Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders

Definitions

• 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.
• an external physical force such as, in particular, pressure.
• 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.
• 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.
• 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.
• dye precursors used for pressure-sensitive recording papers 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.
• Crystal violet lactone is one of the dyes that, due to its constitution, can assume various boundary structures that are responsible for color formation.
• 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.
• 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).
• DE-A8 2 219 556 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).
• 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.
• DE-OS 2 129 467 describes the addition of certain colorless phenothiazines which are substituted with electron-donating groups.
• DE-AS 1 267 961 hydroquinone and phenyl- ⁇ -naphthylamine are added directly during paper manufacture.
• Other such additives such as diaminostilbene and benzimidazole are described in DE-AS 1 809 778.
• This clay-like substance is also predestined to react with triphenylmethane dyes.
• the risk of buying a 'white paper' that is not white at all (ie free of dyes) is very great.
• 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.
• 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.
• 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.
• 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.
• 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
• 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 ⁇ - (3,5, -Di-tert.butyl4-hydroxy-phenyl) propionic acid n-octadecyl ester, the ⁇ - (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 alky
• 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.
• 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 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the processor 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.
• 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.
• 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.
• the individual components of the dye acceptor material according to the invention are ground well together with cellulose fibers and the mixture is then added to the pulp before adding the sizing agent.
• 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.
• 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.
• 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.
• Colored substrates have the advantage in multiple sets that they make it easier to arrange the individual copies when creating them.
• 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 ⁇ m 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.
• 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 ⁇ m is reached. Only then is the hydroxypropyl cellulose added and ground again until 6 ⁇ m 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 .
• 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 ⁇ m 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.
• 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 ⁇ m. The resulting viscous paste is processed as described in Example 17 or 18.
• 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.
• 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 ⁇ m.
• 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.
• 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.
• 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 ⁇ m 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.
• 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.
• 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.
• 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.
• 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 ⁇ m 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.
• 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.
• 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.
• the wax is melted and ground with the active ingredients in a pearl mill to a fineness of maximum 6 ⁇ m.
• the dispersion is then prepared using the wax-in-water method using a dispersing disc and a high-speed stirrer, the wax being emulsified.
• 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.
• 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 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 ⁇ m 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.

Priority Applications (1)

Applications Claiming Priority (4)

Publications (3)

Family

ID=25784293

Family Applications (1)

Country Status (6)

Families Citing this family (26)

Citations (2)

Family Cites Families (39)

• 1981
  • 1981-02-27 EP EP81101430A patent/EP0036117B1/de not_active Expired
  • 1981-03-03 IE IE462/81A patent/IE51752B1/en unknown
  • 1981-03-04 AU AU68078/81A patent/AU542008B2/en not_active Ceased
  • 1981-03-09 US US06/241,523 patent/US4379721A/en not_active Expired - Fee Related
  • 1981-03-11 CA CA000372708A patent/CA1158437A/en not_active Expired
  • 1981-03-13 DK DK115981A patent/DK152185C/da active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events