compound of the general formula contains ^ C = O in which A is a substituted or unsubstituted radical of the naphthalene series, R is a hydrogen atom, a lower alkyl, hydroxyalkyl, aralkyl or optionally substituted aryl group, X is a hydrogen or halogen atom or a lower alkyl group, Y is a hydrogen or halogen atom, Z a hydrogen or halogen atom, a lower alkyl, haloalkyl, hydroxy, alkoxy, carbalkoxy, trifluoromethyl or nitro group, an optionally substituted amino, carbonamido or sulfamido group or Y Tand Z together the remainder of the general formula BATH 209808/1592 bildOJ ¹ I where ] \ riin above j e.-i '.-' in te Bed ^ ut uuy h; ·. t, η din numbers 0-2 and m means the numbers 0 · - 4. ORIGINAL BATHROOM 209808/159?