EP0036117A2 - Pressure-sensitive recording material - Google Patents

Abstract

The present invention relates to a pressure-sensitive recording material having improved storage stability, light fastness and heat resistance, which consists of a unit containing a dye precursor or its solution and a unit containing a dye acceptor material which is capable of color formation by reaction with the dye precursor. The pressure-sensitive recording material according to the invention is characterized in that the dye acceptor material consists of an intimate mixture which a) a 2-hydroxy-benzophenone of the formula I <IMAGE> or 3,5,7,3 ', 4'-pentahydroxy-flavon of the formula II <IMAGE> b) contains a substituted benzotriazole of the formula III <IMAGE> and optionally an inert wax-like binder. The invention also relates to further embodiments of this recording material and to processes for producing the pressure-sensitive recording materials according to the invention.

Description

The present invention relates to a sheet-like or web-shaped recording material with improved storage stability, light fastness and heat resistance. In particular, it relates to a novel dye acceptor or color developer material which, together with the carrier material with which it is coated or incorporated, forms a unit of the pressure-sensitive recording paper and which is used with a large number of known dye precursors or color formers in pressure-sensitive recording materials can be.

Pressure-sensitive recording papers according to the invention are referred to as chemical recording papers or carbon-free papers. They generally consist of a unit carrying a dye precursor or color former or its solution (in sheet or web form, the dye precursor incorporated into the support material or layered on the support material) and a unit carrying the dye acceptor or color developer in the same way, for Color formation is capable of reacting with the dye precursor when, by the action of an external physical force, such as, in particular, pressure, the Dye precursor or its solution comes into contact with the dye acceptor. In this way, a mark or drawing is generated in accordance with the external force acting on it. The web-like or sheet-like unit having the dye precursor or color former generally carries this on its back and is then called a CB sheet
Sheet ") or CB web, the unit having the dye acceptor generally carries it on its front side and is then called CF sheet
or CF train. The sheet-like or web-like carrier material carrying the dye-acceptor layer can in turn carry on its other surface a dye-precursor or a layer containing its solution, which is combined with a further sheet-like or sheet-like CF unit containing dye-acceptor, so that a three-sheet recording material is obtained that can make two copies at the same time. Multi-page sets for the simultaneous production of an even larger number of copies can also be put together.

Basically, the formation of markings or drawings on pressure-sensitive recording papers takes place by reacting a colorless or slightly colored dye precursor or chromogenic color former with a material which is capable of forming the dye by reaction with the dye precursor, i.e. a dye acceptor, the color being formed in the reaction. The dye precursors used in such papers are not generally dyes in the broad sense, but materials that can form color by reaction with the dye acceptor, whether by physico-chemical absorption or by chemical reaction.

Numerous compounds are known as dye precursors used for pressure-sensitive recording papers. They are colorless or weakly colored aromatic organic compounds with double bonds, which are converted into a more polarized conjugated and thus colored form when they are reacted with an acidic sensitizer. A preferred class of such dye precursors or chromogenic materials include phthalide-type compounds such as crystal violet lactone (3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide) and malachite green lactone. (3,3-bis (p-dimethylaminophenyl) ) -phthalide), indole-substituted pyromellitides, leucoauramines and benzospiropyrans as detailed in DE-OS 23 06 454, also triphenylmethane dye precursors of the phthalane type, as described in DE-PS 14 21 393, benzodifuran derivatives as in DE-PS 14 21 394 described or pyridine carboxylic acid lactones such as are disclosed in DE-PS 24 12 640.

In order to clarify the advantages of the recording material according to the invention over the previously known recording materials, the color formation mechanism must be discussed. He is best known representative of the dye precursors of the triphenylmethane series, the crystal violet lactone (CVL for short).

Crystal violet lactone is one of the triphenylmethane dyes which, due to their constitution, can assume various boundary structures responsible for the color formation.

In addition, the trityl boundary structure which has a carbenium ion and is customary for triphenylmethane compounds is likely to be present:

Steric effects prevent these radicals from dimerizing into hexaarylate derivatives. Since free radicals of the latter constitution are colored more consistently and intensively than the other border structures, this border structure should be sought.

In carbonless paper coatings, the aim now is to break the lactone ring of the crystal violet lactone by reaction with other substances (dye acceptors) and thus to form the other gene structures and to get the color effect. The best-known reactants for crystal violet lactone are the so-called clays. These are inorganic products such as clays, silicates, attapulgite, argosit, calcined diatomaceous earth, activated silica, sodium aluminum zeolite, pyrophyllite, bentonite, magnesium montmorillonite and the like. All of these products are electron acceptors.

However, since these substances cause the color effect to develop very slowly, it was proposed to add metal salts to them. According to DE-AS 1 771 641, the addition of aluminum and zinc salts or the activation of clays by acid treatment and subsequent calcination at 200 to 1000 ^° C. has been proposed. According to DE-AS 1 809 778, the use of acid-treated montmorrillonite is proposed, the color developing ability being achieved by increasing the surface area of the dye acceptor. A further improvement is described in DE-PS 2 023 152, according to which alkali salts of organic acids are added to the clay materials.

The next major advance in the field of color development sheets (sheets with dye acceptors) was the use of phenolic bodies for color development (for example GB-PS 1 090 866, GB-PS 1 416 755, GB-PS 1 421 395, DE-PS 1 421 397, DE-OS 1 511 277, DE-AS 1 671 561, DE-AS 1 805 844, DE-AS 1 926 370). Starting from the pure mechanism of color formation, the alkyl and halogen-substituted phenols used in DE-PS 1 934 457 for polycondensation made further progress, since halogen atoms have a high electron affinity and they increase the acidity of the phenolic proton. This accelerates the cleavage of the lactone ring of crystal violet lactone and similar compounds and thus the color formation. Further phenol groups which are substituted with electron-depressing groups, ie those with a positive mesomerism effect, were incorporated into the polycondensate, as a result of which the dye is more stable after its formation. However, the relative toxicity of many substances in this group is disadvantageous.

Furthermore, it has been proposed to use phenol aldehyde and phenol acetylene resins with various additives in connection with the dye acceptor layer (for example DE-AS 2 120 920, DE-AS 2 127 852, DE-AS 2 128 518, DE-PS 2 129 467, DE- AS 2 132 849, DE-PS 2 164 512). To improve the stability of the resulting color, it was proposed according to DE-AS 2 219 556 to coat a phenol-formaldehyde polymer onto basic pigments. Pigments that absorb light in the range of 230-370 nm are described as being suitable. Examples of these are calcium carbonate, magnesium oxide and calcium and magnesium phosphate (cf. also DE-OS 2 342 596, 2 426 678 and 2 407 622). DE-AS 2 242 250 then proposes that the metal ions important for the rapid development of the color in the dye acceptor layer in the form of salicylic acid salts, i.e. to combine with the clays in the form of a phenol-like body (see US Pat. Nos. 4,063,754, 4,112,138 and 4,090,619).

To increase the color effect, so-called secondary color developers are also used in carbonless papers. A common secondary color developer is benzoyl leucomethylene blue, 3,7-bis (dimethylamino) -10-benzoyl-phenothiazine. ' Its color development is slow due to air oxidation. This cleaves the benzoyl residue 2,7-bis (dimethylamino) phenothiazonium benzoate). This dye is largely lightfast. With the to the Phenolic bodies or metal salts added to the clay mixtures frequently occur when the benzoic acid anion is exchanged for the anion of the salt. If, for example, metal chlorides are used, the corresponding 2,7-bis (dimethylamino) phenothiazonium chloride, the blue colored methylene blue, forms. This salt tends to absorb water. However, if it is in the form of a double zinc chloride salt, which occurs with larger excesses of zinc chloride, the brown copper colored zinc chloride double salt is formed, which leads to considerable undesirable discoloration, the more the primary dye fades due to its lack of lightfastness. In systems in which the zinc chloride is arranged on the CB side and the dye precursors are arranged on the CF side, this can result in severe brown-stained discoloration if stored incorrectly, when pressure is applied to the paper, or if the roll-up of web-shaped recording materials is too tight The back of the sheet is created by transferring the water-soluble phenothiazonium double salt from the front to the next back above, as the hygroscopic zinc chloride always accumulates some moisture there. This undesirable effect is therefore not the "penetration" of the dyes through the double-coated middle sheets, which is otherwise observed in practice when using inferior papers, but the effect mentioned can also arise on a CB-coated cover sheet after the writing set has been put together has been.

Attempts have also been made to protect the lightfastness of the primary color developer, ie the triphenolmethane dye, from fading, ie from the action of light, by adding other substances. On the one hand, the alkaline earth metal carbonates, which absorb UV light, are used for this purpose. In DE-OS 2 129 467 describes the addition of certain colorless phenothiazines which are substituted with electron-donating groups. According to DE-AS 1 267 961, hydroquinone and phenyl-β-naphthylamine are added directly during paper manufacture. cheerful such additives such as diaminostilbene and benzimidazole are described in DE-AS 1 809 778.

In addition to the unwanted fading of the writing after it was intended, there is a second major problem with carbonless papers, namely the premature development of discolourations which make the carbonless paper appear soiled. Above all, this problem occurs with papers containing clays. The individual clay particles protrude to a certain degree from the surface of the layer containing them and give them a certain roughness. When storing large stacks of paper, they exert pressure on the adjacent sheet and burst the microcapsules with the color formers there. On the one hand, the color formers already produce color effects to a certain extent with the clays. This can also not be avoided by providing "spacers" such as round cellulose particles in the layer carrying the clay particles. Such round spacers also exert the pressure described on the adjacent sheet and do not prevent the bursting of microcapsules with color formers. It is essential, however, that an additional reason for the undesirable color effects is a reaction of the color former or color acceptor with paper constituents and additives, the nature of which the manufacturer of carbonless papers often does not know, and complete full analyzes are ultimately too costly and cumbersome. Therefore, reaction stabilizers must be added to the system. Especially with wood-containing papers, extremely unpleasant surprises can occur after a certain period of storage. Papers made from cheap, fast-growing tropical woods may contain the following compounds:

It can easily be seen that papers containing such products are predestined to give discolorations with triphenylmethane dyes. Even in the absence of triphenylmethane dyes, such compounds are responsible for the fact that woody papers are usually yellowish in color. However, caution should also be exercised with white-appearing papers, since many papers are coated with kaolin, a type of clay or contain tannin, which can then react with the metal ions often contained in dye-acceptor layers and form discolourations, so that the discoloration here is not caused by the dye becomes. Ultramarine, which corresponds approximately to the empirical formula ^S i ₃ A1 ₃ Na ₄ S ₂ 0 ₁₂ , is often added to yellow papers. Ultramarine makes the paper appear white through a complementary color reaction. This clay-like substance is also predestined to react with triphenylmethane dyes. With regard Given the large volume that ultramarine is sold in the paper industry, the risk of buying "white paper" that is not white at all (ie free of dyes) is very great.

To avoid the two types of premature discoloration described, urea or urea derivatives such as thiourea, triethanolamine, monoethanolamine, cyclohexylamine, diethylene triamine, acid amides, morpholine or unsaturated, nitrogen and oxygen-containing heterocycles have been used (for example GB-PS 789 396, DE-PS 2 153 043, DE-PS 2 164 512, DE-OS 2 426 678 and DE-OS 2 443 576). Such additives have the disadvantage, however, that if the dosage is too high, the color effect desired by the action of pressure develops only too weakly or not at all. However, a dosage that is not too high can often not be predicted, since the nature and the amount of the products causing such premature discoloration in the paper used are unknown to the manufacturer of carbonless papers. Amines also cause health problems.

Not only components of the paper, but also the solvents used in the production of printed carbonless papers can have a considerable undesirable influence on the desired color effect due to solvatochromatic phenomena. Crystal violet and phenolic bodies produce a blue color which is decolorized when ketones, ethers, esters, sulfoxides, sulfones, sulfides, nitriles and amines are added as solvents, but is not influenced by benzene, toluene or xylene. Crystal violet with lower fatty acids such as acetic acid, propionic acid or butyric acid gives a blue color, which in contrast is caused by benzene, Toluene or xylene is decolorized. In contrast, with higher fatty acids, such as caproic acid, crystal violet gives no color; by adding methanol, ethanol or propanol, on the other hand, such fatty acids cause a coloration which disappears when benzene, toluene or xylene are added. The blue color produced by crystal violet and benzoic acid is also enhanced by methanol, but fades when the aromatic solvents mentioned are added. The coloration caused by the combination of crystal violet and salicylic acid is not decolorized by solvents of a polar nature, however, when alcohols are added, there is a decrease in color, but not decolorization. The mentioned decolorization of the coloration occurring with the combination of crystal violet with phenols with esters such as ethyl acetate, however, is not decolorized by the ethyl ester of chloroacetic acid. The series of corresponding phenomena can be extended considerably and explains that without precise knowledge of the papers used in the manufacture of the papers used as supports in carbonless papers and similar pressure-sensitive recording materials and of the printing inks and solvents used for the manufacture of printed carbonless papers, the manufacture of such stocks pressure-sensitive recording materials and their storage and use is extremely difficult and the occurrence of one or other or more of the disadvantages described cannot be foreseen at all.

It is an object of the present ^/ invention to provide a dye acceptor material, the permanent one with all possible Triphenylmethanfarbstoffvorläufern or analogously reacting dye formers to form, reacts sufficiently strong coloring effect and thereby the above-described undesirable Avoids side effects as comprehensively as possible and thus, regardless of whether arranged in a CB or CF arrangement or on a support material coated on both sides or incorporated into the support material, enables the production of pressure-sensitive recording materials with improved storage stability, lightfastness and heat resistance.

• a) entweder
  • aa) ein 2-Hydroxy-benzophenon der Formel I
    
    worin R₁ eine Hydroxygruppe, ein'unsubstituierter Alkoxyrest mit 1 bis 18 Kohlenstoffatomen oder ein Alkoxyrest mit 1 bis 4 Kohlenstoffatomen ist, der 1 oder 2, gegebenenfalls mit einer gesättigten oder olefinisch ungesättigten Carbonsäure mit 2 bis 4 Kohlenstoffatomen veresterte Hydroxygruppen trägt, R₂ Wasserstoff, ein Phenylrest, die Sulfonsäuregruppe -SO₃H oder die Gruppe -S0₃Me ist, wobei Me ein Alkalimetall ist, R₃ Wasserstoff, die Hydroxygruppe, ein Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Alkoxygruppe mit 1 bis 18 Kohlenstoffatomen oder ein Phenylrest ist, und R₄ Wasserstoff, die Hydroxygruppe, ein Phenylrest, die Carboxygruppe -COOH, die Gruppe -COOMe ist, wobei Me ein Alkalimetall ist, oder
  • _bb) das Hydroxyflavon Quercetin, d.h. das 3,5,7,3',4'-Pentahydroxy-flavon der Formel II
    
    und
• b) ein substituiertes Benztriazol der Formel III
  
  worin R₁ Wasserstoff oder die tert. Butylgruppe, R₂ ein Alkylrest mit 1 bis 12 Kohlenstoffatomen, ein Alkoxyrest mit 1 bis 12 Kohlenstoffatomen, der Cyclohexylrest, die Sulfosäuregruppe -S0₃H oder die Gruppe -SO₃Me ist, wobei Me ein Alkalimetall ist, und R₃ Wasserstoff oder Chlor ist,
  und gegebenenfalls ein inertes wachsartiges Bindemittel enthält.

The pressure-sensitive recording material according to the invention with improved shelf life, light fastness and heat resistance consists of a unit containing a dye precursor or its solution and a unit containing a dye acceptor material which is capable of forming color by reaction with the dye precursor, or a plurality of such unit pairs, for example in the form of a writing set for the simultaneous production of a plurality of prints. The pressure-sensitive recording material according to the invention is characterized in that the dye acceptor material consists of an intimate mixture which

• a) either
  • aa) a 2-hydroxy-benzophenone of the formula I.
    
    wherein R _{1 is} a hydroxyl group, an unsubstituted alkoxy radical having 1 to 18 carbon atoms or an alkoxy radical having 1 to 4 carbon atoms, the 1 or 2, optionally esterified with a saturated or olefinically unsaturated carboxylic acid having 2 to 4 carbon atoms carries groups, R _{2 is} hydrogen, a phenyl radical, the sulfonic acid group -SO ₃ H or the group -S0 ₃ Me, where Me is an alkali metal, R _{3 is} hydrogen, the hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a phenyl radical, and R _{4 is} hydrogen, the hydroxyl group, a phenyl radical, the carboxy group -COOH, the group -COOMe, where Me is an alkali metal, or
  • _b b) the hydroxyflavon quercetin, ie the 3,5,7,3 ', 4'-pentahydroxyflavon of the formula II
    
    and
• b) a substituted benzotriazole of the formula III
  
  wherein R _{1 is} hydrogen or the tert. Butyl group, R ₂ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, the cyclohexyl radical, the sulfonic acid group -S0 ₃ H or the group -SO ₃ Me, where Me is an alkali metal, and R ₃ is hydrogen or chlorine is
  and optionally contains an inert waxy binder.

According to a preferred embodiment, the color acceptor material consists of an intimate mixture which additionally contains a phenol with a special steric configuration, namely one or more phenols from the group 2,4,6-tris (3,5-di-tert.butyl-4 -hydroxybenzyl) mesitylene, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-tert-butyl-phenyl) -butane, the β- (3,5, -di-tert. butyl-4-hydroxy-phenyl) -propionic acid n-octadecyl ester, the β- (3,5, -di-tert.butyl-4-hydroxy-phenyl) -propionic acid ester of pentaerythritol and a 2-n-alkylthio- 4,6-di- (3 ', 5'-di-tert-butyl-4'-hydroxy-phenoxy) -1, 3, 5-triazine with 4 to 12 carbon atoms in the alkylthio radical. Due to the complex structures of these special phenols, the triphenylmethane dyes are "shielded" after they have been formed, so that they provide additional light protection.

A really optimal protection against color fastness is always achieved only by mixing one or more of the special phenol derivatives with both the α-ketophenols of the formulas I or II and the benzotriazole derivative of the formula III, the special additional phenols in the dye acceptor material according to the invention being used to achieve advantageous effects can be omitted as the benzotriazole derivatives of the formula III.

A further improvement in the color fastness and shelf life of the color effects produced with triphenylmethane dyes is obtained if, in addition to the α-keto-phenols of the formula I or II and the substituted benzotriazole derivatives of the formula III and, if appropriate, the special phenols, the dye acceptor material is a metal complex salt of the formula IV

admixed in which R ₁ and R ₂ , which may be the same or different, are branched-chain, preferably tertiary alkyl radicals having 6 to 12 carbon atoms, R _{3 is} a straight-chain or branched-chain alkyl radical having 3 to 12 Is carbon atoms, in which case R ₄ and R _{5 are} hydrogen, or one, two or three of the radicals R ₃ , R ₄ and R _{5 are} hydroxy-lower alkyl radicals having 2 to 6 carbon atoms, the other radicals being hydrogen atoms, and Me Is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va. R ₃ is preferably an n-alltyl group having 3 to 5 carbon atoms or the 3,3-dimethylbutyl radical and is Me Co, Ni, Mn, Zn or Fe.

The addition of these compounds in particular stabilizes the dye acceptor layer against premature color reaction when storing large amounts of paper in the pressure-sensitive recording material or when the roll winding of web-shaped pressure-sensitive recording material is too tight. Furthermore, an additional stabilization of the generated color effect is brought about.

Dieser aus dem Bereich der Medizin wohlbekannte Wirkstoff ist nicht nur befähigt, mit der in 9-Stellung vorhandenen phenolischen Hydroxygruppe mit den Triphcnylmethanfarbstoffvorläuferprodukten zu reagieren, sondern er kann aufgrund seiner durch die benachbarte Doppelbindung aktivierten Säureamidgruppe und durch die in 10-Stellung vorhandene Aminogruppe, die ihrerseits durch die in 9-Stellung vorhandene phenolische Hydroxygruppe aktiviert wird, anstelle der vorbekannten, vorerwähnten Harnstoffderivate mit verbessertem Ergebnis eingesetzt werden und dabei ein vorzeitiges Reagieren der Farbstoffvorläuferprodukte mit den Komponenten des Farbstoffakzeptormaterials bei Druck durch hohe Papierstapel bzw. zu eng gewickelten Rollen von bahnförmigem druckempfindlichem Aufzeichnungsmaterial vermeiden.According to a further embodiment, the dye acceptor material contains 0.1 to 1% by weight, preferably 0.1 to 0.5% by weight, 5.10 in addition to the components of the formulas I or II and III and preferably also in addition to the other components listed above , 11,11α-tetrahydro-9,11-dihydroyy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide Formula V

This active ingredient, which is well known from the field of medicine, is not only able to react with the phenolic hydroxyl group present in the 9-position with the triphcnylmethane dye precursor products, but because of its acid amide group activated by the adjacent double bond and the amino group present in the 10-position, it can is in turn activated by the phenolic hydroxyl group present in the 9-position, is used instead of the known, aforementioned urea derivatives with improved results and thereby a premature reaction of the dye precursor products with the components of the dye acceptor material when printing through high paper stacks or too tightly wound rolls of web-like pressure-sensitive Avoid recording material.

According to a preferred embodiment, the dye acceptor according to the invention contains, in addition to the components of the formulas I or II and III, both at least one of the special phenols, one of the complex metal salts of the formula V and the benzodiazepine-2-acrylamide derivative mentioned in the stated amount.

All of the above-mentioned components of the dye acceptor material according to the invention are white to off-white products. If a delicately colored dye acceptor layer is now desired, a [1-phenyl-3-methyl-4-allcyl ether pyrazolate (5)] can advantageously be used together with the special phenols listed. -Ne (II) complex salt can be used, the alkyl group in the alkyl ether residue containing 1 to 12 carbon atoms in a straight or branched arrangement and Me being Co, Ni, Mn, Zn, Fe, Cu, Cr or Va. The nickel complexes are colored pale green. The before mentioned added metal complexes result in an additional deepening of the color effect, and the light fastness of the color effects caused is further increased.

Mixtures of the individual components of the dye acceptor material according to the invention can be applied from the melt of waxy binders to the paper serving as a carrier, which is not only environmentally friendly, but also reduces the usual workload to a minimum and saves solvent and drying energy. A faster machine order is also possible, which makes the manufacturing process even more economical. After weighing in, dosing and mixing, the constituents are, if necessary, added to a premelted wax / plastic mixture or natural wax / synthetic wax mixture with constant stirring and then ground in a pearl mill until a fineness is achieved which corresponds to the grinding of carbon paper colors. The finished mass should be stirred, pumped over or, if necessary, treated with ultrasound during the application in order to obtain an always perfect, homogeneous layer.

If the dye acceptor material is to be applied to the CF side of the paper sheets or webs, it is applied in an amount of 0.5 to 4 g / m ² . If the dye acceptor material is to be applied to the CB side, somewhat larger layer thicknesses are required. It is expedient to apply in an amount between 2 to 6 g / m ² . If necessary, fillers such as tallow or. Cellulose fibers are ground with the mass and incorporated into it.

Commercially available machines are suitable for application from the melt, e.g. Machines of the type CCB-Spezial, Kst 250/900 or DS 400/600 from the company Spezial-Papiermaschinenfabrik August Alfred Krupp GmbH & Co, D-4010 Hilden, whereby with individual machine types the layer can be printed simultaneously in one operation if desired is.

However, it is also possible, if desired by the processor for any reason, to dye the dye acceptor material of the invention from a solvent e.g. a lower alkanol, especially isopropanol. This alcohol has a pleasant smell, can be processed in a high workplace concentration and does not require large amounts of energy for drying. In practice, the procedure is such that, after grinding, the alcohol is added to the finished wax melt enriched with the components with constant stirring using a high-speed stirrer. If the dispersion is stirred until it cools, a paste-like mass results which is easy to apply.

A particular advantage of the dye acceptor material according to the invention is that even thin papers with weights between 15 and 30 g / m ² can be processed at high machine speeds. For example, 17.5 g / m ² papers are processed in the production of single-use carbon paper. With such papers, sets of 20 to 40 copies can be made with good legibility of all sheets. Let go so-called snapout sets can also be produced with such thin papers if papers of conventional thickness of approximately 30 to 70 glm ² are combined with the thin paper.

It is also possible to incorporate the individual components of the dye acceptor material according to the invention directly into the paper during papermaking. For this purpose, the components are ground well together with cellulose fibers and the mixture is then added to the pulp before adding the sizing agent.

The following examples serve to further illustrate the present invention without restricting it thereto. Quantities in parts are parts by weight unless otherwise stated.

Examples 1-18: Application from the melt

General processing information for the products of Examples 1-18:

Depending on the recipe, the active ingredients and any fillers such as barium sulfate and cellulose derivatives are mixed in the oil products and, if necessary, pasted with the fat products or added to the melted waxes or their mixtures with wax-like plastics and in a ball mill with additional heat (depending on the type of mill) Grind for 3 to 4 hours until a degree of grinding is achieved that is otherwise customary for carbon paper inks (degree of fineness approx. 6 - 10 µm).

Commercially available coating devices can be used for further processing and paper coating.

The thickness of the paper coating is generally 0.5 - 4 g / m if the paste is applied to the CF side and serves as a receiver for capsule papers. In this area it can still be written on with a ballpoint pen.

If, in certain systems, for example if the CF side is printed with a printing ink containing dye precursors, the product obtained according to the examples is to be applied to the CB side, it can be transferred by printing if it has a layer thickness of between 2 and 6 g / m ^{2 is} applied. The paper material is the material that is customary in the production of carbon-free papers used depending on the number of copies in the set.

The products of Examples 5 to 11 are preferably used for CF applications, while those of Examples 1 to 4 and 12 to 16 are suitable for both CF and CB applications.

The best contrasts are naturally achieved if those are selected as the dye precursors which give blue and black color formations with the dye acceptor layer according to the invention. Colored substrates have the advantage in multiple sets that they make it easier to arrange the individual copies when creating them.

example 1

• 3 parts compressor oil according to DIN 51506, kinematic viscosity at 40 ° C: 1.06-10 ^-4 m2 s ^-1 (+ -10%)
• 3 parts compressor oil according to DIN 51506, kinematic viscosity at 40 ° C: 9.8 · 10 ^-5 _m ² s ^{- 1} ( ₊ - _10% )
• 50 parts of low-pressure polyethylene containing paraffin,
• 20 parts of micro wax,
• 10 parts of soft paraffin,
• 5 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone-5-sulfonic acid sodium,
• 3 parts of 2- (2'-hydroxy-3'-tert.butyl-5'-septyloxyphenyl) benzotriazole,
• 2 parts of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerithritol,
• 2 parts of [2,2'-thio-bis- (4-tert.hexylphenolato)] - cyclohexylamine-Co (II),
• 2 parts of [1-phenyl-3-methyl-4-propoxoxy pyrazolate (5)] 2 Cu (II).

Example 2

• 12 parts special oil according to DIN 51525, kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² s- ¹ ( _{+ -10%} )
• 40 parts hard paraffin from Fischer-Tropsch synthesis,
• 10 parts micro wax,
• 10 parts of paraffin-containing low-pressure polyethylene,
• 8 parts of soft paraffin,
• 8 parts of 2,2 ', 4,4'-tetrahydroxy-benzophenone,
• 6 parts of 2- (2'-hydroxy-3 ', 5'-di-tert.butylphenyl) benzotriazole,
• 3 parts of 2,4,6-tris (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) mesitylene,
• 0 4 parts 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepin-2- (trans) -acrylamide ,
• 2.6 parts of [1-phenyl-3-methyl-4-tert-octylohypyrazolate (5)] ₂ Mn (II).

Example 3

• 5 parts multi-grade oil HD 20/50,
• 2 parts special oil according to DIN 51525 kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² s ^-1 (+ - 10%)
• 2 parts compressor oil according to DIN 51506 kinematic viscosity at 40 ° C: 9.8 · 10 ^-5 _m ² s ^-1 ( ₊ - _10% )
• 2 parts of Vaseline,
• 30 parts of partially saponified ester wax based on raw montage light,
• 25 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of micro wax,
• 10 parts of 2-hydroxy-4-n-oxtoxy-benzophenone,
• 2 parts of 2- (2'-hydroxy-3'-tert.butyl-5'-tert.octylphenyl) -5-chloro-benzotriazole,
• 1.5 parts of 2-n-octylthio-4,6-di- (4'-hydroxy-3 ', 5'-di-butylphenoxy) -1,3,5-triazine,
• 0.5 parts of 5,10,11,11aC-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide.

Example 4

• 7 parts claw oil,
• 30 parts of low-pressure polyethylene containing emulsifier,
• 20 parts partially saponified ester wax based on raw montane,
• 10 parts of acid wax on raw montane basis (light),
• 5 parts carboxymethyl cellulose,
• 5 parts CaS0 ₄
• 10 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone-5-sulfonic acid sodium,
• 8 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-dodecylphenyl) -5-chloro-benzotriazole,
• 5 parts [2,2'-thio-bis- (4-tert.octyl-4'-tert.dodecylphenolato)] - n-decylamine-Zn (II).

Example 5

• 5 parts industrial oil according to DIN 51501: H oil kinematic viscosity at 40 ° C 1.0 · 10 ^-4 _m ² s ^-1 ( ₊ - ₁₀ %)
• 2 parts claw oil,
• 3 parts of Vaseline,
• 10 parts catalytically oxidized wax from Fischer-Tropsch and Ziegler paraffins,
• 10 parts of low-pressure polyethylene with 30% paraffin content,
• 10 parts of low-pressure polyethylene containing emulsifier,
• 30 parts micro wax,
• 5 parts of cellulose acetate (38.3% acetate content),
• 5 parts barium sulfate,
• 14 parts of 2,2'-dihydroxy-4-octoxy-benzophenone,
• 6 parts of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole.

Example 6

• 3 parts industrial oil according to DIN 51517 CLP oil kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² s ^-1 ( ₊ - 10%)
• 1 part industrial oil according to DIN 51501: N oil kinematic viscosity at 40 ° C: 4.6 · 10 ^-5 _m ² _s - ¹ ( ₊ -10%)
• 2 parts claw oil,
• 2 parts of Vaseline,
• 30 parts hard paraffin,
• 10 parts micro wax,
• 20 parts of low-pressure polyethylene containing emulsifier,
• 10 parts of low-pressure polyethylene with 30% paraffin content,
• 5 parts of cellulose acetopropionate (3% acetyl content and 39.2% propionyl content),
• 5 parts barium sulfate,
• 5 parts of 2-hydroxy-4-dodecyloxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 4 parts of B- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerythritol.

Example 7

• 4 parts industrial oil according to DIN 51502 H oil kinematic viscosity at 40 ° C: 1.5 · 10 ^-4 _m ² _s -1 ( ₊ -19 ^% )
• 2 parts industrial oil according to DIN 51524 HL oil kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² s ^-1 ( ₊ -10%)
• 5 parts of Vaseline,
• 20 parts of low-pressure polyethylene containing emulsifier,
• 20 parts micro wax,
• 10 parts partially saponified ester wax on raw montane basis (light),
• 10 parts of acid wax,
• 10 parts of cellulose acetobutyrate (13.5% acetyl content, 37% butyryl content),
• 8 parts barium sulfate,
• 6 parts of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid,
• 2 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 1 part of 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene,
• 2 parts [2,2'-thio-bis- (4-tert.octylphenolato)] - n-butylamine-Ni (II).

Example 8

• 5 parts special hydraulic oil according to DIN 51525 kinematic viscosity at 40 ° C: 1.45 · 10 ^-4 _m ² _s - ¹ ( ₊ -10%)
• 3 parts of Vaseline,
• 30 parts hard paraffin,
• 15 parts of partially saponified ester wax,
• 15 parts of acid wax,
• 10 parts methyl cellulose,
• 8 parts barium sulfate,
• 4 parts of 2-hydroxy-4-methoxy-4'-methyl-benzophenone,
• 3 parts of 2- (2'-hydroxy-3 ', 5'-di-tert.butyl-phenyl) -benziazole,
• 3 parts of [2,2'-thio-bis- (4-tert-dodecylphenolato)] - n-hexylamine-Co (II),
• 4 parts of β- (3,5-di-tert-butyl-4-hydr-oxy-phenyl) propionic acid ester of pentaerithritol.

Example 9

• 5 parts hydraulic oil according to DIN 51525 kinematic viscosity at 40 ° C: 1.02.10 ^-4 _m ² s ^-1 (+ -10%)
• 7 parts of Vaseline,
• 35 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of micro wax,
• 3 parts of methyl hydroxypropyl cellulose,
• 8 parts barium sulfate,
• 8 parts of 2,2 ', 4,4'-tetrahydroxy-benzophenone,
• 8 parts of 2 - (2'-hydroxy-5'-methylphenyl) benzotriazel,
• 2 parts [2,2'-thio-bis- (4-tert-hexylphenolato)] - cyclohexylamine-Mn (II),
• 3.5 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 0.5 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-B-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide.

Example 10

• 8 parts special oil according to DIN 51525 kinematic viscosity at 40 ° _C: 6.8 · 10 ^-5 _m 2 s ^-1 (+ -10%)
• 20 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of micro wax,
• 20 parts of soft paraffin,
• 15 parts of hydroxypropylmethyl cellulose,
• 9 parts of 2-hydroxy-4- (2'-hydroxy-3'-methacryloxy) propoxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-sulfonyloxy-phenyl) -5-chloro-benzotriazole,
• 5 parts [2,2'-thio-bis- (4-tert-octylphenolato)] - n-butylamine-Zn (II).

Example 11

• 8 parts special oil according to DIN 51525 kinematic viscosity at 40 ° C: 6.8 · 10 ^{* 5} _m ² s ^-1 ( ₊ - _10% )
• 20 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of micro wax,
• 20 parts of soft paraffin,
• 15 parts of hydroxypropylmethyl cellulose,
• 9 parts quercetin (1,3,7,3 ', 4'-pentahydroxy-flavon),
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-sulfonyloxyphenyl) -5-chloro-benzotriazole,
• 5 parts [2,2'-thio-bis- (4-tert-octylphenolato)] - n-butylamine-Zn (II).

Example 12

• 10 parts of Vaseline,
• 2 parts claw oil,
• 50 parts of low-pressure polyethylene containing emulsifier,
• 10 parts of paraffin-containing low-pressure polyethylene (30% paraffin content),
• 10 parts micro wax,
• 5 parts soft paraffin,
• 6.5 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone,
• 6 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-sulfonyloxy-phenyl) benzotriazole, sodium salt,
• 0.5 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepin-2- (trans) - acrylamide.

Example 13

• 4 parts industrial oil according to DIN 51524 HL oil kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² _s - ¹ ( ₊ - _10% )
• 4 parts industrial oil according to DIN 51525 HLP oil kinematic viscosity at 40 ° C: 1.05 · 10 ^-4 _m ² _s - ¹ ( _{+ -10%} )
• 2 parts of Vaseline,
• 20 parts of partially saponified wax,
• 30 parts of paraffin-modified low-pressure polyethylene (30% paraffin content),
• 10 parts catalytically oxidized wax from Fischer-Tropsch and Ziegler paraffins,
• 5 parts micro wax,
• 10 parts of soft ester wax,
• 5 parts of 2,4-dihydroxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 5 parts of [1-phenyl-3-methyl-4-methoxy-pyrazolot (5)] ₂ -Ni (II).

Example 14

• 5 parts compressor oil according to DIN 51506 kinematic viscosity at 40 ° C: 1.03.10 ^-4 _m 2 s ^-1 (+ -10%)
• 1 part claw oil,
• 1 part soybean oil,
• 3 parts of Vaseline,
• 20 parts of low pressure polyethylene containing paraffin,
• 10 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of raw wax based ester wax (light),
• 5 parts of soft ester wax based on raw montane,
• 15 parts micro wax,
• 11 parts of 2-hydroxy-4- (2'-hydroxy-3'-methacryloxy) prop-oxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-undecyloxyphenyl) benzotriazole,
• 1 part [2,2'-thio-bis- (4-tert-butylphenolato)] - n-nonylamine-Mn (II),
• 3.8 parts of 2-n-octyl-thio-4,6-di- (4'-hydroxy-3 ', 5'-di-tert-butylphenoxy) -1,3,5-triazine,
• 0.2 parts 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c,] [1.4] -benzodiazepin-2- (trans) -acrylamide,
• 1 part [1-phenyl-3-methyl-4-undecanoyl-pyrozolate (5)] ₂ -Zn (II).

Example 15

• 1 part industrial oil according to DIN 51525 kinematic viscosity at 40 ° C: 2.2 · 10 ^-4 _m ² s ^-1 (+ -10%)
• 5 parts industrial oils according to DIN 51524 HL oil kinematic viscosity at 40 ° C: 1.0.10 ^-5 m ² s ^-1 (+ -10%)
• 4 parts of Vaseline,
• 30 parts of low-pressure polyethylene, modified with 30% paraffin,
• 10 parts hard paraffin from the Fischer-Tropsch synthesis,
• 5 parts of low-pressure polyethylene containing emulsifier,
• 20 parts micro wax,
• 10 parts raw wax based ester wax,
• 5 parts of 2-hydroxy-2'-phenyl-4-methoxy-4'-methyl-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 3 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 4 parts [1-phenyl-3-methyl-4-ethoxy-pyrazolate (5)] ₂ Zn (II).

Example 16

• 2 parts industrial oil according to DIN 51524 HLP oil kinematic viscosity at 40 ° C: 6.8 · 10 ^-5 _m ² _s - ¹ ( ₊ - _10% )
• 8 parts industrial oil according to DIN 515 KA oil kinematic viscosity at 40 ° C: 2.2 · 10 ^-5 m ² s ^-1 (+ -10%)
• 2 parts of Vaseline,
• 20 parts of acid wax on a raw montane basis,
• 30 parts of microcrystalline wax,
• 5 parts refined paraffin,
• 8 parts of emulsifier-containing wax based on polyethylene,
• 14 parts of 2-hydroxy-4-methoxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-3'-tert.butyl-5'-nonylphenyl) benzotriazole,
• 1.8 parts of 2-n-octylthio-4,6-di- (4'-hydroxy-3 ', 5'-ditert. Butylphenoxy) -1,3,5-triazine,
• 4 parts [2,2'-thio-bis- (4-tert.hexyl-4'-tert.octyl - phenolato)] - n-octylamine zinc (II),
• 0.2 parts 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1 H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide .

Examples 17 to 22 illustrate the application of the product mixtures from solvents.

Example 17

• 10 parts of partially saponified ester wax,
• 10 parts of soft ester wax,
• 20 parts of non-emulsifiable special polyethylene wax,
• 40 parts isopropanol,
• 8 parts of 2,4-dihydroxybenzophenone,
• 6 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 1 part of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 5 parts [2,2'-thio-bps- (4-tert.octyl-phenolato)] - 3,3-dimethylbutyl-amine-Zn (II).

The waxes are melted on a water bath and placed in a heatable pearl mill. Then the active ingredient mixture is slowly poured into the running mill and ground until a particle size of 6 μm is no longer exceeded.

The wax melt is cooled until it just begins to crystallize out. Then the isopropanol is added with rapid stirring using a dispersing disc, ice is quickly added to the water bath and stirring is continued until a creamy mass has formed.

This mass is then applied on a commercial machine in an amount of 1.5 to 6 g / m ² to the CF paper side of a paper with a weight of 40 g / m ² and freed from the solvent in the usual way.

Example 18

• 60 parts of partially neutralized polymethyl vinyl ether - maleic acid monoethyl ester (50% in isopropanol),
• 10 parts hydroxypropyl cellulose,
• 10 parts barium sulfate,
• 11 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone-5-sulfonic acid, sodium salt,
• 5 parts of 2- (2'-hydroxy-3 ', 5'-di-tert.butylphenyl) benzotriazole,
• 2 parts of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerithritol,
• 2 parts of [2,2'-thio-bis- (4-tert-octylphenolato)] - n-butylamine-Ni (II).

The polyvinylmethyl ether-maleic acid monoethyl ester solution is placed in a bead mill. The barium sulfate and the active substances are then added to the running mill and grinding is continued until a particle size of approximately 6 μm is reached. Only then is the hydroxypropyl cellulose added and ground again until 6 µm is reached. The cellulose is partially dissolved. The undissolved amount of cellulose is dispersed.

This results in a pasty mass, which preferably is used for the CF job, wherein the job in the print spot method using a commercially available device in an amount of 1.5 to 6 g / m ² is made to a paper of 4 ₀ g / m ^2.

Example 19

• 30 parts of acrylic polymer, 40% dispersion,
• 1.5 parts of dimethylamino ethanol,
• 35 parts isopropanol,
• 20 parts of low-pressure polyethylene modified,
• 5 parts of 2-hydroxy-2'-phenyl-4-methoxy-4'-methyl-benzophenone,
• 4 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 2 parts of 2,4,6-tris (3 ', 5'-ditert.butyl-4'-hydroxy-benzyl) mesitylene,
• 0.5 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-IH-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide ,
• 1 part [1-phenyl-3-methyl-4-tert-butyloxy-pyrazolate (5)] ₂ Zn (II),
• 1 part [2,2'-thio-bis- (4-tert.hexylphenolato)] - cyclohexylamine Zn (II).

The low pressure polyethylene is melted. The acrylate dispersion and the dimethylaminoethanol are then added with stirring. The mixture is heated with stirring until the water has evaporated. It is then placed in a heatable bead mill, mixed with the active ingredients and ground until a fineness of at least 6 µm is achieved.

The mass is then slowly added to isopropanol at about 30 ° C. while stirring with a dispersing disc and stirring is continued until a uniform paste is obtained. The paste is preferably processed further on a device of Example 19 and applied in an amount of 1.5-6 g / m ² to the CF paper side.

Example 20

• 60 parts of physically drying, oil-free alkyd resin, 50% in isopropanol,
• 20 parts of barium sulfate,
• 6 parts of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid,
• 6 parts of 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chloro-benzotriazole,
• 2 parts of 1,1,3-tris- (2'-methyl-4'-hydroxy-5 '- (tert.butyl - phenyl) butane,
• 6 parts [2,2'-thio-bis- (4-tert.dodecylphenolato)] - diethanolamine-Cu (II).

The active ingredients are placed together with the barium sulfate in a bead mill which had previously been filled with the alkyd resin solution. It is ground until there are no more particles with a particle size of more than 6 μm. The resulting viscous paste is processed as described in Example 17 or 18.

Example 21

• 50 parts of physically drying, alkyd resin containing abietic acid, 40% in isopropanol,
• 15 parts of barium sulfate,
• 15 parts of hydroxypropyl cellulose,
• 12 parts of 2-hydroxy-4-n-octoxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-3'-tert.butyl-5-nonyloxyphenyl) benzotriazole,
• 3 parts [1-phenyl-3-methyl-4-isobutylohypyrazolate (5172Zn (II).

The mixture of active ingredients is further processed to a particle size of at most 6 microns and according to Example 17 or 18.

Example 22 Solvent application

• 60 parts of diglycol esters of petrexic acid, 50% in isopropanol,
• 20 parts talcum powder,
• 11 parts of 2,4-dihydroxybenzophenone,
• 4 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-undecyloxyphenyl) benzotriazole,
• 4 parts [2,2'-thio-bis- (4-tert.octyl-4'-tert.hexylphenolato)] - n-hexylamine-Co (II),
• 1 part 2-n-octylthio-4,6-di- (4'-hydroxy-3 ', 5'-ditert. Butyl-phenoxy) -1,3,5-triazine.

The active ingredients and the talcum powder are mixed in a ball mill with balls with a minimum diameter of 1.5 cm for about 4 hours and ground intimately. The degree of fineness should be between 6 and 10 pm. This mixture is added by means of a shaking sieve to the 50% isopropanol solution of the diglycol ester of petrexic acid with rapid stirring until a uniformly creamy mass has formed, which is processed as described in Example 17 or 18.

Examples 23 to 29 illustrate the application of the product mixture from aqueous dispersion.

Example 23

• 30 parts of partially saponified wax,
• 10 parts of emulsifier-containing polyethylene wax,
• 40 parts of 57% polyvinyl acetate dispersion with cellulose derivative as protective colloid,
• 4 parts of water
• 1 part barium sulfate,
• 7 parts of 2,2 ', 4,4'-tetrahydroxy-benzophenone,
• 4 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 1 part of 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxy-benzyl) mesitylene,
• 2 parts of [1-phenyl-3-methyl-4-methoxy-pyrazolate (5)] ₂ Zn (II),
• 1 part [2,2'-thio-bis- (4-tert-octyl-4'-tert-butyl-phenolato)] - n-dodecylamine-Zn (II).

The wax mixture is melted and transferred to a heated bead mill. The barium sulfate is added to the running mill using a shaking sieve. After thorough mixing, the active ingredients are also added using a shaking sieve and the mixture is ground for 2-4 hours until a fineness of at most 10 µm is reached.

The mixture of waxes and solids is added to the PVA dispersion with rapid stirring and the additional water is also added with rapid stirring.

The processable paste is layered on a 55 g / m ² paper in a quantity of 6 g / m ² as a CF application using a commercially available channel coating machine.

Example 24

• 30 parts of modified polyethylene wax containing emulsifier,
• 10 parts of carnauba wax,
• 20 parts water,
• 25 parts of hydroxyethyl cellulose,
• 7 parts of 2-hydroxy-4-dodecyloxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-sulfonic acid - phenyl) -5-chloro-benzotriazole,
• 3 parts [2,2'-thio-bis- (4-tert-dodecylphenolato)] - n-propylamine-Ni (II).

The waxes are melted and the active substances and the hydroxyethyl cellulose are slowly added to them in a bead mill during the milling and then well milled for 2-4 hours. When a level of 6 µm is reached, the wax-solid mixture is gradually dispersed into a vessel with hot water with constant stirring. Part of the wax is emulsified, another part is very finely dispersed together with the solids.

After the mixture has cooled slowly with stirring, it can be processed further. It is layered as a CF application on paper of 50 g / m ² using a commercially available machine in an amount of 4 g / m ² .

Example 25

• 15 parts Chinaclay,
• 15 parts of chemically passive aluminum-containing magnesium silicate with high adsorption capacity,
• 15 parts Attasorb,
• 5 parts water glass,
• 10 parts of acrylic dispersion (50%),
• 40 parts water,
• 8 parts of 2,2'-dihydroxy-4-methoxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 4 parts of [1-phenyl-3-methyl-4-tert-pentoxy-pyrazolate (5)] ₂ Zn (II).

The active ingredients are thoroughly ground with clay, Attasorb and water glass. The mixture is then added to the acrylate dispersion with constant stirring and then diluted to the final concentration with water.

The product obtained is suitable for CF application as described in Example 23 or 24.

Example 26

• 30 parts barium sulfate,
• 5 parts water glass,
• 15 parts of acrylic dispersion (50%),
• 25 parts water,
• 12 parts of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid,
• 6 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 5 parts of 2-n-octylthio-4,6-di- (4'-hydroxy-3 ', 5'-di-tert-butyl-phenoxy) -1,3,5-triazine,
• 2 parts [1-phenyl-3-methyl-4-ethoxy-pyrazolate (5)] ₂ Zn (II).

The aqueous dispersion is prepared in accordance with Example 24 and applied to paper as a CF application.

Example 27

• 10 parts of partially saponified wax with a non-ionic emulsifier added by the manufacturer,
• 10 parts of low-pressure polyethylene containing emulsifier,
• 5 parts of polyvinylpyrrolidone,
• 25 parts water,
• 10 parts of hydroxyethyl cellulose,
• 20 parts BaS04,
• 8 parts of 2-hydroxy-4- (2'-hydroxy-3'-methacryloxy) propoxy-benzophenone,
• 8 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 4 parts [2,2'-thio-bis- (4-tert.hexylphenolato)] - n-octylamine-Ni (II).

The wax and the polyethylene are melted and transferred to a heated bead mill. Using a shaking sieve, polyvinylpyrrolidone, barium sulfate and hydroxyethyl cellulose are then added to the running mill. Then the active substances are added in the same way and the mixture is ground for 2-4 hours until a fineness of at most 10 pm is reached. The mixture obtained is poured into hot water, as in Example 23, with rapid stirring, the waxes emulsifying and the solids being dispersed. The mixture is slowly stirred until it cools.

The dispersion obtained is coated as a CF application on paper as described in Examples 23 and 24.

Example 28

• 25 parts of low-pressure polyethylene containing emulsifier,
• 30 parts of polyacrylate dispersion (46%),
• 1 part olein,
• 10 parts of ethyl hydroxyethyl cellulose,
• 10 parts barium sulfate,
• 5 parts cross-linked polyvinylpyrrolidone,
• 11 parts of 2,2'-dihydroxy-4-methoxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert.butyl-5'-tert.octylphenyl) -5-chlorobenzotriazole,
• 2 parts of 2-n-octylthio-4,6-di- (4'-hydroxy-3 ', 5'-di-tert-butyl-phenoxy) -1,3,5-triazine,
• 0.5 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] L1.47-benzodiazepine-2- (trans) -acrylamide,
• 1.5 parts of [2,2'-thio-bis- (4-tert.octylphenolato)] - n-butylamine-Ni (II),
• 1 part [1-phenyl-3-methyl-4-propoxy-pyrazolate (5)] Fe (II).

The aqueous dispersion is prepared in accordance with Example 24, the wax-solid mixture being added to the polyacrylate dispersion with rapid stirring.

The paper coating as a CF application is carried out as described in Example 23 or 24.

Example 29

• 5 parts cross-linked polyvinylpyrrolidone,
• 25 parts of sodium polyacrylate dispersion (14%),
• 20 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of barium sulfate,
• 10 parts of ethyl hydroxyethyl cellulose,
• 15 parts of 2-hydroxy-4-n-octoxy-benzophenone,
• 2 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-sulphonic acid - phenyl) -5-chloro-benzotriazole,
• 2 parts of [2,2'-thio-bis- (4-tert.octylphenolato)] - n-butylamine-Zn (II),
• 1 part [1-phenyl-3-methyl-4-hexyloxy-pyrazolate (5)] ₂ -Zn (II).

The aqueous dispersion is prepared and CF coated as described in Examples 27 and 23.

Examples 30 to 35 illustrate the processing of the product mixtures into the pulp in the paper machine.

Example 30

• 15 parts of partially saponified wax AV 1551,
• 17 parts of 2-hydroxy-4-dodecyloxy-benzophenone,
• 14 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 11 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) butane,
• 3 parts L2,2'-thio-bis- (4-tert.octyl-4'-tert.butyl - phenolato)] - n-dodecylamine-Zn (II),
• 40 parts of water.

The wax is melted and ground with the active ingredients in a pearl mill to a fineness of maximum 6 pm. The dispersion is then prepared using the wax-in-water method using a dispersing disc and a high-speed stirrer, the wax being emulsified.

15 parts of the dispersion thus obtained are added with stirring to 85 parts of sulfite wood pulp with an impact ratio of 45 ° SR (Schopper-Riegler freedom), which had been diluted with water to 0.8% in the Dutch after the treatment.

The resulting total slurry is then further processed in such a way that it is metered onto a Foudrinier paper machine by means of an outlet box. The active substance-filled paper felt is then created on the forming sieve, which is further processed as usual.

The paper thus obtained can either be coated with capsules itself (single-layer paper) or serve as a CF sheet for existing capsule paper.

Examples 31 to 35

The ingredients of the composition given below are mixed in a large ball mill and ground simultaneously. The well-mixed mixture is then metered into the filling kaolin by means of a shaking sieve in such a way that, based on the kaolin addition, about 3 to 6% of the active ingredient mixture is obtained. The storage container for the active ingredients should expediently be attached in such a way that the elevator, which, as is customary in paper machines, conveys the kaolin from the discharge funnel into the dissolving pulp, can be dosed, the active ingredients there with the sulfite-sulfate pulp in water using conventional paper-making chemicals be mixed up. The entire slurry is processed from there in the usual way.

The following active ingredient mixtures were used:

Example 31

• 8 parts of 2,4-dihydroxy-benzophenone,
• 6 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole,
• 1 part of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) butane,
• 5 parts of [2,2'-thio-bis- (4-tert.octylphenolato)] - 3,3-dimethylbutyl-amine-Zn (II).

Example 32

• 12 parts of 2-hydroxy-4-n-octoxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-3'-tert.butyl-5'-nonylphenyl) benzotriazole,
• 3 parts [1-phenyl-3-methyl-4-isobutyloxy-pyrazolate (5)] ₂ Zn (II).

Example 33

• 11 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone-5-sulfonic acid, sodium salt,
• 5 parts of 2- (2'-hydroxy-3 ', 5'-di-tert.butylphenyl) benzotriazole,
• 2 parts of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerithritol,
• 2 parts [2,2'-thio-bis- (4-tert.octylphenolato)] - n-butylamine-Ni (II).

Example 34

• 5 parts of 2-hydroxy-2'-phenyl-4-methoxy-4'-methyl-benzophenone,
• 4 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 2 parts of 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxy-benzyl) mesitylene,
• 0.5 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide,
• 1 part [1-phenyl-3-methyl-4-tert-butyloxy-pyrazolate (5)] ₂ Zn (II),
• 1 part [2,2'-thio-bis- (4-tert.hexylphenolato)] - cyclohexylamine Zn (II).

Example 35

• 6 parts of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid,
• 6 parts of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole,
• 2 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 6 parts [2,2'-thio-bis- (4-tert.dodecylphenolato)] - diethanolamine-Cu (II).

Examples 36 and 37 illustrate the incorporation of the active ingredient mixtures into an ink base.

Example 36

• 50 parts of finished varnish (viscosity 65 Pas)
• 10 parts of blown linseed oil (viscosity 6 Pas)
• 10 parts barium sulfate,
• 12 parts of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone,
• 12 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole
• 3 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 3 parts [2,2'-thio-bis- (4-tert.octyl-phenolato)] - cyclohexyl-diethanolamine-Ni (II).

The active ingredients are pasted with the linseed oil and then milled together with the barium sulfate and the finished varnish in a pearl mill until a grain size of less than 4 µm is reached. The finished printing paste, which is particularly suitable for the production of rolled goods such as continuous forms, is layered onto continuous paper of 60 g / m ² in an amount of 0.5 g / m ² on a device of a commercial design.

Example 37 Processing as printing ink

• 70 parts of finished printing varnish (viscosity 45 Pas),
• 5 parts of blown linseed oil,
• 10 parts of 2-hydroxy-4-methoxy-benzophenone,
• 9 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 6 parts of 2,4,6-tris (3 ', 5-di-tert-butyl-4'-hydroxy-benzyl) mesitylene.

The ingredients are mixed, ground and processed as described in Example 36.

Claims (15)

1. Pressure-sensitive recording material with improved shelf life, light fastness and heat resistance, which consists of a unit containing a dye precursor or its solution and a unit containing a dye acceptor material which is capable of color formation by reaction with the dye precursor, characterized in that the dye acceptor material consists of a there is an intimate mixture a) either aa) a 2-hydroxy-benzophenone of the formula I.

wherein R _{1 is} a hydroxyl group, an unsubstituted alkoxy radical with 1 to 18 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms, which carries 1 or 2, optionally esterified with a saturated or olefinically unsaturated carboxylic acid with 2 to 4 carbon atoms, R _{2 is} hydrogen, is a phenyl group, the sulfonic acid group -S0 ₃ H or the group _-S03Me , where Me is an alkali metal, R _{3 is} hydrogen, the hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a Is phenyl and R _{4 is} hydrogen, the hydroxyl group, a phenyl group, the carboxy group -COOH, the group -COOMe, where Me is an alkali metal, or bb) 3,5,7,3 ', 4'-pentahydroxy-flavon of formula II

and b) a substituted benzotriazole of the formula. III

wherein R _{1 is} hydrogen or the tert. Butyl group, R ₂ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, the cyclohexyl radical, the sulfonic acid group -SO ₃ H or the group -S0 ₃ Me, where Me is an alkali metal, and R ₃ is hydrogen or chlorine is
and optionally contains an inert waxy binder. 2. Pressure-sensitive recording material according to claim 1, characterized in that the dye acceptor material additionally 2,4,6-tris (3 ', 5-di-tert-butyl-4'-hydroxy-benzyl) mesitylene, 1,1,3 -Tris- (2'-methyl-4'-hydroxy-5'-tert-butyl-phenyl) -butane, ß- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid-n- octadecyl ester, β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerythritol and / or a 2-n-alkylthio-4,6-di- (3 ', 5'- di-tert.butyl-4'-hydroxy-phenoxy) -1,3,5-triazine, the alkylthio radical having 4 to 12 carbon atoms. 3. Pressure-sensitive recording material according to claim 1 or 2, characterized in that the dye acceptor material additionally a compound of formula IV

wherein R ₁ and R ₂ , which may be the same or different, are branched-chain alkyl groups with 6 to 12 carbon atoms, R _{3 is} an alkyl group with 3 to 12 carbon atoms or a cycloaliphatic radical, in which case R ₄ and R _{5 are} hydrogen atoms, or one, two or three of the radicals R ₃ , R ₄ and R _{5 are} hydroxyalkyl radicals having 2 to 6 carbon atoms and the other radicals are hydrogen atoms, and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va. 4. Pressure-sensitive recording material according to one or more of claims 1 to 3, characterized in that the dye acceptor material 0.1 to 0.5 wt .-% 5,10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl -5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzorliazepin-2- (trans) -acrylamide contains. 5. Pressure-sensitive recording material according to one or more of claims 1 to 4, characterized in that the dye acceptor material is coated on one side of the sheet-like or web-shaped support material in an amount of 0.5 to 6 g / m ^{2 of} support material. 6. Pressure-sensitive recording material according to one or more of claims 1 to 5, characterized in that the dye acceptor material contains [1-phcnyl-3-methyl-4-alkyl ether pyrazolate (5)] - Me complex salt, the alkyl ether residue having an alkoxy group Is 1 to 12 carbon atoms and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va. 7. A method for producing pressure-sensitive recording materials according to one or more of claims 1 to 6, characterized in that either a) a melt of the components of the dye acceptor material or a solution thereof in a suitable solvent is applied to one side of the carrier material in an amount of 0.5-6 g / m ² and the carrier material coated in this way is further processed as usual or b) Cellulose fibers are ground with the components of the dye acceptor material to the desired particle size and the product is mixed with the paper pulp intended for the production of the sheet or web-shaped carrier material before the sizing agent is added, and the paper pulp thus obtained is further processed in the usual manner to form the sheet or web-shaped carrier material. 8. A sheet-like or web-shaped unit containing a dye acceptor material for pressure-sensitive recording materials, comprising a unit containing a dye precursor or its solution and a unit containing a dye acceptor material which is capable of forming color by reaction with the dye precursor, characterized in that the dye acceptor material consists of an intimate mixture , the a) either aa) a 2-hydroxy-benzophenone of the formula I.

wherein R _{1 is} a hydroxyl group, an unsubstituted alkoxy radical with 1 to 18 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms, which carries 1 or 2, optionally esterified with a saturated or olefinically unsaturated carboxylic acid with 2 to 4 carbon atoms, R _{2 is} hydrogen, is a phenyl group, the sulfonic acid group -S0 ₃ H or the group -SO ₃ Me, where Me is an alkali metal, R _{3 is} hydrogen, the hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a phenyl group , and R _{4 is} hydrogen, the hydroxyl group, a phenyl radical, the carboxy group -COOH, the group -COOMe, where Me is an alkali metal, or bb) 3,5,7,3,4'-pentahydroxy-flavon of the formula II

and b) a substituted benzotriazole of the formula III

wherein R _{1 is} hydrogen or the tert. Butyl group, R ₂ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, the cyclohexyl radical, the sulfonic acid group -SO ₃ H or -SO ₃ Me, where Me is an alkali metal, and R ₃ is hydrogen or chlorine is
and optionally contains an inert waxy binder. 9. sheet or web-shaped, dye acceptor material-containing unit according to claim 8 for pressure-sensitive recording materials with multiple copies, characterized in that the carrier material coated on one side with the dye acceptor material and optionally the inert wax-like binder and on the other hand with the dye precursor in a conventional manner is. 10. Sheet or web-shaped unit containing dye acceptor material according to patent claims 8 or 9 for pressure-sensitive recording materials, characterized in that the dye acceptor material additionally contains 2,4,6-tris (3 ', 5'-di-tert.butyl-4'- hydroxybenzyl) mesitylene, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-tert-butyl-phenyl) -butane, β- (3,5-di-tert-butyl-4 -hydroxyphenyl) -propionic acid-n-octadecyl ester, ß- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid ester of pentaerythritol and / or a 2-n-alkylthio-4,6-di- ( 3 ', 5'-di-tert-butyl-4'-hydroxy-phenoxy) -1,3,5-triazine, the alkylthio radical having 4 to 12 carbon atoms. 11. Sheet or web-shaped, dye acceptor material containing unit according to one or more of claims 8 to 10 for pressure-sensitive recording materials, thereby characterized in that the dye acceptor material additionally a compound of formula IV

wherein R ₁ and R _29, which may be the same or different, are branched chain alkyl groups with 6 to 12 carbon atoms, R _{3 is} an alkyl group with 3 to 12 carbon atoms or a cycloaliphatic radical, in which case R ₄ and R _{5 are} hydrogen atoms, or one or two or three of the radicals R ₃ , R ₄ and R _{5 are} hydroxyalkyl radicals having 2 to 6 carbon atoms and the other radicals are hydrogen atoms, and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va. 12. Sheet or web-shaped unit containing dye acceptor material according to one or more of claims 8 to 11, characterized in that the dye acceptor material 0.1 to 0.5 wt .-% 5,10,11,11α-tetrahydro-9,11 -dihydroxy-8-methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide contains. 13. Sheet or web-shaped unit containing dye acceptor material according to one or more of claims 8 to 12, characterized in that the dye acceptor material [1-phenyl-3-methyl-4-alkyl ether] contains pyrazolate (5L7-Me complex salt, the alkyl ether radical being an alkoxy group having 1 to 12 carbon atoms and Me being Co, Ni, Mn, Zn, Fe, Cur, Cr or Va. ₁₄ . Sheet or sheet-shaped unit containing dye acceptor material according to one or more of claims 8 to 13, characterized in that the dye acceptor material is coated on one side of the sheet or sheet-shaped support material in an amount of 0.5 to 6 g / m ^{2 of} support material . 15. A process for the preparation of the sheet-like or sheet-shaped unit containing dye acceptor material according to one or more of claims 8 to 14, characterized in that either a) a melt of the components of the dye acceptor material or a solution thereof in a suitable solvent is applied to one side of the carrier material in an amount of 0.5-6 g / m ² and the carrier material coated in this way is further processed as usual or b) Cellulose fibers are ground with the components of the dye acceptor material to the desired particle size and the product is mixed with the paper pulp intended for the production of the sheet or web-shaped carrier material before the sizing agent is added, and the paper pulp thus obtained is further processed in the usual manner to form the sheet or web-shaped carrier material.