DE2558829A1 - PRESSURE OR HEAT SENSITIVE RECORDING MATERIAL - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Baset

^ F!

/ -if- j

Case 1-9736 / + GERMANY

Pressure or heat sensitive recording material.

The present invention relates to pressure- or heat-sensitive recording material containing as Color former at least one compound of the general formula

(D

where mean:

609828/0688

405?

R-, and R ~, which can be the same or different, hydrogen, unsubstituted or substituted by cyano or halogen alkyl with a maximum of 12 carbon atoms, alkoxyalkyl with 2 to 8 carbon atoms, benzyl or phenyl,

R ~ hydrogen, halogen, nitro, alkyl of 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms,

X and Y, which can be the same or different, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, unsubstituted or ring-substituted phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenyl or through Alkyl groups with 1 to 4 carbon atoms, preferably Phenyl substituted with methyl, nitro, halogen or an amino group, the amino group having alkyl groups with 1 to 12 Carbon atoms, acyl groups with 1 to 8 carbon atoms or benzyl can be mono- or disubstituted and

Z alkyl with 1 to 12 carbon atoms, alkenyl with at most 12 carbon atoms, unsubstituted or ring-substituted phenyl-C, -C, -alkyl or aryl or an unsubstituted or substituted heterocyclic radical.

The substituents R 1, R 1, X, Y and Z represent alkyl groups they can be branched or, preferably, straight-chain alkyl radicals.

Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, η-butyl, sec. Butyl, n-hexyl, n-octyl or n-dodecyl.

If the alkyl radicals In R _{1 and R 2 are} substituted, then it is primarily ilalogenalkyl and gyanoalkyl, each with 2 to 4 carbon atoms, such as, for example, β-chloroethyl and β-cyanoethyl.

If R _{1 and R 2 represent} alkoxyalkyl groups, these can have 1 to 4 carbon atoms in each of the alkyl units; preferred alkoxyalkyl radicals are ß-methoxyethyl and β- ethoxyä thyI.

R-, X and Y are preferred as alkoxy groups Methoxy or ethoxy. The alkyl radicals in the N-substituted aminophenyl radicals X and Y are, for example, methyl, ethyl, n ~ Butyl, n-hexyl, n-octyl or n-dodecyl. Alkenyl in Z is for example for allyl, 2-methallyl, 2-ethyIaIIyI, 2-butenyl or octenyl.

Phenylalkyl in the meaning of X ₃ Y and Z can be phenylethyl or, preferably, benzyl. If the benzene nucleus of these araliphatic radicals is substituted, it can contain, for example, halogen, nitro, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms.

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The aryl radical in the meaning of Z can be phenyl, Be diphenyl or naphthyl. These aromatic carbocycles can be substituted, for example by halogen, cyano, nitro, alkyl and / or alkoxy each with 1 to 4 carbon atoms, Methylenedioxy, dialkylamino groups with 1 to 4 carbon atoms in any alkyl moiety or by acyl of 1 to 8 carbon atoms. Among those in X, Y and Z that may be present Acyl groups are the alkanoy groups that have 2 to 4 carbon Atoms, such as acetyl or propionyl, are particularly preferred.

Examples of the aromatic radicals of Z and also of X and Y are phenyl, o-, m- or p-chlorine, bromine or -Fluorophenyl, o-, m- or ρ-methylphenyl, ο-, m- or p-methoxyphenyl, o-, m- or p-nitrophenyl, 3,4-dimethoxyphenyl or 3,4-dichlorophenyl.

As a heterocyclic radical, Z primarily represents a 5- or 6-membered, preferably oxygen, sulfur or nitrogen-containing heterocycle of aromatic character. Examples of such heterocycles are thienyl, Furyl, pyrrolyl, pyrazolyl, pyrazolonyl, 1,2,3-triazolyl, 1, '2,4-triazolyl, pyridyl, thiazinyl or oxazinyl radicals. Included Z can also represent a polynuclear, heterocyclic ring system.

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This preferably contains a fused-on benzene or naphthalene ring, such as an optionally substituted benzothiophene, indole, indazole, benzothiazole, Benzotriazole, naphthotriazole, quinoline, carbazole, phenothiazine or phenoxazine radical. heterocyclic radicals can have substituents of the type listed above, in particular halogen, cyano, nitro, Alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, Acyl of 1 to 8 carbon atoms or phenyl.

The preferred, heterocyclic radicals in the meaning of Z are 2-Fury1, 2-thienyl, 4-pyridyl, 1,2,3-triazol-4-yl, 1-phenyl-3-methy1-5-pyrazolon-4-yl, 3-indolyl, 1-acetyl-3-indolyl or 1-ethyl-2-methyl-3-indolyl.

Halogen atoms in connection with the above substituents are for example fluorine, bromine or preferential prices chlorine.

Practically important compounds of the triaryl-pyrazolonylmethanes the formula (1) correspond to the general formula

8/0688

(2)

where mean:

R, and R ₁ -, independently of one another, hydrogen, alkyl having 1 to 4 carbon atoms or benzyl,

Rß hydrogen, methyl, methoxy or chlorine,

X ₁ alkyl with 1 to 12 carbon atoms »phenyl or phenyl substituted by halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or nitro,

Y-, alkyl with 1 to 4 carbon atoms, preferably methyl or phenyl and

Z, a phenyl radical which is optionally ^{substituted in each alkyl by halogen, methyl-oxydiox3 r} , nitro, alk} ⁷ "! With 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or a dialkylamino group with 1 to 4 carbon atoms, or an ITaphtLyl, furyl, thionyl · - ·, pyrrolyl ·, Fyra ™ zolyl, pyrazolonyl, 1,2,3-triazolyl, pyridyl, indolyl or quinolyl radical, where the · mononuclear or polynuclear heterocycle is optionally substituted by halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, acyl with 2 to 4 carbon atoms or phenyl.

Particularly valuable color formers are compounds of the general formula

609828 / 068B

• Ν - / "V

■ Χ-

wherein R,, Rc and R, - the meaning given for formula (2) to have,

Y _? Methyl or phenyl and

X «and Z ~, independently of one another phenyl or by halogen, Nitro, methyl or methoxy substituted phenyl.

Of these compounds of the formula (3), preference is given to those in which R _{1 and R 1 are} both methyl or ethyl, R 1 is hydrogen, Y 1 is methyl, and X 2 and Z are phenyl. Z2 is also preferably 2-furyl.

Some of the compounds of the formulas (1) to (3) are known, for example from J. Gen. Chem. U.S.S.R., _23, 1103-1106, (1953), however, represent a new class of color formers. They can be produced by processes known per se. One process for preparing the compounds of formula (1) is that one is a carbinol or -ether compound the formula

609878/0688

(4)

0 —R

wherein R is hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl and R,, R ^, R ^ and Z have the meaning given have, with a pyrazolone of the general formula

(5)

wherein X and Y have the same meaning as for formula (1).

The reaction is conveniently carried out in the presence of a Alcohol, preferably methanol and at reflux temperature. The starting materials of the formula (4), in which R is hydrogen, are usually made by oxidation of a leucomethylene dye the formula

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(6)

R,

CH-Z

using the usual oxidizing agents, e.g. chromates, Bichromates, chlorates, peroxides, manganese dioxide, iron III salts or permanganates can be used. If desired, the carbinol compounds obtained can be mixed with an alkanol to be etherified.

The compounds of the formulas (1) to (3) are normally colorless or at most slightly yellow in color. if these color formers are brought into contact with an acidic developer, i.e. an electron acceptor they are blue to green shades that are extremely lightfast. That is why they are very valuable when mixed with others known color formers, e.g. crystal violet lactone, 3,3- (bis-aminophenyl) -phthalide, 3- (aminophenyl) -3-indolylphthalide, 2,6-diaminofluorane or benzoyl-leucomethylene blue, to give blue, navy blue, gray or black colorations.

The color formers of the formulas (1) to (3) are suitable

suitable for use in a pressure-sensitive recorder

B0982B / 0688

nungsmaterlal, the both copying and recording material can be. Such a material includes, for example, at least one pair of sheets containing at least one color former of the formula (1) or the subgroup form in dissolved in one organic solvents and an electron acceptor substance as a developer.

Typical examples of such electron acceptors are Attapuigus-Tonj Silton-Clay, silicon dioxide, bentonite, Halloysite, aluminum oxide, aluminum sulphate, aluminum phosphate, Zinc chloride, kaolin, or any acidic clay or acidic reacting polymeric material such as e.g. a phenolic polymer, an alkylphenol acetylene resin, a maleic acid / rosin resin or a partial or complete hydrolyzed polymer of maleic anhydride with styrene, ethylene, vinyl methyl ether or carboxypolymethylene. Preferred Developers are attapulgus clay, Silton clay or a phenol-formaldehyde resin. These electron acceptors are preferably applied in the form of a layer on the front side of the receiving sheet upset.

The color image delivers slowly at the points where it comes into contact with the electron acceptor substance a colored marking within a period of approx. 1 to 4 minutes.

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In order to prevent these color formers, which are contained in the pressure-sensitive recording material, become active early on, they are usually from the electron acceptor substance separated. This can be achieved by making the color formers foam, sponge or honeycomb Incorporated structures. Preferably the color formers are enclosed in pressure breakable microcapsules.

When the capsules are broken by pressure, for example with a pencil, and when the color former solution is transferred in this way to an adjacent sheet which is coated with an electron acceptor creates a colored image. .

This new color results from the dye formed in the process, which is in the visible range of the electron magnetic Spectrum absorbed.

Some methods of manufacturing microcapsules have long been known. Known methods are for example in U.S. Patents 2,183,053, 2,797,201, 2,800,457, 2,800,458, 2,964,331, 3,016,308, 3,171,878, 3, -265,630, 3,405,071, 3,418,250, 3,418,656, 3,424,827 and 3,427,250. Further procedures are in the UK U.S. Patent 989,264 and more particularly in British Patents 1,156,725, 1,301,052 and 1,355,124. Any of these methods and other methods are suitable

for encapsulating the color formers

60982B / OBB8

The color formers are preferably encapsulated in the form of solutions in organic solvents. Examples suitable solvents are non-volatile solvents, e.g. polyhalogenated diphenyl, such as trichlorodiphenyl or a mixture thereof with liquid paraffin, tricresyl phosphate, di-pbutyl phthalate, Dioctyl phthalate, trichlorobenzene, nitrobenzene, trichloroethyl phosphate, petroleum ether, hydrocarbon oils, such as Paraffin, alkylated derivatives of naphthalene or diphenyl, Terphenyls, partially hydrogenated terphenyl or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons. The capsule walls can be made uniform by coacervation forces are formed around the droplets of the color former solution, the encapsulating material e.g. Gum arabic as described, for example, in U.S. Patent 2,800,457.

The capsules can also be formed from an aminoplast or modified aminoplast by polycondensation as described in British Patents 989,264 and 1,156,725.

The microcapsules containing the color formers of the formula (1) can be used for the production of pressure-sensitive copying materials of various known types can be used. The various systems differ essentially from each other through the arrangement of the capsules, the color reactants and through the carrier material.

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A preferred arrangement is where the encapsulated color former is in the form of a layer on the back of a transmission sheet and the electron absorber substance are applied in the form of a layer to the front side of a receiving sheet.

However, the components can also be used in the paper pulp.

Another arrangement of the components is that the microcapsules containing the color former and the color reactants in or on the same sheet in the form of one or more individual layers or in the paper pulp are present.

Such pressure-sensitive copying materials are described, for example, in U.S. Patents 2,730,457, 2,932,582, 3,418,250, 3,418,656, 3,427,180 and 3,516,846. Other systems are in British Patents 1,042,5 ^ 6, 1,042,597, 1,042,598, 1,042,599, 1,053,935 and 1,517,650 described. Microcapsules which contain the color formers of the formula (1) are suitable for each of these systems and for others Systems.

The capsules are preferably attached to the carrier by means of a suitable adhesive. Because paper is preferred Is the carrier material, these adhesives are mainly paper coating agents, such as gum arabic, Polyvinyl alcohol, hydroxymethylceliulose, casein,

Methyl cellulose or dextrin.

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The term "paper" used here includes not only normal papers made of cellulose fibers ^ but also papers, in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers,

The color formers of the formulas (1) to (3) are surprisingly characterized by a high speed for color development with acidic developers in a thermoreactive Recording material and straight through high lightfastness. This recording material consists at least from a carrier, a color former, an electron acceptor substance and optionally a binder, thermoreactive recording systems include, for example, thermosensitive Record «- and copy rrriat he babble and -papers. These systems are used, for example, for recording of information, e.g. in electronic computers, remote printers or teleprinters, used in measuring instruments. The image generation (marking generation) can also be carried out manually done with a heated pen. Another means of generating markings by means of heat are laser beams. The thermoreactive recording material can be constructed in such a way that the color former is in a binder layer is dissolved or dispersed and in a second layer the electroneiiak ::; eptorsubst: anz as a developer in dissolved or dispersed in the binder. Another Possibility is that both the color former as

6 Π 9 B i B / Π G 8 B

also the developer are dispersed in one layer. The binder becomes image-wise in specific areas by means of heat softens and at these points where heat is applied, the color former comes with the electron acceptor substance in contact and immediately develops the desired color.

The developers are the same electron-accepting substances as they are in pressure-sensitive substances Papers are used. The developer is advantageously solid at room temperature and melts or softens above 50 ° C. Examples of such products are the clay minerals and phenolic resins already mentioned, or phenolic compounds such as 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyloxide, oc-naphthol, ß-naphthol, 4-hydroxybenzoic acid methyl ester, 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4,4'-isopropylidenediphenol, 4,4'-isoprolylidene-bis (2-methylphenol), 4,4'-bis (hydroxyphenyl) valeric acid, Hydroquinone, pyrogallol, phloroglucinol, p-, m-, o-hydroxybenzoic acid, gallic acid, l-hydroxy-2-naphthoic acid, as well as boric acid and aliphatic dicarboxylic acids such as tartaric acid, oxalic acid, maleic acid, Citraconic acid, citric acid or succinic acid.

Preferably, meltable, film-forming materials are used for the production of the thermoreactive recording material Binder used. These binders are usually water soluble, while the color formers and the developer are in

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Are insoluble in water. The binder should be able to handle the color former and the developer at room temperature to disperse and fix.

When exposed to heat, the binder softens or melts, so that the color former comes into contact with the developer comes and can form a color. Water-soluble or at least water-swellable binders are, for example, hydrophilic Polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose. Polyacrylamide, polyvinylpyrrolidone, gelatin and starch.

If the color former and the developer are in two separate layers, water-insoluble layers can occur Binders, i.e. binders that are soluble in non-polar or only slightly polar solvents, such as natural rubber synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethyl methacrylates, Ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used. However, the preferred arrangement is the one in which the color former and the developer are contained in a layer in a water-soluble binder are.

The coatings of the thermoreactive material can contain further additives. To improve the degree of whiteness, to make it easier to print on the papers and to prevent the heated spring from sticking, these coatings _{5 can,} for example, be talc, TiO ₉ , ZnO or CaCO ₀ or else

609878 ^ 0688

contain organic pigments.

In order to ensure that the color is only formed within a limited temperature range, substances, such as urea, thiourea, acetanilide, phthalic anhydride or other corresponding fusible products that contain the induce simultaneous melting of the color former and the developer.

Typical thermoreactive recording materials in which the color formers are used are, for example in German Offenlegungsschriften 2,110,854 and 2,228,581, in French patent specification 1,524,826 and in Swiss patents 164 976, 407 184, 444 196 and 444 197.

In the following manufacturing instructions and examples, the percentages relate, unless otherwise is indicated on the weight,

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Manufacturing regulations

1. 6.93 g of malachite green carbinol base and 3.48 g of 1-phenyl-3-methyl-5-pyrazolone are stirred at reflux temperature in 100 ml of methanol for 13 hours. After cooling, the precipitated reaction product is filtered off, which is then stirred in 50 ml of methanol for a further 3 hours. It is cooled to 20 ^° C. and the product obtained is filtered off. 6.6 g of 4,4'-Ν, Ν, Ν ', N ¹ -tetramethyldiaminotriphenyl- (l "-phenyl-3 ^M -methyl-pyrazole - 5 ⁿ -on-4" -yl) met: Hans.

If one replaces the malachite green carbinol base in production specification 1 and the l-phen / l-3-ynethyl-5-pyraz-olone by equivalent amounts of appropriate carbinol bases and 5-pyrazolone compounds, so are the compounds of the formula listed in the table below

(7)

3 2 ^R 7- -f ^R 8

Rr

obtain. The last column of the table shows the color tones that are produced when the color formers are used in Brought into contact with Siltonton.

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rabelle

i. 1 year ^R 7 ^R 8 R ₉ ^X 3 ^Y 3 ^Z 3 colour 2 -C ₂ H ₅ - ^C 2 ^H 5 H p-tolyl -CH ₃ Phenyl green 3 -GH, H Phenyl -CH ₃ Phenyl green ά - CH ^ CH ₉ CN H Phenyl -CH ₃ Fn aryl green 5 -CH " PU PTJ OPU
-UtIo U JCIq UuH ο H Phenyl -CH ₃ Phenyl green 6th -CH ₃ -CH ₀ -2-Cl Phenyl -CH ₃ Phenyl green 7th - ^CK 2 "O -2-CK ₃ Phenyl -CH ₃ Phenyl green to π -CH ₂ CH ₂ CN -CH ₂ CH ₂ CN -2-OCH ₃ Phenyl -CH ₃ Phenyl green Xi Q -CE- TJ
X J- p-nitrophersyl
* -CH ₃ Phenyl green σο
co 10 -CH ₇ CH ₂ Cl H o-anisyl -CH ₃ Phenyl green 11 -CH ₃ -CH ₃ H Phenyl Phenyl Phenyl green 12th -C ₂ H ₅ -2-Cl ρ-dimethy1-
aminophenyl Phenyl Phenyl green
ho
cn I 13th - ^CH 2 -O 2 ¹ 5 -2-CH ₃ o-chlorophenyl -CH ₃ Phenyl green ^ ^1
0 00 -C ₂ H ₅ -C ₂ H ₅ H Phenyl -CH ₃ o-tolyl 00
turquoise ' ^Γν3
co

Tabel

No.

15 16

17 18

19 20

22 23 24 25

R.

-C ₂ H ₅

-CH,

-CH,

-CH ₂ - / Λ

-CH,

-CH,

-CH,

-C ₂ H ₅

-CH ₂ CH ₂ CN

-CH ₂ - /

^C 2 ^H 5

-C ₂ H ₅

-2-CH,

X,

Phenyl phenyl

Phenyl

Phenyl

Phenyl

Phenyl

Phenyl

p-anisyl

Phenyl

Phenyl

Phenyl

-CH ₃ -CH ₃

-CH ₃ -CH ₃

-CH ₃

-CH ₃

-CH ₃

Phenyl

-CH "

-CH

-CH,

m-anisyl

ρ-fluorine-
phenyl green p-nitro
phenyl green 3,4-dichloro
phenyl green 1-naphthyl green 4-pyridyl green 2-Fury1 blue 2-Fury1 blue 2-Fury1 green, blue 2-thienyl green 3,4-methylene
dioxyphenyl green

colour

green

example 1

A solution of 3 g of 4,4'-N, N, N ¹ , N'-tetramethyldiamino triphenyl- (1 ^ri -phenyl-3 "-methyl-pyrazol-5 ^II -on-4 ^M -yl-) methane in 100 g trichlorodiphenyl is emulsified at 50 ⁰ C in a solution of 12 g of gelatin in 88 g water. Then, the solution of 12 g gum arabic in 88 g of water at 50 ⁰ C are added and thereafter 200 ml of water at 45 ° to 50 "C. added. The emulsion obtained is poured into 600 g of a mixture of ice and water and stirred until the temperature is 20.degree. Sheets of paper are then coated with the mixture and dried. A second sheet of paper is coated with Silton clay. The first sheet and the sheet coated with Silton clay are placed on top of one another with the coatings adjacent to one another. With writing under pressure on the first sheet, the clay coated sheet slowly develops a green color over a period of approximately 2 minutes. The green copy obtained has a good intensity and is lightfast. Absorption maxima at 630 and 425 nm.

Instead of the 4,4'-Ν, Ν, Ν ¹ , N'-tetramethyl-diaminotriphenyl- (1 ^M -phenyl-3 ^M -methylpyrazole-5 "-on-4 ⁿ -yl -) - methane prepared according to regulation 1 The color formers 2 to 25 listed in the table can also be used, with lightfast and color-intensive copies also being produced.

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Example 2

a) 7 g of 4,4'-N, N, N ¹ , N'-tetramethyldiaminotriphenyl- (1 "-phenyl-3" -methyl-pyrazol-5 "-on-4" -yl-) inethane, 300 g of one 10% aqueous polyvinyl alcohol solution and 130 ml of water are rubbed together for one hour, so that an aqueous preparation with a viscosity of 23 to centipoise results. The diameter of the color former particles is about 1 to 3 µ

b) At the same time, 70 g of 4,4'-isopropylidene-diphenol are added and 300 g of 10% aqueous polyvinyl alcohol solution triturated with 130 ml of water for one hour. After this When rubbed in, the particles still have a diameter of 1 to

c) “6 g of the color former and 134 g of the phenol dispersion are now mixed and applied to a sheet of paper, with an application of 0.3 to 0.45 g / cm will. The dried paper contains 3% color former, 67% Ent wrapper and 30% polyvinyl alcohol coated. By touching a heating pin, ground on the top of this The paper immediately formed green marks.

Instead of the above color former, the color former 2 to 25 of the table can also be used with success.

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Example 3

6 g of an aqueous dispersion containing 1.57% 4,4'-N ₅ N ₅ N ', N'-tetramethyl-diaminotriphenyl- (1 "-phenyl-3 ^M -methyl-pyrazol-5" -on-4 " -yl) methane and 6.1% polyvinyl alcohol are mixed with 134 g of an aqueous dispersion containing 14% 4,4-isopropylidenediphenol and 6% polyvinyl alcohol. This mixture is applied to a paper and dried. By touching the paper with a heated ballpoint pen, a green color which has excellent lightfastness is obtained.

Similar results will be obtained using any of the other color formers listed in the table 2 to 25 received.

6 Π 9 8 7 ft / Π R 8 8

Claims (12)

Claims ι U pressure- and heat-sensitive recording material, characterized in that there is at least one compound of the general formula as a color former ^ΙΓ ^ _Η _ ^ Λ Ν — X R, and R ^, which can be the same or different, hydrogen, unsubstituted or by. Cyano or halogen substituted alkyl with a maximum of 12 carbon atoms, alkoxyalkyl with 2 to 8 carbon atoms, benzyl or phenyl, Ro hydrogen, halogen, nitro, alkyl of 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, X and Y, which can be the same or different, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 Carbon atoms, unsubstituted or ring-substituted phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenyl or by alkyl with 1 to 4 carbon atoms, nitro, Halogen or an amino group substituted phenyl, the amino group with alkyl having 1 to 12 carbon atoms, 6098? 8/0688 Acyl with 1 to 8 carbon atoms or benzyl mono- or can be disubstituted and Z alkyl with 1 to 12 carbon atoms, alkenyl with at most 12 carbon atoms, unsubstituted or ring-substituted phenyl-C-, -C-, -alkyl or aryl or an unsubstituted or substituted heterocyclic radical mean. 2. Recording material according to claim 1, characterized in that the color former of the general formula ^R / "V" R, ν -: corresponds to where R, and R ₅ , independently of one another, hydrogen, alkyl having 1 to 4 carbon atoms or benzyl, Rg hydrogen, methyl, methoxy or chlorine, X, alkyl having 1 to 12 carbon atoms, phenyl or through Halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or nitro substituted phenyl and 609828/0688 Y-. Denote alkyl with 1 to 4 carbon atoms or phenyl, and Z-. Phenyl that is unsubstituted or substituted by halogen, methylenedioxy, Nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or a dialkylamino group with 1 to 4 carbon atoms in each alkyl part is substituted, or naphthy1, furyl, thienyl, pyrrolyl, pyrazolyl, pyrazolonyl, Represents pyridyl, 1,2,3-triazolyl, indolyl or quinolyl, where the mononuclear or polynuclear keterocycle is unsubstituted or by calogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, Alkoxy with 1 to 4 carbon atoms, acyl with 2 to 4 carbon atoms or phenyl is substituted. 3. Recording material according to claim 2, characterized in that the color former of the general formula (3) '4. ^l 5 • X ' corresponds to where R /, Rc and R, - have the meaning given in claim 2, Yy methyl or phenyl and X2 and Z ^ _3, independently of one another, denote phenyl or phenyl substituted by halogen, nitro, methyl or methoxy. 609828/0 6 88 ■ - 27- 4. Recording material according to claim 3, characterized in that the color former corresponds to the formula (3) in which R 1 and R ^ are both methyl or ethyl, R ^ hydrogen,. Y _{2 represent} methyl, X ₂ and Z _{2 represent} phenyl. 5. Recording material according to one of claims 1 to 3, characterized in that it is pressure-sensitive. 6. Pressure-sensitive recording material according to claim 5, characterized in that there is at least one color former specified in one of claims 1 to 4 Formula dissolved in an organic solvent and containing an electron acceptor substance. 7. Pressure-sensitive recording material according to claim 6, characterized in that the color former, dissolved in an organic solvent, in by pressure breakable microcapsules is included. 8. Pressure-sensitive recording material according to one of claims 6 and 7, characterized in that it is as Electron acceptor substance Attapulgus clay, Silton clay or a phenol-formaldehyde resin contains. 9. Pressure-sensitive recording material according to claim 7, characterized in that the encapsulated color 609828/0688 color former in the form of a layer on the back of a transfer sheet and the electron acceptor substance are applied in the form of a layer to the front side of the receiving sheet. 10. Pressure-sensitive recording material after at least one of claims 5 to 9, characterized in that the color former together with one or more other color formers is included. 11. Heat-sensitive recording material which in at least one layer at least one color former, one electron acceptor and optionally a binder contains, characterized in that the color former has the general specified in one of claims 1 to 4 Formula has. 12. Heat-sensitive recording material according to claim 11, characterized in that it is used as a color developer Attapulgus clay, Silton clay, phenolic compounds or contains resins or an organic acid. 609828/0688