EP0159295A2 - Chromogene bis-quinazoline compounds, process for their preparation and their use as a dye precursor in pressure-sensitive or heat-sensitive registration materials - Google Patents
Chromogene bis-quinazoline compounds, process for their preparation and their use as a dye precursor in pressure-sensitive or heat-sensitive registration materials Download PDFInfo
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- EP0159295A2 EP0159295A2 EP85810163A EP85810163A EP0159295A2 EP 0159295 A2 EP0159295 A2 EP 0159295A2 EP 85810163 A EP85810163 A EP 85810163A EP 85810163 A EP85810163 A EP 85810163A EP 0159295 A2 EP0159295 A2 EP 0159295A2
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- 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
- B41M5/136—Organic colour formers, e.g. leuco dyes
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- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
Definitions
- the present invention relates to chromogenic bis-quinazoline compounds, processes for their preparation and their use as color formers in pressure-sensitive or heat-sensitive recording materials.
- Ring B may be unsubstituted or substituted by cyano, halogen, lower alkyl, for example methyl or lower alkoxy such as methoxy
- ring D is a hydrogenated five- or six-membered nitrogen heterocycle, which optionally has a further heteroatom, for example oxygen, sulfur or nitrogen, and is unsubstituted or by Halogen, cyano, hydroxyl, lower alkyl, lower alkoxy, C 5 -C 6 cycloalkyl, benzyl or C 3 -C 6 alkylene is mono- or C-substituted, depending on the substituent.
- Lower alkyl and lower alkoxy in the definition of the residues of the bis-quinazoline compounds are groups or group components which have 1 to 5, preferably 1 to 3, carbon atoms, such as e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl or methoxy, ethoxy, isopropoxy or tert-butoxy.
- Q represents the meaning of an aliphatic radical in particular an alkylene group which is optionally substituted by halogen atoms, especially chlorine.
- the alkylene group can contain 2 to 8 carbon atoms and can be straight-chain or branched.
- the alkylene group preferably has 2 to 5 carbon atoms. These are, for example, the -CH 2 CH 2 -, CH 2 CH 2 -, , , -CH 2 CH 2 CH 2 CH 2 -, -CH 2 - (CH 2 ) 3 -CH 2 -, -CH 2 - (CH 2 ) 4 -CH 2 - or -CH 2 (CH 2 ) 6 -CH 2 group.
- the aliphatic hydrocarbon radical can be interrupted by oxygen atoms and thus represent the remainder of a polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol or polybutylene glycol.
- Q advantageously means the rest of the formula wherein m are 1 to 9, particularly 1 to 3 and s 1 to 5, preferably 1 or 2.
- Q means, for example, the 1,2-cyclopentylene group, the 1,2-cyclohexylene group, the 1,3-cyclohexylene group, the 1,4-cyclohexylene group or
- cycloaliphatic radicals can have one or two methyl groups.
- Q can be used as an araliphatic radical, for example represent.
- Q is preferably the aliphatic or cycloaliphatic radical, in particular alkylene having 2 to 4 carbon atoms and especially ethylene.
- Ring A is preferably not further substituted. If it has substituents it is primarily halogen, lower alkyl or lower alkoxy e.g. further substituted by chlorine, methyl, isopropyl, tert-butyl or methoxy. There may advantageously be 1 or 2 substituents per benzene ring.
- substituents X 1 and X 2 are alkyl groups, they can be straight-chain or branched.
- alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-octyl, isooctyl or n-dodecyl.
- alkyl radicals in X 1 and X 2 are substituted, they are primarily cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl, the alkyl parts preferably having 2 to 4 carbon atoms, such as, for example, ⁇ -cyanoethyl, ⁇ -chloroethyl, ⁇ -hydroxyethyl, ⁇ -methoxyethyl or ⁇ -ethoxyethyl.
- cycloalkyl in the meaning of X 1 and X 2 are cyclopentyl or preferably cyclohexyl.
- the cycloalkyl radicals can contain one or more C 1 -C 4 -alkyl radicals, preferably methyl groups. They preferably have a total of 5 to 10 carbon atoms.
- Preferred substituents in the benzyl and phenyl group of X 1 and X 2 are, for example, halogens, cyano, methyl, methoxy or carbomethoxy.
- Examples of such araliphatic or aromatic radicals are methylbenzyl, chlorobenzyl, cyanophenyl, tolyl, xylyl, chlorophenyl, methoxyphenyl or carbomethoxyphenyl.
- X 1 and X 2 together with the common nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, such as, for example, N-methylpiperazino.
- Preferred heterocyclic radicals for NX 1 X 2 are pyrrolidino, piperidino or morpholino.
- X 1 and X 2 are , independently of one another, preferably lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl.
- X 3 preferably denotes hydrogen, chlorine, methyl, methoxy or ethoxy.
- Ring B is preferably unsubstituted. However, it can advantageously have a methyl group.
- the ring D is preferably six-membered and especially C-substituted by 1, 2 or 3 methyl groups.
- Z is preferably lower alkyl, benzyl or ⁇ -cyanoethyl.
- Y represents an aminophenyl radical of the formula (3a)
- X 4 and X 5 are lower alkyl or benzyl.
- X 6 is preferably hydrogen.
- Q 1 is preferably alkylene with 2 to 4 carbon atoms and in particular ethylene or propylene.
- Q 1 is preferably also CH 2 CH 2 -O-CH 2 CH 2 - or the cyclohexylene radical.
- the ring A 1 is preferably unsubstituted.
- the N-substituent Z is in particular benzyl, ⁇ -cyanoethyl or alkyl with 1 to 8 carbon atoms, for example n-octyl, n-butyl, isopropyl or especially methyl or ethyl.
- V 1 and V 2 ) or (V 3 and V 4 ) together mean alkylene, they advantageously have 4 or 5 carbon atoms and form a cyclopentane or cyclohexane ring with the carbon atom connecting them.
- bis-quinazoline compounds of the formula (5) in which Q 2 is C 2 -C 4 -alkylene, preferably propylene or especially ethylene or is also -CH 2 CH 2 -O-CH 2 -CH 2 - .
- X 7 and X 8 are preferably benzyl or especially lower alkyl.
- W and T 4 are preferably hydrogen.
- Halogen in compounds with the above substituents in formulas (1) to (5) means, for example, fluorine, bromine or preferably chlorine.
- the bis-quinazoline compounds of the formula (1) according to the invention are prepared by adding 1 mol of a diol compound of the formula (6) HO ⁇ Q ⁇ OH where Q has the meaning given, with 2 mol of a 4-haloquinazoline compound of the formula wherein A and Y have the meaning given and Hal means halogen, such as bromine, fluorine or preferably chlorine.
- the reaction of the compound of formula (6) with the compound of formula (7) is advantageously carried out in the presence of an acid-binding agent, such as, for example, an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as, for example, pyridine or trialkylamines, and preferably also in the presence of a quaternary ammonium salt, such as tetrabutylammonium bromide, optionally in an organic solvent or in an aqueous-organic two-phase medium and at the reflux temperature.
- an acid-binding agent such as, for example, an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as, for example, pyridine or trialkylamines, and preferably also in the presence of a quaternary ammonium salt, such as tetrabutylammonium bromide, optionally in an organic solvent or in an aqueous-organic two-phase medium and at
- solvents examples include cycloaliphatic or aromatic hydrocarbons, such as e.g. Cyclohexane, benzene, toluene or xylene; Chlorinated hydrocarbons, e.g. Chloroform, ethylene chloride or chlorobenzenes, especially dichlorobenzene; Ethers such as Diethyl ether or glycol dimethyl ether; cyclic ethers, e.g. Dioxane or tetrahydrofuran; as well as dimethylformamide, diethylformamide, dimethyl sulfoxide or acetonitrile.
- cycloaliphatic or aromatic hydrocarbons such as e.g. Cyclohexane, benzene, toluene or xylene
- Chlorinated hydrocarbons e.g. Chloroform, ethylene chloride or chlorobenzenes, especially dichlorobenzene
- Ethers such as Diethyl ether or
- the starting materials of the formula (7) can be prepared by, for example, a 2-amino-benzoic acid amide from Fermel with an aldehyde of the formula to a 1,2,3,4-tetrahydro-quinazolone (4) compound of the formula converts this into a compound of the formula oxidized, then the hydroxyl group on the heterocyclic ring of the quinazoline system by a halogen atom, for example by means of phosphorus oxi chloride in dichlorobenzene or thionyl chloride in dimethylformamide to form the starting material of the formula (7).
- the 4-haloquinazoline compound obtained can be used without being isolated.
- oxidizing agents are e.g. Chromates, bichromates, chlorates, chlorites, peroxides, e.g. Hydrogen peroxide, manganese dioxide, lead dioxide, molecular oxygen, air, perborates, permanganates, nitrites, chlorine, bromine and especially chloranil or bisulfites.
- 4-haloquinazoline compounds of formula (7) and 4-quinazolone compounds of formula (13) and their preparation are e.g. in European Patent Publication No. 33716.
- the bis-quinazolines of the formulas (1) to (5) are normally colorless or at most weakly colored. If these color formers are brought into contact with a preferably acidic developer, ie an electron acceptor, they result in intense yellow or orange hues which are outstandingly lightfast and above all sublimation-fast.
- color formers for example 3,3- (bis-aminophenyl) phthalides, 3-indolyl-3-aminophenyl-azaphthalides, 3,3- (bis-indolyl- ) phthalides, 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines, spiropyrans, Spirodipyrans, chromenoindoles, phenoxazines, phenothiazines, monoquinazolines, carbazolylmethanes or other triarylmethane leuco dyes to give blue, gray or black colors.
- 3- (bis-aminophenyl) phthalides 3-indolyl-3-aminophenyl-azaphthalides
- 3,3- (bis-indolyl- ) phthalides 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines, spiropyrans, Spi
- the bis-quinazolines of formulas (1) to (5) show excellent color intensity, sublimation and light fastness both on phenolic substrates and especially on activated clays. They are particularly suitable as rapidly developing color formers for use in a heat-sensitive or, in particular, pressure-sensitive recording material, which can be both copying and registration material.
- a pressure-sensitive material consists, for example, of at least one pair of sheets which contain at least one color former of the formulas (1) to (5) dissolved in an organic solvent and an electron acceptor as developer.
- Typical examples of such developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any sound.
- active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any sound.
- Other developers are acidic, organic compounds, such as optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, furthermore an acidic, polymeric material, such as a phenolic polymer, an alkylphenol acetylene resin, a maleic acid rosin resin, or a partial or Fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene. It can mixtures of the polymeric compounds mentioned can also be used.
- Particularly preferred developers are acid clays, zinc salicylates or the condensation products of p-substituted phenols with formaldehyde. The latter can also contain zinc.
- the developers can also be mixed with other per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV adsorbers, such as 2- (2-hydroxyphenyl) benzotriazoles.
- pigments are: talc, titanium dioxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, for example urea-formaldehyde condensates (BET surface area 2-75 m 2 / g) or melamine-formaldehyde condensation products.
- the color former provides a colored marking at the points where it comes into contact with the electron acceptor.
- these are usually separated from the electron acceptor. This can conveniently be achieved by incorporating the color formers into foam, sponge or honeycomb structures.
- the color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
- the color former solution When the capsules are broken by pressure, for example using a pencil, the color former solution is transferred to an adjacent sheet coated with an electron acceptor, thereby producing a colored area. The color results from the dye formed, which absorbs in the visible range of the electromagnetic spectrum.
- the color formers are preferably encapsulated in the form of solutions in organic solvents.
- suitable solvents are preferably non-volatile solvents, for example polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, furthermore tricresyl phosphate, di-n-butyl phthalate, di octyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic ethers such as benzylphenyl ether, hydrocarbon oils such as paraffin or kerosene, for example derivatives of diphenyl, naphthalene or terphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, dibenzyltoluene, partially hydrogenated terphenol Xylenes, mono- to tetramethylated diphenylalkan
- Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
- the capsule walls can be formed evenly around the droplets of the color former solution by coacervation forces, the encapsulation material e.g. may consist of gelatin and gum arabic, such as e.g. in U.S. Patent 2,800,457.
- the capsules can preferably also be formed from an aminoplast or modified aminoplast by polycondensation, as described in British Patents 989,264, 1 156 725, 301 052 and 1 355 124.
- Microcapsules formed by interfacial polymerization such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
- the color formers of the formulas (1) to (5) containing microcapsules can be used to produce pressure-sensitive copying materials of various known types.
- the different systems differ essentially from each other in the arrangement of the capsules, the color reactants and the carrier material.
- the encapsulated color former is in the form of a layer on the back of a transfer sheet and the electron acceptor is in the form of a layer on the front of a receiver sheet.
- microcapsules containing the color former and the developer are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
- the capsules are preferably attached to the carrier by means of a suitable binder.
- this binder is primarily paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch or starch derivatives or polymer latices.
- the latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
- the paper used is not only normal papers made of cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made of synthetic polymers.
- the compounds of formulas (1) to (5) can also be used as color formers in a thermoreactive recording material.
- This usually contains at least one layer support, a color former, an electron acceptor and optionally also a binder and / or wax.
- Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, for example in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, such as, for example, electrocardiographs.
- the image generation (marking) can also be done manually done with a heated spring.
- Another device for producing markings by means of heat is laser beams.
- thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved and dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
- the binder becomes more specific. Districts softened by heat and at these points where heat is applied, the color former comes into contact with the electron acceptor and the desired color develops immediately.
- the same electron acceptors are suitable as developers.
- developers are the clay minerals already mentioned and especially phenolic resins, or also phenolic compounds, such as are described for example in DE-PS 12 51 348, e.g.
- 4-tert-butylphenol 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, ⁇ -naphthol, 4-hydroxy-diphenyl-sulfone, 4-hydroxybenzoic acid methyl ester or benzyl ester, 4-hydroxyacetophenone, 2,2'-dihydroxy -diphenyl, 4,4'-isopropylidenediphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 2,2-methylene-bis- (4-phenylphenol), 4,4'-bis- (hydroxyphenyl) - valeric acid, hydroquinone, pyrogallol, phloroglucin, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, as well as boric acid and organic, preferably aliphatic dicarboxylic acids, such as, for example Tartaric acid, oxalic acid,
- Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water-soluble, while the bis-quinazolines and developer are sparingly soluble or insoluble in water are. The binder should be able to disperse and fix the color former and developer at room temperature.
- Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, CarSoxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
- hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, CarSoxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
- water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
- binders soluble in non-polar or only weakly polar solvents
- Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
- the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
- thermoreactive layers can contain further additives.
- these layers for example talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (for example chalk), clays or even organic pigments, such as for example urea Formaldehyde polymers.
- substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal stearates, such as, for example, zinc stearate, phthalic acid nitrile, dimethyl terephthalate products or other corresponding, meltable products induce the simultaneous melting of the color former and the developer will.
- Thermographic recording materials preferably contain waxes, for example carnauba wax, montana wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
- Example 1 29.3 g of the quinazolone compound of the formula 16 g of phosphorus oxychloride are added to 70 g of xylene (isomer mixture, bp. 138-142 ° C) at 90 ° C. The reaction mixture is stirred at this temperature for 1 hour and a dark red solution of the 4-chloro-2- (4'-diethylaninophenyl) -quinazoline compound of the formula is obtained
- the solution is added dropwise to a suspension of 3.1 g of ethylene glycol, 100 g of sodium hydroxide solution (50%) and 1 g of tetrabutylammonium bromide.
- the suspension is then stirred under reflux for one hour and then 150 ml of water are added at 90.degree.
- the xylene phase is separated and washed several times with hot water.
- the xylene phase is then allowed to cool with stirring and 100 g of methanol are added at 35.degree.
- the maximum reflectance of this bis-quinazoline compound on acid-coated paper is 464 nm.
- Example 15 17 g of the quinazolone compound of the formula are suspended in 90 g of toluene at 90 ° C. The mixture is chlorinated by metering in 8 g of phosphorus oxitrichloride at 90 ° C. for 30 minutes. The red reaction solution of the compound of the formula
- Recrystallization from toluene / isopropyl alcohol 7: 3 gives the pure product with a melting point of 228-229 ° C.
- This color former develops a yellow color with good light fastness on acid clay.
- the color former is also characterized by excellent sublimation fastness.
- a solution of 3 g of the bis-quinazoline compound of the formula (21) in 80 g of partially hydrogenated terphenyl and 17 g of kerosene is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, mixed with starch solution and spread on a sheet of paper.
- a second sheet of paper is coated on the front with acid-activated bentonite as a color developer.
- the first sheet and the paper coated with color developer are placed on top of each other with the coatings adjacent. Writing by hand or with the typewriter on the first sheet exerts pressure, and an intense yellow copy develops on the sheet coated with the developer, which is excellent in sublimation and lightfastness.
- Example 18 1 g of the bis-quinazoline compound of the formula (21) is dissolved in 17 g of toluene. 12 g of polyvinyl acetate, 8 g of calcium carbonate and 2 g of titanium dioxide are added to this solution with stirring. The suspension obtained is diluted in a weight ratio of 1: 1 with toluene and spread on a sheet of paper using a 10 ⁇ m doctor blade. A second sheet of paper is placed on this sheet of paper, the underside of which has been coated with a mixture consisting of 1 part of an amide wax, 1 part of a stearic wax and 1 part of zinc chloride at an application weight of 3 g / m 2 . By writing by hand or with a typewriter on the top sheet, pressure is exerted and an intense, sublimation and lightfast yellow color develops on the sheet coated with the color formers.
- Example119 Production of a heat sensitive recording material
- the two dispersions are combined and coated onto a paper with a dry application weight of 5.5 g / m 2 .
- a paper with a dry application weight of 5.5 g / m 2 By touching the paper with a heated ballpoint pen, an intense yellow color is obtained which has excellent sublimation and light fastness.
- Intense and lightfast yellow colors can also be obtained using any of the other color formers of formula (22) given in Preparation Examples 2-15.
- Example 20 2.7 g of the bis-quinazoline compound of the formula (21), 24 g of N-phenyl-N '- (1-hydroxy-2,2,2-trichloroethyl) urea, 16 g are placed in a ball mill Stearic acid amide, 59 g of an 88% hydrolyzed polyvinyl alcohol and 58 ml of water ground until the particle size is 2-5 ⁇ m. This suspension is spread on a sheet of paper at a dry application weight of 5.5 g / m 2 . By touching the paper with a heated ballpoint pen, an intense, sublimation and lightfast yellow color is obtained.
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Abstract
Chromogene Bis-Chinazolinverbindungen der Formel <IMAGE> worin der Ring A unsubstituiert oder durch Cyano, Nitro, Halogen, Nieder-alkyl, Phenyl, Benzyl, Niederalkoxy oder Niederalkoxy-carbonyl substituiert ist, Q einen aliphatischen Rest mit einem Molekulargewicht von 28 bis 450 oder einen cycloalphatischen oder araliphatischen Rest und Y den Rest der Formel (2a) <IMAGE> oder der Formel (2b) <IMAGE> bedeuten, worin B, D, X1, X2, X3 und Z, die im Anspruch 1 angegebene Bedeutung haben. Diese Verbindungen eignen sich insbesondere als Farbbildner in druck- oder wärmeempfindlichen Aufzeichnungsmaterialien und ergeben intensive gelbe oder orange Farbtöne von ausgezeichneter Lich-und vor allem Sublimationsechtheit.Chromogenic bis-quinazoline compounds of the formula <IMAGE> wherein ring A is unsubstituted or substituted by cyano, nitro, halogen, lower alkyl, phenyl, benzyl, lower alkoxy or lower alkoxycarbonyl, Q is an aliphatic radical with a molecular weight of 28 to 450 or a cycloalphatic or araliphatic radical and Y is the radical of the formula (2a) <IMAGE> or of the formula (2b) <IMAGE>, where B, D, X1, X2, X3 and Z have the meaning given in claim 1. These compounds are particularly suitable as color formers in pressure- or heat-sensitive recording materials and produce intense yellow or orange hues of excellent light and, above all, sublimation fastness.
Description
Die vorliegende Erfindung betrifft chromogene Bis-Chinazolinverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Farbbildner in druckempfindlichen oder wärmeempfindlichen Aufzeichnungsmaterialien.The present invention relates to chromogenic bis-quinazoline compounds, processes for their preparation and their use as color formers in pressure-sensitive or heat-sensitive recording materials.
Die neuen Bis-Chinazolinverbindungen entsprechen der allgemeinen Formel
- der Ring A unsubstituiert oder durch Cyano, Nitro, Halogen, Niederalkyl, Phenyl, Benzyl, Niederalkoxy oder Niederalkoxycarbonyl substituiert sein kann,
- Q einen aliphatischen Rest mit einem Molekulargewicht von 28 bis 450 oder einen cycloaliphatischen oder araliphatischen Rest mit höchstens 10 Kohlenstoffatomen und
- Y den Rest der Formel
- X1 und X2, unabhängig voneinander, je Wasserstoff, unsubstituiertes oder durch Halogen, Hydroxy, Cyano oder Niederalkoxy substituiertes Alkyl mit höchstens 12 Kohlenstoffatomen, Cycloalkyl, Phenyl, Benzyl oder durch Halogen, Nitro, Cyano, Niederalkyl, Niederalkoxy oder Niederalkoxycarbonyl substituiertes Phenyl oder Benzyl
- oder X und X2 zusammen mit dem sie verbindenden Stickstoffatom einen fünf- oder sechsgliedrigen, vorzugsweise gesättigten, heterocyclischen Rest,
- X3 Wasserstoff, Halogen, Niederalkyl, Niederalkoxy oder Niederalkoxycarbonyl und
- Z Wasserstoff oder unsubstituiertes oder durch Halogen, Cyano oder Niederalkoxy substituiertes Alkyl mit höchstens 8 Kohlenstoffatocen, Cycloalkyl oder Benzyl und wobei der
- ring A can be unsubstituted or substituted by cyano, nitro, halogen, lower alkyl, phenyl, benzyl, lower alkoxy or lower alkoxycarbonyl,
- Q is an aliphatic radical with a molecular weight of 28 to 450 or a cycloaliphatic or araliphatic radical with at most 10 carbon atoms and
- Y the rest of the formula
- X 1 and X 2 , independently of one another, are each hydrogen, unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, cycloalkyl, phenyl, benzyl or phenyl substituted by halogen, nitro, cyano, lower alkyl, lower alkoxy or lower alkoxycarbonyl or Benzyl
- or X and X 2 together with the nitrogen atom connecting them a five- or six-membered, preferably saturated, heterocyclic radical,
- X 3 is hydrogen, halogen, lower alkyl, lower alkoxy or lower alkoxycarbonyl and
- Z is hydrogen or unsubstituted or substituted by halogen, cyano or lower alkoxy alkyl with at most 8 carbonocene, cycloalkyl or benzyl and where the
Ring B unsubstituiert oder durch Cyano, Halogen, Niederalkyl z.B. Methyl oder Niederalkoxy wie Methoxy substituiert sein kann und der Ring D einen hydrierten fünf- oder sechsgliedrigen Stickstoffheterocyclus darstellt, der gegebenenfalls als Ringglied ein weiteres Heteroatom z.B. Sauerstoff, Schwefel oder Stickstoff aufweist und unsubstituiert oder durch Halogen, Cyano, Hydroxyl, Niederalkyl, Niederalkoxy, C5-C6-Cycloalkyl, Benzyl oder C3-C6-Alkylen einfach oder je nach Substituenten mehrfach C-substituiert ist.Ring B may be unsubstituted or substituted by cyano, halogen, lower alkyl, for example methyl or lower alkoxy such as methoxy, and ring D is a hydrogenated five- or six-membered nitrogen heterocycle, which optionally has a further heteroatom, for example oxygen, sulfur or nitrogen, and is unsubstituted or by Halogen, cyano, hydroxyl, lower alkyl, lower alkoxy, C 5 -C 6 cycloalkyl, benzyl or C 3 -C 6 alkylene is mono- or C-substituted, depending on the substituent.
Niederalkyl und Niederalkoxy stellen bei der Definition der Reste der Bis-Chinazolinverbindungen\solche Gruppen oder Gruppenbestandteile dar, die 1 bis 5, vorzugsweise 1 bis 3 Kohlenstoffatome aufweisen, wie z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, tert.Butyl oder Amyl bzw. Methoxy, Ethoxy, Isopropoxy oder tert.Butoxy.Lower alkyl and lower alkoxy in the definition of the residues of the bis-quinazoline compounds are groups or group components which have 1 to 5, preferably 1 to 3, carbon atoms, such as e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl or methoxy, ethoxy, isopropoxy or tert-butoxy.
Q stellt in der Bedeutung eines aliphatischen Restes insbesondere eine Alkylengruppe dar, die gegebenenfalls durch Halogenatome, besonders Chlor, substituiert ist. Die Alkylengruppe kann 2 bis 8 Kohlenstoffatome enthalten und geradkettig oder verzweigt sein. Die Alkylengruppe weist vorzugsweise 2 bis 5 Kohlenstoffatome auf. Es handelt sich beispielsweise um die -CH2CH2-,
Der aliphatische Kohlenwasserstoffrest kann durch Sauerstoffatome unterbrochen sein und somit den Rest eines Polyalkylenglykols,' wie z.B. Polyäthylenglykols, Polypropylenglykols oder Polybutylenglykols darstellen. Dabei bedeutet Q vorteilhafterweise den Rest der Formel
Als cycloaliphatischer Rest bedeutet Q z.B. die 1,2-Cyclopentylengruppe, die 1,2-Cyclohexylengruppe, die 1,3-Cyclohexylengruppe, die 1,4-Cyclohexylengruppe oder
Diese cycloaliphatischen Reste können eine oder zwei Methylgruppen aufweisen.These cycloaliphatic radicals can have one or two methyl groups.
Als araliphatischer Rest kann Q beispielsweise
Vorzugsweise bedeutet Q den aliphatischen oder cycloaliphatischen Rest, insbesondere Alkylen mit 2 bis 4 Kohlenstoffatomen und vor allem Ethylen.Q is preferably the aliphatic or cycloaliphatic radical, in particular alkylene having 2 to 4 carbon atoms and especially ethylene.
Der Ring A ist vorzugsweise nicht weiter substituiert. Falls er Substituenten aufweist, ist er in erster Linie durch Halogen, Niederalkyl oder Niederalkoxy z.B. durch Chlor, Methyl, Isopropyl, tert.Butyl oder Methoxy weitersubstituiert. Pro Benzolring können vorteilhafterweise 1 oder 2 Substituenten vorhanden sein.Ring A is preferably not further substituted. If it has substituents it is primarily halogen, lower alkyl or lower alkoxy e.g. further substituted by chlorine, methyl, isopropyl, tert-butyl or methoxy. There may advantageously be 1 or 2 substituents per benzene ring.
Stellen die Substituenten X1 und X2 Alkylgruppen dar, so können sie geradkettig oder verzweigt sein. Beispiele für solche Alkylreste sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, Amyl, n-Hexyl, 2-Ethyl-hexyl, n-Octyl, Isooctyl oder n-Dodecyl.If the substituents X 1 and X 2 are alkyl groups, they can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-octyl, isooctyl or n-dodecyl.
Sind die Alkylreste in X1 und X2 substituiert, so handelt es sich vor allem um Cyanoalkyl, Halogenalkyl, Hydroxyalkyl oder Alkoxyalkyl, wobei die Alkylteile vorzugsweise 2 bis 4 Kohlenstoffatome aufweisen, wie z.B. β-Cyanoethyl, ß-Chloroethyl, ß-Hydroxyethyl, β-Methoxyethyl oder β-Ethoxyethyl.If the alkyl radicals in X 1 and X 2 are substituted, they are primarily cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl, the alkyl parts preferably having 2 to 4 carbon atoms, such as, for example, β-cyanoethyl, β-chloroethyl, β-hydroxyethyl, β-methoxyethyl or β-ethoxyethyl.
Beispiele für Cycloalkyl in der Bedeutung von X1 und X2 sind Cyclopentyl oder vorzugsweise Cyclohexyl. Die Cycloalkylreste können einen oder mehrere Cl-C4-Alkylreste, vorzugsweise Methylgruppen, enthalten. Vorzugsweise weisen sie insgesamt 5 bis 10 Kohlenstoffatome auf.Examples of cycloalkyl in the meaning of X 1 and X 2 are cyclopentyl or preferably cyclohexyl. The cycloalkyl radicals can contain one or more C 1 -C 4 -alkyl radicals, preferably methyl groups. They preferably have a total of 5 to 10 carbon atoms.
Bevorzugte Substituenten in der Benzyl- und Phenylgruppe von X1 und X2 sind z.B. Halogene, Cyano, Methyl, Methoxy oder Carbomethoxy. Beispiele für derartige araliphatische bzw. aromatische Reste sind Methylbenzyl, Chlorbenzyl, Cyanophenyl, Tolyl, Xylyl, Chlorphenyl, Methoxyphenyl oder Carbomethoxyphenyl.Preferred substituents in the benzyl and phenyl group of X 1 and X 2 are, for example, halogens, cyano, methyl, methoxy or carbomethoxy. Examples of such araliphatic or aromatic radicals are methylbenzyl, chlorobenzyl, cyanophenyl, tolyl, xylyl, chlorophenyl, methoxyphenyl or carbomethoxyphenyl.
Wenn X1 und X2 zusammen mit dem gemeinsamen Stickstoffatom einen heterocyclischen Rest darstellen, so ist dieser beispielsweise Pyrrolidino, Piperidino, Pipecolino, Morpholino, Thiomorpholino oder Piperazino, wie z.B. N-Methylpiperazino. Bevorzugte heterocyclische Reste für NX1X2 sind Pyrrolidino, Piperidino oder Morpholino.If X 1 and X 2 together with the common nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, such as, for example, N-methylpiperazino. Preferred heterocyclic radicals for NX 1 X 2 are pyrrolidino, piperidino or morpholino.
X1 und X2 bedeuten, unabhängig voneinander, vorzugsweise Niederalkyl, Benzyl, Phenyl, Niederalkylphenyl oder Niederalkoxyphenyl. X3 bedeutet vorzugsweise Wasserstoff, Chlor, Methyl, Methoxy oder Ethoxy.X 1 and X 2 are , independently of one another, preferably lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl. X 3 preferably denotes hydrogen, chlorine, methyl, methoxy or ethoxy.
Der Ring B ist vorzugsweise unsubstituiert. Er kann jedoch vorteilhafterweise eine Methylgruppe aufweisen. Der Ring D ist vorzugsweise sechsgliedrig und vor allem durch 1, 2 oder 3 Methylgruppen C-substituiert.Ring B is preferably unsubstituted. However, it can advantageously have a methyl group. The ring D is preferably six-membered and especially C-substituted by 1, 2 or 3 methyl groups.
Z ist vorzugsweise Niederalkyl, Benzyl oder β-Cyanoethyl.Z is preferably lower alkyl, benzyl or β-cyanoethyl.
Unter den Bis-Chinazolinverbindungen der Formel (1) sind diejenigen, in denen Y einen Rest der Formel (2a) darstellt,bevorzugt.Among the bis-quinazoline compounds of the formula (1), those in which Y represents a radical of the formula (2a) are preferred.
Praktisch wichtige chromogene Bis-Chinazolinverbindungen entsprechen der Formel
- Y1 einen Aminophenylrest der Formel
- einen 5-Indolinylrest der Formel
- einen Tetrahydrochinolinylrest der Formel
- einen Tetrahydrochinolinylrest der Formel
- oder einen Benzomorpholinorest der Formel
- m1 1 bis 3
- X4 und X5, unabhängig voneinander, Niederalkyl, Cyano-Niederalkyl, Benzyl, Phenyl, Niederalkylphenyl oder Niederalkoxyphenyl oder
- X4 und X5 zusammen mit dem sie verbindenden Stickstoffatom Pyrrolidino, Piperidino oder Morpholino,
- X6 Wasserstoff, Halogen, Niederalkyl oder Niederalkoxy,
- Z1 Wasserstoff, C1-C8-Alkyl, C2-C6-Alkoxyalkyl, β-Cyanoethyl oder Benzyl,
- T Wasserstoff, Halogen, Niederalkyl, Niederalkoxy, C1-C4-Acyl- amino, wie z.B. Acetylamino oder Propionylamino,oder Phenyl,
- T1 und T2 je Wasserstoff, Halogen, Hydroxy, Niederalkyl oder Niederalkoxy und
- V1, V2, V3 und V4 je Wasserstoff, Niederalkyl, Cycloalkyl oder Benzyl oder (V1 und V2) oder (V3 und V4) je zusammen Alkylen bedeuten und
der Ring A1 unsubstituiert oder durch einen oder zwei Substituenten ausgewählt aus Cyano, Halogen, Niederalkyl, Phenyl und Niederalkoxy substituiert sein kann.Practically important chromogenic bis-quinazoline compounds correspond to the formula
- Y 1 is an aminophenyl radical of the formula
- a 5-indolinyl radical of the formula
- a tetrahydroquinolinyl radical of the formula
- a tetrahydroquinolinyl radical of the formula
- or a benzomorpholino radical of the formula
- m 1 1 to 3
- X 4 and X 5 , independently of one another, lower alkyl, cyano-lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl or
- X 4 and X 5 together with the nitrogen atom connecting them pyrrolidino, piperidino or morpholino,
- X 6 is hydrogen, halogen, lower alkyl or lower alkoxy,
- Z 1 is hydrogen, C 1 -C 8 alkyl, C 2 -C 6 alkoxyalkyl, β-cyanoethyl or benzyl,
- T is hydrogen, halogen, lower alkyl, lower alkoxy, C 1 -C 4 -acylamino, such as acetylamino or propionylamino, or phenyl,
- T 1 and T 2 each hydrogen, halogen, hydroxy, lower alkyl or lower alkoxy and
- V 1 , V 2 , V 3 and V 4 each represent hydrogen, lower alkyl, cycloalkyl or benzyl or (V 1 and V 2 ) or (V 3 and V 4 ) each together represent alkylene and
the ring A 1 can be unsubstituted or substituted by one or two substituents selected from cyano, halogen, lower alkyl, phenyl and lower alkoxy.
Unter den Bis-Chinazolinverbindungen der Formel (3) sind diejenigen, in denen Y einen Aminophenylrest der Formel (3a) darstellt, bevorzugt. Dabei sind X4 und X5 Niederalkyl oder Benzyl. X6 ist vorzugsweise Wasserstoff. Q1 ist vorzugsweise Alkylen mit 2 bis 4 Kohlenstoffatomen und insbesondere Ethylen oder Propylen. Q1 ist bevorzugt auch CH2CH2-O-CH2CH2- oder der Cyclohexylenrest. Der Ring A1 ist vorzugsweise unsubstituiert.Among the bis-quinazoline compounds of the formula (3), those in which Y represents an aminophenyl radical of the formula (3a) are preferred. X 4 and X 5 are lower alkyl or benzyl. X 6 is preferably hydrogen. Q 1 is preferably alkylene with 2 to 4 carbon atoms and in particular ethylene or propylene. Q 1 is preferably also CH 2 CH 2 -O-CH 2 CH 2 - or the cyclohexylene radical. The ring A 1 is preferably unsubstituted.
Bei den Bis-Chinazolinverbindungen der Formel (3), in der Y1 einen Rest der Formel (3b), (3c), (3d) oder (3e) darstellt, ist der N-Substituent Z insbesondere Benzyl,ß-Cyanoethyl oder Alkyl mit 1 bis 8 Rohlenstoffatomen, z.B. n-Octyl, n-Butyl, Isopropyl oder vor allem Methyl oder Ethyl.In the bis-quinazoline compounds of the formula (3), in which Y 1 represents a radical of the formula (3b), (3c), (3d) or (3e), the N-substituent Z is in particular benzyl, β-cyanoethyl or alkyl with 1 to 8 carbon atoms, for example n-octyl, n-butyl, isopropyl or especially methyl or ethyl.
Dabei ist
- Y1 in erster Linie der Tetrahydrochinolinrest der Formel (3d).
- T ist vorzugsweise Wasserstoff oder Methyl.
- T ist vorzugsweise Wasserstoff, Methyl, Hydroxyl oder Chlor.
- T2 ist vorzugsweise Wasserstoff, Methyl oder Ethyl.
- V1 und V2 bedeuten vorzugsweise Wasserstoff oder Methyl.
- V3 und V4 bedeuten vorzugsweise jeweils Niederalkyl und insbesondere jeweils Methyl.
- Y 1 is primarily the tetrahydroquinoline residue of the formula (3d).
- T is preferably hydrogen or methyl.
- T is preferably hydrogen, methyl, hydroxyl or chlorine.
- T 2 is preferably hydrogen, methyl or ethyl.
- V 1 and V 2 are preferably hydrogen or methyl.
- V 3 and V 4 preferably each represent lower alkyl and in particular each methyl.
Bedeuten (V1 und V2) oder (V3 und V4) zusammen Alkylen, so weisen sie mit Vorteil 4 oder 5 Kohlenstoffatome auf und bilden mit dem sie verbindenden Kohlenstoffatom einen Cyclopentan- oder Cyclohexanring.If (V 1 and V 2 ) or (V 3 and V 4 ) together mean alkylene, they advantageously have 4 or 5 carbon atoms and form a cyclopentane or cyclohexane ring with the carbon atom connecting them.
Von grossem Interesse sind Bis-Chinazolinverbindungen der Formel
- Q geradkettiges oder verzweigtes Alkylen mit 2 bis 4 Kohlenstoffatomen, -CH2CH2-O-CH2CH2-, (-CH2CH2O-)2CH2CH2-,
- X7 und X8 Niederalkyl oder Benzyl oder -NX7X8 Piperidino,
- X9 Wasserstoff, Methyl, Methoxy oder Ethoxy,
- Z2 Alkyl mit 1 bis 8 Kohlenstoffatomen, β-Cyanoethyl oder Benzyl,
- T3, V5 und V6 je Niederalkyl, insbesondere Methyl oder Ethyl,
- T4 Wasserstoff oder Methyl und
- W Halogen, Methyl, Methoxy oder besonders Wasserstoff bedeuten.
- Q straight-chain or branched alkylene with 2 to 4 carbon atoms, -CH 2 CH 2 -O-CH 2 CH 2 -, (-CH 2 CH 2 O-) 2 CH 2 CH 2 -,
- X 7 and X 8 lower alkyl or benzyl or -NX 7 X 8 piperidino,
- X 9 is hydrogen, methyl, methoxy or ethoxy,
- Z 2 alkyl with 1 to 8 carbon atoms, β-cyanoethyl or benzyl,
- T 3 , V 5 and V 6 each lower alkyl, in particular methyl or ethyl,
- T4 is hydrogen or methyl and
- W is halogen, methyl, methoxy or especially hydrogen.
Im Vordergrund des Interesses stehen Bis-Chinazolinverbindungen der Formel (5), in der Q2 C2-C4-Alkylen, vorzugsweise Propylen oder vor allem Ethylen bedeutet oder auch -CH2CH2-O-CH2-CH2- darstellt. X7 und X8 sind vorzugsweise Benzyl oder vor allem Niederalkyl. W und T4 sind vorzugsweise Wasserstoff.Of primary interest are bis-quinazoline compounds of the formula (5) in which Q 2 is C 2 -C 4 -alkylene, preferably propylene or especially ethylene or is also -CH 2 CH 2 -O-CH 2 -CH 2 - . X 7 and X 8 are preferably benzyl or especially lower alkyl. W and T 4 are preferably hydrogen.
Halogen in Verbindungen mit den vorstehenden Substituenten in Formeln (1) bis (5) bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen in compounds with the above substituents in formulas (1) to (5) means, for example, fluorine, bromine or preferably chlorine.
Die erfindungsgemässen Bis-Chinazolinverbindungen der Formel (1) werden dadurch hergestellt, dass man 1 Mol einer Diolverbindung der Formel
(6) HO―Q―OH worin Q die angegebene Bedeutung hat, mit 2 Mol einer 4-Halogenchinazolinverbindung der Formel
(6) HO ― Q ― OH where Q has the meaning given, with 2 mol of a 4-haloquinazoline compound of the formula
Die Umsetzung der Verbindung der Formel (6) mit der Verbindung der Formel (7) erfolgt zweckmässig in Anwesenheit eines säurebindenden Mittels, wie z.B. eines Alkalimetallhydroxides, Alkalimetallcarbonates, einer tertiären Stickstoffbase, wie z.B. Pyridin oder Trialkylaminen, und vorzugsweise in Gegenwart auch eines quaternären Ammoniunsalzes, wie z.B. Tetrabutylammoniumbromides, gegebenenfalls in einem organischen Lösungsmittel oder in einem wässerig-organischen zweiphasigen Medium und bei Rückflusstemperatur.The reaction of the compound of formula (6) with the compound of formula (7) is advantageously carried out in the presence of an acid-binding agent, such as, for example, an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as, for example, pyridine or trialkylamines, and preferably also in the presence of a quaternary ammonium salt, such as tetrabutylammonium bromide, optionally in an organic solvent or in an aqueous-organic two-phase medium and at the reflux temperature.
Als Lösungsmittel kommen beispielsweise cycloaliphatische oder aromatische Kohlenwasserstoffe, wie z.B. Cyclohexan, Benzol, Toluol oder Xylol; Chlorkohlenwasserstoffe, wie z.B. Chloroform, Ethylenchlorid oder Chlorbenzole insbesondere Dichlorbenzol; Ether, wie z.B. Diethylether oder Glykoldimethylether; cyclische Ether, wie z.B. Dioxan oder Tetrahydrofuran; sowie Dimethylformamid, Diethylformamid, Dimethylsulfoxid oder Acetonitril in Betracht.Examples of solvents are cycloaliphatic or aromatic hydrocarbons, such as e.g. Cyclohexane, benzene, toluene or xylene; Chlorinated hydrocarbons, e.g. Chloroform, ethylene chloride or chlorobenzenes, especially dichlorobenzene; Ethers such as Diethyl ether or glycol dimethyl ether; cyclic ethers, e.g. Dioxane or tetrahydrofuran; as well as dimethylformamide, diethylformamide, dimethyl sulfoxide or acetonitrile.
Diolverbindungen der Formel (6), die als Ausgangsstoffe für die Umsetzung mit den Chinazolinverbindungen der Formel (7) eingesetzt werden können, entsprechen vorzugsweise der Formel
- Q' Alkylen mit 2 bis 8 Kohlenstoffatomen,Cyclohexylen,
- n 1 bis 10 und insbesondere 1 bis 4 ist.
- Q 'alkylene with 2 to 8 carbon atoms, cyclohexylene,
- n is 1 to 10 and in particular 1 to 4.
Als Beispiele für als Ausgangsstoffe der Formel (6) dienende Diole seien genannt:
- Ethylenglykol, Propylenglykol (1,2) oder (1,3), Butylenglykol (1,3), (1,4) oder (2,3), 2-Methyl-propandiol (1,3), 3-Chlor-propandiol (1,2), 2,2-Dimethyl-l,3-proandiol, Neopentylglykol, Pinakon, Pentandiol (1,5), 3-Methyl-pentandiol (1,5), 2-Methyl-pentandiol (2,4), Hexandiol (1,6) oder (2,5), Octandiol (1,8), Cyclohexandiol (1,2), (1,3) oder (1,4), Cyclohexan-1,4-dimethanol, Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, Dibutylenglykol, 4-Hydroxybenzylalkohol, 4-Hydroxy-phenylethanol oder 4-Hydroxyphenoxyethanol.
- Ethylene glycol, propylene glycol (1,2) or (1,3), butylene glycol (1,3), (1,4) or (2,3), 2-methyl-propanediol (1,3), 3-chloropropanediol (1,2), 2,2-dimethyl-l, 3-proanediol, neopentylglycol, Pinakon, pentanediol (1.5), 3-methylpentanediol (1.5), 2-methylpentanediol (2.4) , Hexanediol (1.6) or (2.5), octanediol (1.8), cyclohexanediol (1.2), (1.3) or (1.4), cyclohexane-1,4-dimethanol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol, 4-hydroxybenzyl alcohol, 4-hydroxyphenylethanol or 4-hydroxyphenoxyethanol.
Die Ausgangsstoffe der Formel (7) können dadurch hergestellt werden, dass man beispielsweise ein 2-Amino-benzoesäureamid der Fermel
Die Oxidation der Umsetzungsprodukte der Formel (12) zu den 4-Chinazolon-verbindungen der Formel (13)erfolgt mit Oxidationsmitteln. Geeignete Oxidationsmittel sind z.B. Chromate, Bichromate, Chlorate, Chlorite, Peroxide, z.B. Wasserstoffperoxid, Mangandioxid, Bleidioxid, molekularer Sauerstoff, Luft, Perborate, Permanganate, Nitrite, Chlor, Brom und vor allem Chloranil oder Bisulfite.The oxidation of the reaction products of the formula (12) to the 4-quinazolone compounds of the formula (13) is carried out using oxidizing agents. Suitable oxidizing agents are e.g. Chromates, bichromates, chlorates, chlorites, peroxides, e.g. Hydrogen peroxide, manganese dioxide, lead dioxide, molecular oxygen, air, perborates, permanganates, nitrites, chlorine, bromine and especially chloranil or bisulfites.
Die besten Ergebnisse in Bezug auf Ausbeute und Reinheit der erhaltenen 4-Chinazolon-verbindungen erzielt man mit Chloranil als bevorzugtes Oxidationsmittel. Oekologische Vorteile bietet die Oxidation mit Natriumbisulfit. Auf analoge Weise wie in Synthesis 1981, (1), 35 beschrieben, erhält man unter Verwendung dieses Oxidationsmittels Chinazolonverbindungen der Formel (13) in guter Reinheit und Ausbeute.The best results in terms of yield and purity of the 4-quinazolone compounds obtained are achieved with chloranil as the preferred oxidizing agent. Oxidation with sodium bisulfite offers ecological advantages. In an analogous manner to that described in Synthesis 1981, (1), 35, quinazolone compounds of the formula (13) are obtained in good purity and yield using this oxidizing agent.
4-Halogenchinazolinverbindungen der Formel (7) und 4-Chinazolon- verbindungen der Formel (13) und deren Herstellung werden z.B. in der europäischen Patentveröffentlichung Nr. 33716 beschrieben.4-haloquinazoline compounds of formula (7) and 4-quinazolone compounds of formula (13) and their preparation are e.g. in European Patent Publication No. 33716.
Die Bis-Chinazoline der Formeln (1) bis (5) sind normalerweise farblos oder höchstens schwach gefärbt. Wenn diese Farbbildner mit einem vorzugsweise sauren Entwickler, d.h. einem Elektronenakzeptor, in Kontakt gebracht werden, so ergeben sie intensive gelbe oder orange Farbtöne, die ausgezeichnet lichtecht und vor allem sublimationsecht sind. Sie sind deshalb auch sehr wertvoll im Gemisch mit einem oder mehreren anderen bekannten Farbbildnern, z.B. 3,3-(Bis-aminophenyl)-phthaliden, 3-Indolyl-3-amino-phenyl-azaphthaliden, 3,3-(Bis-indolyl-)phthaliden, 3-Aminofluoranen, 2,6-Diaminofluoranen, Leukoauraminen, Spiropyranen, Spirodipyranen, Chromenoindolen, Phenoxazinen, Phenothiazinen, Monochinazolinen, Carbazolylmethanen oder weiteren Triarylmethanleukofarbstoffen, um blaue, graue oder schwarze Färbungen zu ergeben.The bis-quinazolines of the formulas (1) to (5) are normally colorless or at most weakly colored. If these color formers are brought into contact with a preferably acidic developer, ie an electron acceptor, they result in intense yellow or orange hues which are outstandingly lightfast and above all sublimation-fast. They are therefore also very valuable when mixed with one or more other known color formers, for example 3,3- (bis-aminophenyl) phthalides, 3-indolyl-3-aminophenyl-azaphthalides, 3,3- (bis-indolyl- ) phthalides, 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines, spiropyrans, Spirodipyrans, chromenoindoles, phenoxazines, phenothiazines, monoquinazolines, carbazolylmethanes or other triarylmethane leuco dyes to give blue, gray or black colors.
Die Bis-Chinazoline der Formeln (1) bis (5) zeigen sowohl auf phenolischen Unterlagen, wie auch besonders auf aktivierten Tonen, eine ausgezeichnete Farbintensität, Sublimations- und Lichtechtheit. Sie eignen sich vor allem als sich schnell entwickelnde Farbbildner für die Verwendung in einem wärmeempfindlichen oder insbesondere druckempfindlichen Aufzeichnungsmaterial, das sowohl Kopier- als auch Registriermaterial sein kann.The bis-quinazolines of formulas (1) to (5) show excellent color intensity, sublimation and light fastness both on phenolic substrates and especially on activated clays. They are particularly suitable as rapidly developing color formers for use in a heat-sensitive or, in particular, pressure-sensitive recording material, which can be both copying and registration material.
Sie zeichnen sich dadurch aus, dass sie in den Kapselölen hervorragend löslich sindThey are characterized by the fact that they are extremely soluble in the capsule oils
Ein druckempfindliches Material besteht beispielsweise aus mindestens einem Paar von Blättern, die mindestens einen Farbbildner der Formeln (1) bis (5) gelöst in einem organischen Lösungsmittel und einen Elektronenakzeptor als Entwickler enthalten.A pressure-sensitive material consists, for example, of at least one pair of sheets which contain at least one color former of the formulas (1) to (5) dissolved in an organic solvent and an electron acceptor as developer.
Typische Beispiele für solche Entwickler sind Aktivton-Substanzen, wie Attapulgus-Ton, Säureton, Bentonit, Montmorillonit, aktivierter Ton, wie z.B. säureaktiviertes Bentonit oder Montmorillonit, ferner Zeolith, Halloysit, Siliciumdioxyd, Aluminiumoxid, Aluminiumsulfat, Aluminiumphosphat, Zinkchlorid, Zinknitrat, aktiviertes Kaolin oder irgendein beliebiger Ton. Weitere Entwickler sind sauer reagierende, organische Verbindungen, wie z.B. gegebenenfalls ringsubstituierte Phenole, Salicylsäure oder Salicylsäureester und deren Metallsalze, ferner ein sauer reagierendes, polymeres Material, wie z.B. ein phenolisches Polymerisat, ein Alkylphenolacetylenharz, ein Maleinsäuere-Kolophonium-Harz, oder ein teilweise oder vollständig hydrolysiertes Polymerisat von Maleinsäureanhydrid mit Styrol, Ethylen oder Vinylmethylether, oder Carboxypolymethylen. Es können auch Mischungen der genannten polymeren Verbindungen eingesetzt werden. Besonders bevorzugte Entwickler sind Säuretone, Zinksalicylate oder die Kondensationsprodukte von p-substituierten Phenolen mit Formaldehyd. Die letzteren können auch Zink enthalten.Typical examples of such developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any sound. Other developers are acidic, organic compounds, such as optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, furthermore an acidic, polymeric material, such as a phenolic polymer, an alkylphenol acetylene resin, a maleic acid rosin resin, or a partial or Fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene. It can mixtures of the polymeric compounds mentioned can also be used. Particularly preferred developers are acid clays, zinc salicylates or the condensation products of p-substituted phenols with formaldehyde. The latter can also contain zinc.
Die Entwickler können zusätzlich auch mit anderen, an sich unreaktiven oder wenig reaktiven Pigmenten oder weiteren Hilfsstoffen wie Kieselgel oder UV-Adsorbern, wie z.B. 2-(2-Hydroxyphenyl-)benzotriazolen gemischt eingesetzt werden. Beispiele für solche Pigmente sind: Talk, Titandioxid, Zinkoxid, Kreide, Tone wie Kaolin, sowie organische Pigmente, z.B. Harstoff-Formaldehyd Kondensate (BET-Oberfläche 2-75 m2/g) oder Melamin-Formaldehyd-Kondensationsprodukte.The developers can also be mixed with other per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV adsorbers, such as 2- (2-hydroxyphenyl) benzotriazoles. Examples of such pigments are: talc, titanium dioxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, for example urea-formaldehyde condensates (BET surface area 2-75 m 2 / g) or melamine-formaldehyde condensation products.
Der Farbbildner liefert an den Punkten, an denen er mit dem Elektronenakzeptor in Kontakt kommt, eine gefärbte Markierung. Um eine frühzeitige Aktivierung der in dem druckempfindlichen Aufzeichnungsmaterial vorhandenen Farbbildner zu verhindern, werden diese in der Regel von dem Elektronenakzeptor getrennt. Dies kann zweckmässig erzielt werden, indem man die Farbbildner in schaum-, schwamm- oder bienenwabenartigen Strukturen einarbeitet. Vorzugsweise sind die Farbbildner in Mikrokapseln eingeschlossen, die sich in der Regel durch Druck zerbrechen lassen.The color former provides a colored marking at the points where it comes into contact with the electron acceptor. In order to prevent early activation of the color formers present in the pressure-sensitive recording material, these are usually separated from the electron acceptor. This can conveniently be achieved by incorporating the color formers into foam, sponge or honeycomb structures. The color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
Beim Zerbrechen der Kapseln durch Druck, beispielsweise mittels eines Bleistiftes, wird die Farbbildnerlösung auf ein benachbartes, mit einem Elektronenakzeptor beschichtetes Blatt übertragen, wodurch eine farbige Stelle erzeugt wird. Die Farbe resultiert aus dem dabei gebildeten Farbstoff, der im sichtbaren Bereich des elektromagnetischen Spektrums absorbiert.When the capsules are broken by pressure, for example using a pencil, the color former solution is transferred to an adjacent sheet coated with an electron acceptor, thereby producing a colored area. The color results from the dye formed, which absorbs in the visible range of the electromagnetic spectrum.
Die Farbbildner werden vorzugsweise in Form von Lösungen in organischen Lösungsmitteln eingekapselt. Beispiele für geeignete Lösungsmittel sind vorzugsweise nichtflüchtige Lösungsmittel, z.B. polyhalogeniertes Paraffin oder Diphenyl,.wie Chlorparaffin, Monochlordiphenyl oder Trichlordiphenyl, ferner Tricresylphosphat, Di-n-butylphthalat, Dioctylphthalat, Trichlorbenzol, Trichlorethylphosphat, aromatische Ether, wie Benzylphenylether, Kohlenwasserstofföle, wie Paraffin oder Kerosin, z.B. mit Isopropyl, Isobutyl, sek.-Butyl oder tert.-Butyl alkylierte Derivate von Diphenyl, Naphthalin oder Terphenyl, Dibenzyltoluol, partiell hydriertes Terphenyl, benzylierte Xylole, mono- bis tetramethylierte Diphenylalkane oder weitere chlorierte oder hydrierte, kondensierte, aromatische Kohlenwasserstoffe. Oft werden Mischungen verschiedener Lösungsmittel, insbesondere Mischungen aus Paraffinölen oder Kerosin und Diisopropylnaphthalin oder partiell hydriertem Terphenyl, eingesetzt, um eine optimale Löslichkeit für die Farbbildung, eine rasche und intensive Färbung und eine für die Mikroverkapselung günstige Viskosität zu erreichen.The color formers are preferably encapsulated in the form of solutions in organic solvents. Examples of suitable solvents are preferably non-volatile solvents, for example polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, furthermore tricresyl phosphate, di-n-butyl phthalate, di octyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic ethers such as benzylphenyl ether, hydrocarbon oils such as paraffin or kerosene, for example derivatives of diphenyl, naphthalene or terphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, dibenzyltoluene, partially hydrogenated terphenol Xylenes, mono- to tetramethylated diphenylalkanes or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons. Mixtures of various solvents, in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
Die Kapselwände können durch Koazervationskräfte gleichmässig um die Tröpfchen der Farbbildnerlösung herum gebildet werden, wobei das Einkapselungsmaterial z.B. aus Gelatine und Gummi arabicum bestehen kann, wie dies z.B. in der US-Patentschrift 2 800 457 beschrieben ist. Die Kapseln können vorzugsweise auch aus einem Aminoplast oder modifizierten Aminoplasten durch Polykondensation gebildet werden, wie es in den britischen Patentschriften 989,264, 1 156 725,1 301 052 und 1 355 124 beschrieben ist. Ebenfalls geeignet sind Mikrokapseln, welche durch Grenzflächenpolymerisation gebildet werden, wie z.B. Kapseln aus Polyester, Polycarbonat, Polysulfonamid, Polysulfonat, besonders aber aus Polyamid oder Polyurethan.The capsule walls can be formed evenly around the droplets of the color former solution by coacervation forces, the encapsulation material e.g. may consist of gelatin and gum arabic, such as e.g. in U.S. Patent 2,800,457. The capsules can preferably also be formed from an aminoplast or modified aminoplast by polycondensation, as described in British Patents 989,264, 1 156 725, 301 052 and 1 355 124. Microcapsules formed by interfacial polymerization, such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
Die Farbbildner der Formeln (1) bis (5) enthaltenden Mikrokapseln können zur Herstellung von druckempfindlichen Kopiermaterialien der verschiedensten bekannten Arten verwendet werden. Die verschiedenen Systeme unterscheiden sich im wesentlichen voneinander durch die Anordnung der Kapseln, der Farbreaktanten und durch das Trägermaterial.The color formers of the formulas (1) to (5) containing microcapsules can be used to produce pressure-sensitive copying materials of various known types. The different systems differ essentially from each other in the arrangement of the capsules, the color reactants and the carrier material.
Bevorzugt wird eine Anordnung, bei der der eingekapselte Farbbildner in Form einer Schicht auf der Rückseite eines Uebertragungsblattes und der Elektronenakzeptor in Form einer Schicht auf der Vorderseite eines Empfangsblattes vorhanden sind.An arrangement is preferred in which the encapsulated color former is in the form of a layer on the back of a transfer sheet and the electron acceptor is in the form of a layer on the front of a receiver sheet.
Eine andere Anordnung der Bestandteile besteht darin, dass die den Farbbildner enthaltenden Mikrokapseln und der Entwickler in oder auf den gleichen Blatt in Form einer oder mehrerer Einzelschichten oder in der Papierpulpe vorliegen.Another arrangement of the components is that the microcapsules containing the color former and the developer are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
Die Kapseln werden vorzugsweise mittels eines geeigneten Binders auf dem Träger befestigt. Da Papier das bevorzugte Trägermaterial ist, handelt es sich bei diesem Binder hauptsächlich um Papierbeschichtungsmittel, wie Gummi arabicum, Polyvinylalkohol, Hydroxymethylcellulose, Casein, Methylcellulose, Dextrin, Stärke oder Stärkederivate oder Polymerlatices. Letztere sind beispielsweise Butadien-Styrolcopolymerisate oder Acrylhomo- oder copolymere.The capsules are preferably attached to the carrier by means of a suitable binder. Since paper is the preferred carrier material, this binder is primarily paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch or starch derivatives or polymer latices. The latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
Als Papier werden nicht nur normale Papiere aus Cellulosefasern, sondern auch Papiere, in denen die Cellulosefasern.(teilweise oder vollständig) durch Fasern aus synthetischen Polymerisaten ersetzt sind, verwendet.The paper used is not only normal papers made of cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made of synthetic polymers.
Die Verbindungen der Formeln (1) bis (5) können auch als Farbbildner in einem thermoreaktiven Aufzeichnungsmaterial verwendet werden. Dieses enthält in der Regel mindestens einen Schichtträger, einen Farbbildner, einen Elektronenakzeptor und gegebenenfalls auch ein Bindemittel und/oder Wachs.The compounds of formulas (1) to (5) can also be used as color formers in a thermoreactive recording material. This usually contains at least one layer support, a color former, an electron acceptor and optionally also a binder and / or wax.
Thermoreaktive Aufzeichnungssysteme umfassen z.B. wärmeempfindliche Aufzeichnungs- und Kopiermaterialien und -papiere. Diese Systeme werden beispielsweise zum Aufzeichnen von Informationen, z.B. in elektronischen Rechnern, Ferndruckern, Fernschreibern oder in Aufzeichnungsgeräten und Messinstrumenten,wie z.B. Elektrocardiographen, verwendet. Die Bilderzeugung (Markierung) kann auch manuell mit einer erhitzten Feder erfolgen. Eine weitere Einrichtung der Erzeugung von Markierungen mittels Wärme sind Laserstrahlen.Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, for example in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, such as, for example, electrocardiographs. The image generation (marking) can also be done manually done with a heated spring. Another device for producing markings by means of heat is laser beams.
Das thermoreaktive Aufzeichnungsmaterial kann so aufgebaut sein, dass der Farbbildner in einer Bindemittelschicht gelöst oder dispergiert ist und in einer zweiten Schicht der Entwickler in dem Bindemittel gelöst und dispergiert ist. Eine andere Möglichkeit besteht darin, dass sowohl der Farbbildner als auch der Entwickler in einer Schicht dispergiert sind. Das Bindemittel wird in spezifischer. Bezirken mittels Wärme erweicht und an diesen Punkten, an denen Wärme angewendet wird, kommt der Farbbildner mit dem Elektronenakzeptor in Kontakt und es entwickelt sich sofort die erwünschte Farbe.The thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved and dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer. The binder becomes more specific. Districts softened by heat and at these points where heat is applied, the color former comes into contact with the electron acceptor and the desired color develops immediately.
Als Entwickler eignen sich die gleichen Elektronenakzeptoren, wie sie . in druckempfindlichen Papieren verwendet werden. Beispiele für Entwickler sind die bereits erwähnten Tonminerale und besonders Phenolharze, oder auch phenolische Verbindungen, wie sie beispielsweise in der DE-PS 12 51 348 beschrieben sind, z.B. 4-tert.-Butylphenol, 4-Phenylphenol, 4-Hydroxydiphenyläther, a-Naphthol, β-Naphthol, 4-Hydroxy-diphenyl-sulfon, 4-Hydroxybenzoesäure-methylester oder -benzylester, 4-Hydroxyacetophenon, 2,2'-Dihydroxy-diphenyl, 4,4'-Isopropylidendiphenol, 4,4'-Isopropyliden-bis-(2-methylphenol), 2,2-Methylen-bis-(4-phenylphenol), 4,4'-Bis-(hydroxyphenyl)-valeriansäure, Hydrochinon, Pyrogallol, Phloroglucin, p-, m-, o-Hydroxybenzoesäure, Gallussäure, 1-Hydroxy-2-naphthoesäure, sowie Borsäure und organische, vorzugsweise aliphatische Dicarbonsäuren, wie z.B. Weinsäure, Oxalsäure, Maleinsäure, Zitronensäure, Citraconsäure oder Bernsteinsäure.The same electron acceptors are suitable as developers. can be used in pressure-sensitive papers. Examples of developers are the clay minerals already mentioned and especially phenolic resins, or also phenolic compounds, such as are described for example in DE-PS 12 51 348, e.g. 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, β-naphthol, 4-hydroxy-diphenyl-sulfone, 4-hydroxybenzoic acid methyl ester or benzyl ester, 4-hydroxyacetophenone, 2,2'-dihydroxy -diphenyl, 4,4'-isopropylidenediphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 2,2-methylene-bis- (4-phenylphenol), 4,4'-bis- (hydroxyphenyl) - valeric acid, hydroquinone, pyrogallol, phloroglucin, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, as well as boric acid and organic, preferably aliphatic dicarboxylic acids, such as, for example Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid.
Vorzugsweise werden zur Herstellung des thermoreaktiven Aufzeichnungsmaterials schmelzbare, filmbildende Bindemittel verwendet. Diese Bindemittel sind normalerweise wasserlöslich, während die Bis-Chinazoline und der Entwickler in Wasser schwer löslich oder unlöslich sind. Das Bindemittel sollte in der Lage sein, den Farbbildner und den Entwickler bei Raumtemperatur zu dispergieren und zu fixieren.Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water-soluble, while the bis-quinazolines and developer are sparingly soluble or insoluble in water are. The binder should be able to disperse and fix the color former and developer at room temperature.
Bei Einwirkung von Wärme erweicht oder schmilzt das Bindemittel, so dass der Farbbildner mit dem Entwickler in Kontakt kommt und sich eine Farbe bilden kann. Wasserlösliche oder mindestens in Wasser quellbare Bindemittel sind z.B. hydrophile Polymerisate, wie Polyvinylalkohol, Polyacrylsäure, Hydroxyethylcellulose, Methylcellulose, CarSoxy-methylcellulose, Polyacrylamid, Polyvinylpyrrolidon, Gelatine, Stärke oder veresterte Maisstärke.When exposed to heat, the binder softens or melts so that the color former comes into contact with the developer and a color can form. Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, CarSoxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
Wenn der Farbbildner und der Entwickler in zwei getrennten Schichten vorliegen, können in Wasser unlösliche Bindemittel, d.h. in nichtpolaren oder nur schwach polaren Lösungsmitteln lösliche Bindemittel, wie z.B. Naturkautschuk, synthetischer Kautschuk, chlorierter Kautschuk, Alkydharze, Polystyrol, Styrol/Butadien-Mischpolymerisate, Polymethylacrylate, Ethylcellulose, Nitrocellulose und Polyvinylcarbazol, verwendet werden. Die bevorzugte Anordnung ist jedoch diejenige, bei der der Farbbildner und der Entwickler in einer Schicht in einem wasserlöslichen Bindemittel enthalten sind.If the color former and developer are in two separate layers, water-insoluble binders, i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used. However, the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
Die thermoreaktiven Schichten können weitere Zusätze enthalten. Zur Verbesserung des Weissgrades, zur Erleichterung des Bedruckens der Papiere und zur Verhinderzung des Festklebens der erhitzten Feder können diese Schichten, z.B. Talk, Titandioxyd, Zinkoxyd, Aluminiumoxyd, Aluminiumhydroxyd, Calciumcarbonat (z.B. Kreide), Tone oder auch organische Pigmente, wie z.B. Harnstoff-Formaldehydpolymerisate, enthalten. Um zu bewirken, dass nur innerhalb eines begrenzten Temperaturbereiches die Farbe gebildet wird, können Substanzen, wie Harnstoff, Thioharnstoff, Diphenylthioharnstoff, Acetamid, Acetanilid, Stearinsäureamid, Phthalsäureanhydrid, Metallstearate,wie z.B. Zinkstearat, Phthalsäurenitril, Dimethylterephthalat oder andere entsprechende, schmelzbare Produkte, welche das gleichzeitige Schmelzen des Farbbildners und des Entwicklers induzieren, zugesetzt werden. Bevorzugt enthalten thermographische Aufzeichnungsmaterialien Wachse, z.B. Carnaubawachs, Montanawachs, Paraffinwachs, Polyethylenwachs, Kondensate höherer Fettsäureamide und Formaldehyd oder Kondensate höherer Fettsäuren und Ethylendiamin.The thermoreactive layers can contain further additives. To improve the degree of whiteness, to facilitate printing on the papers and to prevent the heated spring from sticking, these layers, for example talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (for example chalk), clays or even organic pigments, such as for example urea Formaldehyde polymers. In order to ensure that the color is formed only within a limited temperature range, substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal stearates, such as, for example, zinc stearate, phthalic acid nitrile, dimethyl terephthalate products or other corresponding, meltable products induce the simultaneous melting of the color former and the developer will. Thermographic recording materials preferably contain waxes, for example carnauba wax, montana wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
In den folgenden Beispielen beziehen sich die angegebenen Prozentsätze, wenn nicht anderes angegeben ist, auf das Gewicht.In the following examples, the percentages given are by weight unless otherwise specified.
Beispiel 1: 29,3 g der Chinazolonverbindung der Formel
Man lässt die Lösung auf eine Suspension von 3,1 g Ethylenglykol, 100 g Natriumhydroxidlösung (50%) und 1 g Tetrabutylammoniumbromid zutropfen. Alsdann rührt man die Suspension während einer Stunde unter Rückfluss und versetzt danach bei 90°C mit 150 ml Wasser. Die Xylolphase wird abgetrennt und mehrmals mit heissem Wasser gewaschen. Man lässt dann die Xylolphase unter Rühren abkühlen und fügt bei 35°C 100 g Methanol hinzu. Dabei fällt das Produkt kristallin aus, welches bei 15-20°C abfiltriert, mit Methanol und Wasser gewaschen und getrocknet wird. Man erhält 22 g einer Bis-Chinazolin-Verbindung der Formel
Auf Säureton entwickelt dieser Farbbildner eine intensiv gelbe Farbe mit guter Licht- und hervorragender Sublimierechtheit.On acid clay, this color former develops an intense yellow color with good light and excellent sublimation fastness.
Das Remissionsmaximum dieser Bis-Chinazolin-Verbindung auf Säureton beschichtetes Papier liegt bei 464 nm.The maximum reflectance of this bis-quinazoline compound on acid-coated paper is 464 nm.
Auf gleiche Weise wie in Beispiel 1 beschrieben, erhält man unter Verwendung der entsprechenden Ausgangsstoffe die in der folgenden Tabelle aufgeführten Bis-Chinazolin-Verbindungen der Formel
Beispiel 15: 17 g der Chinazolonverbindung der Formel
wird noch 1 Stunde bei 85-90°C gerührt. Alsdann lässt man die Lösung auf eine Suspension von 1,6 g Ethylenglykol, 30 g Natriumhydroxidlösung (50%) und 1 g Tetrabutylammoniumbromid zutropfen. Man rührt die Emulsion während 2 Stunden bei 90-95°C, trennt die Toluolphase, wäscht diese mit Wasser und fällt das Produkt durch Zugabe von 80 g Methanol bei 40°C kristallin aus. Durch Filtration bei 15°C, waschen mit Methanol und Trocknen erhält man 10,1 g einer praktisch farblosen Bischinazolin-Verbindung der Formel
Durch Umkristallisation aus Toluol/Isopropylalkohol 7:3 erhält man das reine Produkt mit einem Schmelzpunkt von 228-229°C. Auf Säureton entwickelt dieser Farbbildner eine gelbe Farbe mit guter Lichtechtheit. Der Farbbildner zeichnet sich zudem durch eine hervorragende Sublimierechtheit aus.Recrystallization from toluene / isopropyl alcohol 7: 3 gives the pure product with a melting point of 228-229 ° C. This color former develops a yellow color with good light fastness on acid clay. The color former is also characterized by excellent sublimation fastness.
Eine Lösung von 3 g der Bis-Chinazolinverbindung der Formel (21) in 80 g partiell hydriertem Terphenyl und 17 g Kerosin wird auf an sich bekannte Weise mit Gelatine und Gummi arabicum durch Koazervation mikroverkapselt, mit Stärkelösung vermischt und auf ein Blatt Papier gestrichen. Ein zweites Blatt Papier wird auf der Frontseite mit säureaktiviertem Bentonit als Farbentwickler beschichtet. Das erste Blatt und das mit Farbentwickler beschichtete Papier werden mit den Beschichtungen benachbart aufeinandergelegt. Durch Schreiben mit der Hand oder mit der Schreibmaschine auf dem ersten Blatt wird Druck ausgeübt, und es entwickelt sich sofort auf dem mit dem Entwickler beschichteten Blatt eine intensive gelbe Kopie, die ausgezeichnet sublimier- und lichtecht ist.A solution of 3 g of the bis-quinazoline compound of the formula (21) in 80 g of partially hydrogenated terphenyl and 17 g of kerosene is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, mixed with starch solution and spread on a sheet of paper. A second sheet of paper is coated on the front with acid-activated bentonite as a color developer. The first sheet and the paper coated with color developer are placed on top of each other with the coatings adjacent. Writing by hand or with the typewriter on the first sheet exerts pressure, and an intense yellow copy develops on the sheet coated with the developer, which is excellent in sublimation and lightfastness.
Entsprechende intensive, sublimier- und lichtechte gelbe Kopien werden auch bei Verwendung jedes der anderen in den Herstellungsbeispielen 2 bis 15 angegebenen Farbbildner der Formel (22) erzielt.Corresponding intense, sublimation and lightfast yellow copies are also obtained when using each of the other color formers of the formula (22) specified in Preparation Examples 2 to 15.
Beispiel 17: Ersetzt man in Beispiel 16 die Bis-Chinazolinverbindung der Formel (21) durch eine Mischung der folgenden Zusammensetzung
- 1,4 g 3,3-Bis-(4t-dimethylaminophenyl)-6-dimethylamino- phthalid,
- 1,0 g N-Butylcarbazol-3-yl-bis-(4'-N-methyl-N-phenylamino- phenyl-)methan
- 0,6 g der Bis-Chinazolinverbindung der Formel (21)
und 0,5 g 3,3-Bis-(N-n-octyl-2'-methylindol-3'-yl-)phthalid und verfährt im übrigen wie in Beispiel 16 beschrieben, so erhält man ein druckempfindliches Aufzeichnungsmaterial, welches durch Schreiben mit der Hand oder mit der Schreibmaschine eine intensive und lichtechte schwarze Kopie ergibt.Example 17: In Example 16, the bis-quinazoline compound of the formula (21) is replaced by a mixture of the following composition
- 1.4 g of 3,3-bis (4 t- dimethylaminophenyl) -6-dimethylamino-phthalide,
- 1.0 g of N-butylcarbazol-3-yl-bis (4'-N-methyl-N-phenylaminophenyl) methane
- 0.6 g of the bis-quinazoline compound of the formula (21)
and 0.5 g of 3,3-bis- (Nn-octyl-2'-methylindol-3'-yl) phthalide and otherwise proceeding as described in Example 16, a pressure-sensitive recording material is obtained which can be obtained by writing with the Hand or with the typewriter produces an intense and lightfast black copy.
Beispiel 18: 1 g der Bis-Chinazolinverbindung der Formel (21) wird in 17 g Toluol gelöst. Zu dieser Lösung gibt man unter Rühren 12 g Polyvinylacetat, 8 g Calciumcarbonat und 2 g Titandioxyd. Die erhaltene Suspension wird im Gewichtsverhältnis 1:1 mit Toluol verdünnt und mit einem 10 µm Rakel auf ein Blatt Papier gestrichen. Auf dieses Blatt Papier wird ein zweites Blatt Papier gelegt, dessen Unterseite bei einem Auftragsgewicht von 3 g/m2 mit einer Mischung bestehend aus 1 Teil eines Amidwachses, 1 Teil eines Stearinwachses und 1 Teil Zinkchlorid beschichtet worden ist. Durch Schreiben mit der Hand oder mit der Schreibmaschine auf dem oberen Blatt wird Druck ausgeübt, und es entwickelt sich sofort auf dem mit den Farbbildner beschichteten Blatt, eine intensive, sublimier- und lichtechte gelbe Farbe.Example 18: 1 g of the bis-quinazoline compound of the formula (21) is dissolved in 17 g of toluene. 12 g of polyvinyl acetate, 8 g of calcium carbonate and 2 g of titanium dioxide are added to this solution with stirring. The suspension obtained is diluted in a weight ratio of 1: 1 with toluene and spread on a sheet of paper using a 10 μm doctor blade. A second sheet of paper is placed on this sheet of paper, the underside of which has been coated with a mixture consisting of 1 part of an amide wax, 1 part of a stearic wax and 1 part of zinc chloride at an application weight of 3 g / m 2 . By writing by hand or with a typewriter on the top sheet, pressure is exerted and an intense, sublimation and lightfast yellow color develops on the sheet coated with the color formers.
In einer Kugelmühle werden 32 g 4,4'-Isopropylidendiphenol (Bisphenol A), 3,8 g Distearylamid des Ethylendiamins, 39 g Kaolin, 20 g eines zu 88% hydrolysierten Polyvinylalkohols und 500 ml Wasser gemahlen bis die Teilchengrösse ca. 5 µm beträgt. In einer zweiten Kugelmühle werden 6 g der Verbindung der Formel (21), 3 g eines zu 88% hydrolysierten Polyvinylalkohols und 60 ml Wasser zu einer Teilchengrösse von ca. 3;um gemahlen.32 g of 4,4'-isopropylidenediphenol (bisphenol A), 3.8 g of distearylamide of ethylenediamine, 39 g of kaolin, 20 g of an 88% hydrolyzed polyvinyl alcohol and 500 ml of water are ground in a ball mill until the particle size is approximately 5 μm . In a second ball mill, 6 g of the compound of the formula (21), 3 g of an 88% hydrolyzed polyvinyl alcohol and 60 ml of water are obtained to a particle size of approx. 3 ; around ground.
Die beiden Dispersionen werden zusammengegeben und mit einem Trockenauftragsgewicht von 5,5 g/m2 auf ein Papier gestrichen. Durch Berührung des Papiers mit einem erhitzten Kugelschreiber wird eine intensive gelbe Farbe erhalten, die eine ausgezeichnete Sublimier-und Lichtechtheit hat.The two dispersions are combined and coated onto a paper with a dry application weight of 5.5 g / m 2 . By touching the paper with a heated ballpoint pen, an intense yellow color is obtained which has excellent sublimation and light fastness.
Intensive und lichtechte gelbe Farben können auch bei Verwendung jeder der anderen in den Herstellungsbeispielen 2 bis 15 angegebenen Farbbildner der Formel (22) erhalten werden.Intense and lightfast yellow colors can also be obtained using any of the other color formers of formula (22) given in Preparation Examples 2-15.
Beispiel 20: In einer Kugelmühle werden 2,7 g der Bis-Chinazolin- verbindung der Formel (21), 24 g N-phenyl-N'-(1-hydroxy-2,2,2-trichloroethyl)-harnstoff, 16 g Stearinsäureamid, 59 g eines zu 88% hydrolysierten Polyvinylalkohols und 58 ml Wasser gemahlen bis die Teilchengrösse 2-5 µm beträgt. Diese Suspension wird bei einem Trockenauftragsgewicht von 5,5 g/m2 auf ein Blatt Papier gestrichen. Durch Berührung des Papiers mit einem erhitzten Kugelschreiber wird eine intensive, sublimier- und lichtechte gelbe Farbe erhalten.Example 20: 2.7 g of the bis-quinazoline compound of the formula (21), 24 g of N-phenyl-N '- (1-hydroxy-2,2,2-trichloroethyl) urea, 16 g are placed in a ball mill Stearic acid amide, 59 g of an 88% hydrolyzed polyvinyl alcohol and 58 ml of water ground until the particle size is 2-5 µm. This suspension is spread on a sheet of paper at a dry application weight of 5.5 g / m 2 . By touching the paper with a heated ballpoint pen, an intense, sublimation and lightfast yellow color is obtained.
Claims (22)
der Ring B unsubstituiert oder durch Cyano, Halogen, Niederalkyl oder Niederalkoxy substituiert ist und der Ring D einen hydrierten fünf-oder sechsgliedrigen Stickstoffheterocyclus darstellt, der gegebenenfalls als Ringglied ein weiteres Heteroatom aufweist und unsubstituiert oder durch Halogen, Cyano, Hydroxyl, Niederalkyl, Niederalkoxy, C5-C6-Cycloalkyl, Benzyl oder C3-C6-Alkylen einfach oder je nach Substituenten mehrfach C-substituiert ist.1. Chromogenic bis-quinazoline compounds characterized in that they have the formula
the ring B is unsubstituted or substituted by cyano, halogen, lower alkyl or lower alkoxy and the ring D represents a hydrogenated five- or six-membered nitrogen heterocycle which optionally has a further hetero atom as ring member and is unsubstituted or by halogen, cyano, hydroxyl, lower alkyl, lower alkoxy, C 5 -C 6 cycloalkyl, benzyl or C 3 -C 6 alkylene is mono- or C-substituted, depending on the substituent.
der Ring A1 unsubstituiert oder durch einen oder zwei Substituenten ausgewählt aus Cyano, Halogen, Niederalkyl, Phenyl und Niederalkoxy substituiert ist.7. bis-quinazoline compounds according to claim 1, characterized in that they have the formula
the ring A 1 is unsubstituted or substituted by one or two substituents selected from cyano, halogen, lower alkyl, phenyl and lower alkoxy.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH195084 | 1984-04-18 | ||
CH1950/84 | 1984-04-18 |
Publications (3)
Publication Number | Publication Date |
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EP0159295A2 true EP0159295A2 (en) | 1985-10-23 |
EP0159295A3 EP0159295A3 (en) | 1986-10-08 |
EP0159295B1 EP0159295B1 (en) | 1989-03-15 |
Family
ID=4222383
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP85810163A Expired EP0159295B1 (en) | 1984-04-18 | 1985-04-12 | Chromogene bis-quinazoline compounds, process for their preparation and their use as a dye precursor in pressure-sensitive or heat-sensitive registration materials |
Country Status (7)
Country | Link |
---|---|
US (1) | US4668966A (en) |
EP (1) | EP0159295B1 (en) |
JP (1) | JPS60233065A (en) |
DE (1) | DE3568733D1 (en) |
ES (1) | ES542331A0 (en) |
FI (1) | FI87070C (en) |
YU (1) | YU64385A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0384313A1 (en) * | 1989-02-22 | 1990-08-29 | BASF Aktiengesellschaft | Quinoline-4-carboxylic acid derivatives and their application |
RU2702751C1 (en) * | 2019-03-28 | 2019-10-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Pyrimidine derivatives having modulation activity on ampa-type receptors |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4766211A (en) * | 1985-09-06 | 1988-08-23 | Ciba-Geigy Corporation | Chromogenic quinazolines |
US5326766A (en) * | 1992-08-19 | 1994-07-05 | Dreikorn Barry A | 4-(2-(4-(2-pyridinyloxy)phenyl)ethoxy)quinazoline and analogues thereof |
GB9522233D0 (en) * | 1995-10-31 | 1996-01-03 | Wiggins Teape Group The Limite | Pressure-sensitive copying paper |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0033716A1 (en) * | 1980-01-31 | 1981-08-12 | Ciba-Geigy Ag | Chromogenic quinazoline compounds, processes for their preparation and their use as colour constituents in pressure-sensitive or heat-sensitive recording materials |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3340260A (en) * | 1962-12-03 | 1967-09-05 | Ciba Geigy Corp | 4-amino-pyrimidines |
US3574210A (en) * | 1967-07-13 | 1971-04-06 | Squibb & Sons Inc | 2,4-disubstituted-6-nitro-and 6-a minoquinazolines |
US3637693A (en) * | 1968-07-12 | 1972-01-25 | Du Pont | Hydroxyarylquinazolines and their use as uv-absorbers |
US3931179A (en) * | 1974-03-06 | 1976-01-06 | Sandoz Inc. | N,N-Bis(4-Quinazolinyl)alkanediamines |
US3998951A (en) * | 1974-03-13 | 1976-12-21 | Fmc Corporation | Substituted 2-arylquinazolines as fungicides |
US4011323A (en) * | 1974-03-18 | 1977-03-08 | Sandoz, Inc. | Bi-4-[1-(quinazolinyl-4)piperidyls] and bis{4-[1-(quinazolinyl-4)piperidyl]alkanes} |
US4306065A (en) * | 1979-12-19 | 1981-12-15 | A. H. Robins Company, Incorporated | 2-Aryl-4-substituted quinazolines |
JPS57204031A (en) * | 1981-06-09 | 1982-12-14 | Ricoh Co Ltd | Heat development type diazo copying material |
CH657131A5 (en) * | 1982-04-22 | 1986-08-15 | Ciba Geigy Ag | CHROMOGENIC DIHYDROCHINAZOLINE AND THEIR PRODUCTION AND USE. |
GB8329361D0 (en) * | 1983-11-03 | 1983-12-07 | Wiggins Teape Group Ltd | Record material |
-
1985
- 1985-04-11 US US06/721,963 patent/US4668966A/en not_active Expired - Lifetime
- 1985-04-12 EP EP85810163A patent/EP0159295B1/en not_active Expired
- 1985-04-12 DE DE8585810163T patent/DE3568733D1/en not_active Expired
- 1985-04-15 FI FI851493A patent/FI87070C/en not_active IP Right Cessation
- 1985-04-16 YU YU00643/85A patent/YU64385A/en unknown
- 1985-04-17 ES ES542331A patent/ES542331A0/en active Granted
- 1985-04-18 JP JP60081479A patent/JPS60233065A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0033716A1 (en) * | 1980-01-31 | 1981-08-12 | Ciba-Geigy Ag | Chromogenic quinazoline compounds, processes for their preparation and their use as colour constituents in pressure-sensitive or heat-sensitive recording materials |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0384313A1 (en) * | 1989-02-22 | 1990-08-29 | BASF Aktiengesellschaft | Quinoline-4-carboxylic acid derivatives and their application |
RU2702751C1 (en) * | 2019-03-28 | 2019-10-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Pyrimidine derivatives having modulation activity on ampa-type receptors |
Also Published As
Publication number | Publication date |
---|---|
FI851493A0 (en) | 1985-04-15 |
YU64385A (en) | 1988-02-29 |
ES8602770A1 (en) | 1985-12-16 |
FI87070C (en) | 1992-11-25 |
EP0159295A3 (en) | 1986-10-08 |
EP0159295B1 (en) | 1989-03-15 |
FI87070B (en) | 1992-08-14 |
JPH0524904B2 (en) | 1993-04-09 |
JPS60233065A (en) | 1985-11-19 |
US4668966A (en) | 1987-05-26 |
DE3568733D1 (en) | 1989-04-20 |
ES542331A0 (en) | 1985-12-16 |
FI851493L (en) | 1985-10-19 |
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