EP0036117B1 - Pressure-sensitive recording material - Google Patents

Description

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

Such a color developer material is known from GB-A 2,017,730 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 if the dye precursor or its solution comes into contact with the dye acceptor through the action of an external physical force, such as, in particular, pressure. 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 bears this on its back and is then called a CB sheet or web, the unit having the dye acceptor generally bears it on its front and is then called CF sheet or CF sheet. The sheet-like or web-like carrier material carrying the dye-acceptor layer can in turn carry a dye precursor or a layer containing its solution on its other surface, which is combined with a further sheet-like or web-like CF unit containing dye-acceptor, so that a three-sheet recording material is given, with which two copies can be made 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 is carried out 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 during 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 slightly 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-dimethylaminophthalide) 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 described in DE-PS 14 21 394 or Pyridine carboxylic acid lactones such as, for example are disclosed in DE-PS 2412 640.

Daneben dürfte geringfügig ein Carbeniumion aufweisende Tritylgrenzstruktur vorliegen:

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 precursor, crystal violet lactone (CVL for short). Crystalline violet lactone is one of the dyes that, due to its constitution, can assume various boundary structures that are responsible for color formation.

In addition, there is likely to be a trityl border structure with carbenium ion:

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 blow up the lactone ring of the crystal violet lactone by reaction with other substances (dye acceptors) and thus to form the other boundary structures and thus to maintain 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 montmorrillonite 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 great 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. Furthermore, phenol groups substituted with electron-withdrawing groups, i.e. those with a positive mesometric effect built in, so that 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, GB-OS 2 017 730). To improve the stability of the resulting color, it was proposed according to DE-A8 2 219 556 to coat a phenol-formaldehyde polymer on basic pigments and to improve the light stability those for heat-sensitive copying materials e.g. to use benztriazoles known from JP-AS 8023205 as UV absorbers. 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 8alicylic 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 dye precursors are also used in carbonless papers. A common secondary dye precursor 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 metal salts added to the phenolic bodies or the clay mixtures, the exchange of the Benzoic acid anions frequently react against 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 GB 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 'bleeding through' 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 occur on a CB-coated cover sheet after the writing set has been compiled has been.

Attempts have also already been made to improve the lightfastness of the primary dye precursor, i.e. the triphehylmethane dye, by adding other substances before fading, i.e. protect from exposure to light. On the one hand, the alkaline earth metal carbonates, which absorb UV light, are used for this purpose. 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. Other such additives such as diaminostilbene and benzimidazole are described in DE-AS 1 809 778.

In addition to the unwanted fading of the font after its intended creation, there is a second major problem with carbonless papers, namely the premature development of discolourations that make 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 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 storage period. 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.But even with white papers, caution is advised, because many papers are coated with kaolin, a type of clay, or they contain tannin, which then often coats in dye-acceptor layers contained metal ions can react and form discoloration, so that the discoloration is not caused by the dye. Ultramarine is also often added to yellow papers, which approximates the molecular formula SigA! ₃ Na ₄ S ₂ 0 _i2 . Ultramarine makes the paper appear white through a complementary color reaction. This clay-like substance is also predestined to react with triphenylmethane dyes. In view of the large extent to which Ultramarine is sold in the paper industry, the risk of buying a '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 the pressure develops 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 decolorized by benzene, toluene or xylene. 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, coloring occurs with such fatty acids, 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 appearances can still be considerably extended and explains that without precise knowledge of the papers used in the production of the paper used as supports in carbonless papers and similar pressure-sensitive recording materials and the printing inks and solvents used for the production of printed carbonless papers, the production of such pressure-sensitive recording materials and their storage and Use is extremely difficult and the occurrence of one or the other or more of the disadvantages described can not be foreseen at all.

It is an object of the present invention to provide a dye acceptor material which reacts with all of the triphenylmethane dye precursors or dye formers which react analogously to produce a permanent, sufficiently strong color effect, thereby avoiding the undesired side effects described above as comprehensively as possible and thus regardless of whether in CB or CF. Arrangement or arranged on a support material coated on both sides or incorporated into the support material, which enables the production of pressure-sensitive recording materials with improved storage stability, light fastness and heat resistance.

• a) entweder
• aa) ein 2-Hydroxy-benzophenon der Formel
  

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. That the dye acceptor material of the pressure-sensitive recording material according to the invention consists of an intimate mixture that

• a) either
• aa) a 2-hydroxy-benzophenone of the formula
  

• bb) das Hydroxyflavon Quercetin, d.h. das 3,5,7,3',4'Pentahydroxy-flavon der Formel II
  und
  
• b) ein substituiertes Benztriazol der Formel 111
  

wherein R is a hydroxyl group, an unsubstituted alkoxy radical having 1 to 18 carbon atoms or an alkoxy radical having 1 to 4 carbon atoms which carries 1 or 2, optionally hydroxylated 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) the hydroxyflavon quercetin, ie the 3,5,7,3 ', 4'pentahydroxyflavon of the formula II
  and
  
• b) a substituted benzotriazole of the formula 111
  

wherein R _{1 is} hydrogen or the tert. Butyl group, R _{2 is} an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, the cyclohexyl group, 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.

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'-hydroxy5'-tert-butylphenyl) butane, the β- (3,5, -Di-tert.butyl4-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 stability is achieved by mixing one or more of these special phenol derivatives with both the a-ketophenols of the formulas I or II and the benzotriazole derivative of the formula III.

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

in addition, wherein R _i and R ₂ , which are 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 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 Co, Ni, Mn, Zn, Fe, Cu, Is Cr or V. R ₃ is preferably an n-alkyl 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.

According to a further embodiment, the dye acceptor material contains, in addition to the components of the formulas I or II and III and preferably also in addition to the other components listed above, 0.1 to 1% by weight, preferably 0.1 to 0.5% by weight 5, 10,11,11a-tetrahydro-9,11-dihydroxy-8-methyl-5-oxo1H-pyrrolo [2.1-c] [1.4j-benzodiazepine-2- (trans) -acrylamide Formula V

This active ingredient, which is well known in the field of medicine, is not only able to react with the phenolic hydroxyl group present in the 9-position with the triphenylmethane dye precursor products, but due to 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, can be used instead of the previously known urea derivatives with an improved result and thereby a premature reaction of the dye precursor products with the Avoid components of the dye acceptor material when printing through high paper stacks or tightly wound rolls of web-shaped pressure-sensitive recording material.

According to a preferred embodiment, the dye acceptor material according to the invention contains, in addition to the components of the formulas I or II and 111, both at least one of the special phenols, one of the complex metal salts of the formula IV 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-alkyl ether pyrazolate (5) j-Me (II) - Complex salt are used, the alkyl group in the alkyl ether residue containing 1 to 12 carbon atoms in a straight or branched arrangement and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or V. The nickel complexes are colored pale green. The metal complexes which are preferably used 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 around or if necessary treated with ultrasound during the application in order to obtain a layer that is always perfectly homogeneous.

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 can be 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. Furthermore, so-called snapout sets can also be produced with such thin papers if papers of conventional strength of approx. 30 to 70 g / m 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

• Die Wirkstoffe und gegebenenfalls vorhandene Füllstoffe wie Bariumsulfat und Cellulosederivate werden je nach Rezept in den Ölprodukten verrührt und gegebenenfalls mit den Fettprodukten angeteigt bzw. in die geschmolzenen Wachse bzw. deren Gemische mit wachsartigen Kunststoffen gegeben und in einer Kugelmühle unter weiterer Wärmezufuhr (je nach Mühlenart) 3 bis 4 Stunden vermahlen, bis ein Vermahlungsgrad erreicht ist, der sonst für Kehlepapierfarben üblich ist (Feinheitsgrad ca. 6 -10 um).

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 which is otherwise customary for throat paper colors (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 ² when 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 used is the material customary in the production of carbon-free papers, 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 m ² 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 [1-phenyl-3-methyl-4-propoxy-pyrazolate (5) 1 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 of 5 10, 11, 11α-tetrahydro-9, 11-dihydroxy-8methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-2- (trans) -acrylamide,
• 2.6 parts of [1-phenyl-3-methyl-4-tert-octyloxy-pyrazolate (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 (+ -1 G%)
• 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-butyl-phenoxy) -1,3,5-triazine,
• 0.5 parts 5, 10, 11, 11α-tetrahydro-9, 11-dihydroxy-8-methyl5-oxo-1H-pyrroto [2.1-c] [.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 on raw montane basis,
• 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'-dodecyl-phenyl) 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 1.0.70-4 m ² s ^-1 (+ -10%)
• 2 parts claw oil,
• 3 parts of Vaseline,
• 10 parts catalytically oxidized wax from Fischer-Tropschund 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) -5chloro-benzotriazole.

Example 6

• 3 parts industrial oil according to DIN 51517 CLP oil kinematic viscosity at 40 ° 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) -5chlorobenzotriazole,
• 4 parts of ß- (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 ^-3 m ² s ^-1 (+ -10%)
• 5 parts of Vaseline,
• 20 parts of low-pressure polyethylene containing emulsifier,
• 20 parts of 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)] - nbutylamine-Ni (II).

Example 8

• 5 parts of 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)] - nhexylamine-Co (II),
• 4 parts of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ester of pentaerithritol.

Example 9

• 5 parts of 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 methyl hydroxypropyl cellulose,
• 8 parts barium sulfate,
• 8 parts of 2,2 ', 4,4'-tetrahydroxy-benzophenone,
• 8 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
• 2 parts of [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-8-methyl5-oxo-1H-pyrrolo [2.1-c] [.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 of [2,2'-thio-bis- (4-tert.octylphenolato)] - nbutylamine-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 of [2,2'-thio-bis- (4-tert.octylphenolato)] - nbutylamine-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-penyl) benzotriazole, sodium salt,
• 0.5 parts of 5,10,11,11d-tetrahydro-9, 11-dihydroxy-8methyl-5-oxo-1H-pyrrolo [2.1-c] [1.4] -benzodiazepine-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-Tropschund 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 [-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) propoxy-benzophenone,
• 3 parts of 2- (2'-hydroxy-3'-tert-butyl-5'-undecyloxyphenyl) benzotriazole,
• 1 part [2,2'-thio-bis- (4-tert-butylphenolato)] -nnonylamine-Mn (II),
• 3.8 parts of 2-n-octyl-thio-4,6-di- (4'-hydroxy-3 ', 5'-ditert.butyl-phenoxy) -1,3,5-triazine,
• 0.2 parts of 5,10,11,11α-tetrahydro-9,11-dihydroxy-8methyl-5-oxo-1 H-pyrrolo [2.1-c] [.4] -benzodiazepine-2- (trans) -acrylamide,
• 1 part [-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 of 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 01 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'-nonyl-phenyl) 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.octylphenolato)] -n-octylamine zinc (II),
• 0.2 parts 5.10,11,11α-tetrahydro-9,11-dihydroxy-8-methyl5-oxo-1H-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 - ('- methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 5 parts [2,2'-thio-bis- (4-tert.octylphenolato)] - 3,3dimethylbutylamine 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 and 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-butyl-phenyl) 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.octyl-phenolato)] -nbutylamine-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.

A paste-like mass is formed, which is preferably used for the CF application, the application using the pressure spot method using a commercially available device in an amount of 1.5 to 6 g / m ² on a paper of 40 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-methyl5-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 of [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 heated pearl mill, the active ingredients are added and the mixture is 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'-dihert.butyl-phenyl) -5chloro-benzotriazole,
• 2 parts of 1,1,3-tris- (2'-methyl-4'-hydroxy-5 '- (tert.butylphenyl) butane,
• 6 parts of [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-nonyloxy-phenyl) benzotriazole,
• 3 parts of [-phenyl-3-methyl-4-isobutyloxy-pyrazolate (5) ₂ ] Zn (II).

The mixture of the active ingredients is processed up 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 of 2-n-octylthio-4,6-di- (C4'-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 Minoest diameter of 1.5 cm for about 4 hours and ground intimately. The degree of fineness should be between 6 and 10 µm. This chemical mixture is added to the 50% isopropanol solution of the diglycol ester of petrexic acid by means of a shaking sieve, 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 [-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 (11).

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 wax 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 an amount 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-dodecyl-phenolato)] -npropylamine-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 fineness of 6 µm is reached, the wax-solid mixture is gradually dispersed in 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 applied as CF application on paper of 50 g / m ² in a quantity of 4 g / m ² using a commercially available machine.

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 [-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 BaS0 ₄ ,
• 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)] - noctylamine-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 add the active substances in the same way and grind the mass for 2 - 4 hours until a fineness of at most 10 µm 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-methyl5-oxo-1H-pyrrolo [2.1-c] [.4] -benzodiazepin2- (trans) -acrylamide,
• 1.5 parts of [2,2'-thio-bis- (4-tert.octylphenolato)] - nbutylamine-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)] - nbutylamine-Zn (II),
• 1 part [I-phenyl-3-methyl-4-hexyloxy-pyrazolate (5)] ₂ Zn (II).

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

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 [2,2'-thio-bis- (4-tert.octyl-4'-tert.butylphenolato)] - 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 µm. 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 oesame 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)] -3,3dimethylbutylamine Zn (II).

Example 32

• 12 parts of 2-hydroxy-4-n-octoxy-benzophenone,
• 5 parts of 2- (2'-hydroxy-3'-tert-butyl-5-nonyl-phenyl) benzotriazole,
• 3 parts [I-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-butyl-phenyl) 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-octyl-phenolato) 45A -nbutylamine-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 5,10,11,11µ-tetrahydro-9,11-dihydroxy-8-methyl5-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 of [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-butyl-phenyl) 5-chloro-benzotriazole,
• 2 parts of 1,1,3-tris (2'-methyl-4'-hydroxy-5'-tert.butylphenyl) butane,
• 6 parts of [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.octylphenolato)] - 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 which comprises a unit containing a dye precursor or a solution thereof and a unit containing a dye acceptor material, which is capable of color formation by reaction with the dye precursor, said dye acceptor containing benztriazol derivatives for the improvement of storability and lightfastness, characterised in that the dye acceptor material is an intimate mixture comprising, besides the substituted benztriazol of formula III

where R₁ is hydrogen or the tertiary butyl group, R₂ an alkyl residue with from 1 to 12 carbon atoms, an alkoxy residue with from 1 to 12 carbon atoms, the cyclohexyl residue, the sulphonic acid group -S0₃H or the group - S0₃Me, Me being an alkali metal, and R₃ is hydrogen or chlorine, and, possibly, an inert wax binder,
either

a) a 2-hydroxy-benzophenone of formula I

where R₁ is a hydroxy-group, an unsubstituted alkoxy residue with from 1 to 18 carbon atoms or an alkoxy residue with from 1 to 4 carbon atoms, carrying 1 or 2 hydroxy-groups, an alkoxy residue with from 1 to 4 carbon atoms, carrying 1 or 2 hydroxy groups and esterified with a saturated or olefinically unsaturated carboxylic acid with from 2 to 4 carbon atoms, R₂ is hydrogen, a phenyl residue, the sulphonic acid group -S0₃H or the group - S0₃Me, Me being an alkali metal, R₃ is hydrogen, the hydroxy group, an alkyl group with from 1 to 12 carbon atoms, an alkoxy group with from 1 to 18 carbon atoms or a phenyl residue, and R₄ is hydrogen, the hydroxy group, a phenyl residue, the carboxy group -COOH or the group -COOMe, Me being an alkali metal,
or

b) 3,5,7,3',4'-pentahydroxy-flavone of formula II

2. Pressure-sensitive recording material according to claim 1, characterised in that the dye acceptor material, in addition, contains 2,4,6-tris-(3',5'-di-tert.butyl-4'-hydroxybenzyl)-mesitylene, 1,1,3-tris-(2'-methyt-4'-hydroxy-5'-tert.butyl-phenyl)butane, octadecyl β-(3,5-Di-tert.butyl-4-hydroxyphenyl)propionate, pentaerythritol p-(3,5-di- tert.butyl-4-hydroxyphenyl)propionate, or a 2-n-alkylthio-4,6-di-(3',5'-di-tert.butyl-4'-hydroxyphenoxy)1,3,5-triazine, the alkylthio residue having from 4 to 12 carbon atoms and mixtures thereof.

3. Pressure-sensitive recording material according to claim 1 or 2, characterised in that the dye acceptor material, in addition.' contains a compound of formula IV

where R₁ and R₂ which may be identical or different, are branched chain alkyl groups with from 6 to 12 carbon atoms, R₃ is an alkyl group with from 3 to 12 carbon atoms or a cyclo-aliphatic residue, in which case R₄ and R₅ then are hydrogen atoms, or one, two or three of the residues R₃, R₄ and R₅ are hydroxy-alkyl residues with from 2 to 6 carbon atoms, the other residues then being hydrogen atoms, and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va.

4. Pressure-sensitive recording material according to claims 1 to 3, characterised in that the dye acceptor material contains from 0.1 to 0.5 % by weight of 5,10,11,11α-tetryhydro-9,11-dihydroxy-8methyl-5-oxo-1H-pyrrolo[2.1-c][1.4]-benzodiazepine-2-(trans)-acrylamide.

5. Pressure-sensitive recording material according to claims 1 to 4, characterised in that it contains the dye acceptor material on the one side of the sheet- or web-like support material in an amount of 0.5 to 6 g/m² of the support material.

6. Pressure-sensitive recording material according to claims 1 to 5, characterised in that the dye acceptor material contains [I-phenyl3-methyl-4-alkylether-pyrazolate(5)] Me complex salt, the alkyl ether residue being an alkoxy group with from 1 to 12 carbon atoms and Me being Co, Ni, Mn, Zn, Fe, Cu, Cr or Va.

7. Process for producing pressure-sensitive recording materials according to one or several of claims 1 to 6, characterised in that either a) a melt of the components of the dye acceptor material or a solution thereof in a suitable solvent is coated to the one side of the support material in an amount of 0.5 to 6 g/m² and the so coated support material is further processed in usual manners or b) cellulose fibers together with the components of the dye acceptor material are milled to the desired particle size and the thus obtained product is admixed to the paper pulp intended for the production of the sheet or web-like support materialbefore the addition the glue material and the thus obtained paper pulp is further processed to the sheet or web-like support material in usual manners.

8. For a pressure-sensitive recording material comprising 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, a sheet-like, dye acceptor material containing unit consisting of a carrier material which is in sheet or web form, coated on one side with the dye acceptor material and benztriazol derivatives, characterised in that the dye acceptor material is an intimate mixture comprising, besides the substituted benztriazol of formula III

where R, is hydrogen or the tertisry butyl group, R₂ an alkyl residue with from 1 to 12 carbon stoms, an alkoxy residue with from 1 to 12 carbon atoms, the cyclohexyl residue, the sulphonic acid group -SO₃H or the group - S0₃Me, Me being an alkali metal, and R₃ is hydrogen or chlorine, and, possibly, an inert wax binder,
either

a) a 2-hydroxy-benzophenone of formula I _-

where R, is a hydroxy-group, an unsubstituted alkoxy residue with from 1 to 18 carbon atoms or an alkoxy residue with from 1 to 4 carbon atoms, carrying 1 or 2 hydroxy-groups, an alkoxy residue with from 1 to 4 carbon atoms, carrying 1 or 2 hydroxy groups and esterified with a saturated or olefinically unsaturated carboxylic acid with from 2 to 4 carbon atoms, R₂ is hydrogen, a phenyl residue, the sulphonic acid group -S0₃H or the group - S0₃Me, Me being an alksli metal, R₃ is hydrogen, the hydroxy group, an alkyl group with from 1 to 12 carbon atoms, an alkoxy group with from 1 to 18 carbon atoms or a phenyl residue, and R₄ is hydrogen, the hydroxy group, a phenyl residue, the carboxy group -COOH or the group -COOMe, Me being an alkali metal,
or

b) 3,5,7,3',4'-pentahydroxy-flavone of

9. A dye acceptor material containing a sheet-like unit according to claim 8 for multi-copy precursor sensitive recording materials characterized in that the carrier material is coated on the one side with the dye acceptor material and, possibly, a wax binder and on the other side with a dye precursor in usual manners.

10. A dye acceptor material containing sheet-like unit according to claim 8 or 9 for pressure-sensitive recording materials, characterised in that the dye acceptor material, in addition, contains 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, octadecyl β-(3,5-di-tert.Butyl-4-hydroxy-phenyl)propionate, pentaerythritol β-(3,5-di-tert.butyl-4-hydroxy-phenyl)propionate or a 2-n-alkylthio-4,6-di-(3',5'-di-tert.butyl-4'-hydroxy-phenoxy)1,3,5-triazine, the alkylthio residue having from 4 to 12 carbon atoms and mixtures thereof.

11. A dye acceptor material contsining a sheet-like unit according to one or several of claims 8 to 10 for pressure-sensitive recording materials characterised in that the dye acceptor material, in addition, contains a compound of formula IV

where R₁ and R₂, which may be identical or different, are branched chain alkyl groups with from 6 to 12 carbon atoms, R₃ is an alkyl group with from 3 to 10 carbon atoms or s cyclo-aliphatic residue, in which case R₄ and R₅ then are hydrogen atoms, or one, two or three of the residues R₃, R₄ and R₅ are hydroxy-alkyl residues with from 2 to 6 carbon atoms, the other residues then being hydrogen atoms, and Me is Co, Ni, Mn, Zn, Fe, Cu, Cr or Va.

12. A dye acceptor material containing sheet-like unit according to one or several of claims 8 to 11 for pressure-sensitive recording materials characterised in that the dye acceptor msterial contains from 0.1 to 0.5 % by weight of 5,10,11,11αtetrahydro-9,11 -dihydroxxy8-methyl-5-oxo-1H-pyrrolo[2.1-c][1.4]-benzodiazepine-2-(trans)acrylamide.

13. A dye acceptor material containing sheet-like unit according to one or several of claims 8 to 12 for pressure-sensitive recording materials characterised in that the dye acceptor material contains [I-phenyl-3-methyl-4-alkyl ether-pyrazolate(5)] Me complex salt, the alkyl ether residue being an alkoxy group with from 1 to 12 carbon atoms and Me being Co, Ni, Mn, Zn, Fe, Cu, Cr or Va.

14. A dye acceptor material containing sheet-like unit according to one or several of claims 8 to 13 for pressure-sensitive recording msterials characterised in that the dye acceptor material is coated on the carrier material in a quantity of from 0.5 to 6 g/m² of the carrier material.

15. Process for producing dye acceptor material containing sheet-like unit according to one or several of claims 8 to 14, characterised in that
either

a) a melt of the components of the dye acceptor material or a solution thereof in a suitable solvent is coated to the one such of the support material in an amount of 0.5 to 6 g/m² and the so coated support material is further processed in usual manners
or

b) cellulose fibers together with the components of the dye acceptor material are milled to the desired particle size and the thus obtained product is admixed to the paper pulp intended for the production of the sheet or web-like support material before the addition the glue material and the thus obtained psper pulp is further processed to the sheet or web-like support material in usual manners.