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
  • B41M5/136—Organic colour formers, e.g. leuco dyes
• • 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
  • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring

Definitions

• the color images are usually produced by exerting pressure on the microcapsules applied to the paper, which enclose the chromogenic substance, the color reaction between the chromogen and the acceptor taking place in the presence of solvents.
• Components (A), (B) and (C) come into contact with each other by pressure and leave records on the carrier material.
• the color is produced in accordance with the type of components (A) and (B), which represent the electron donor and form the chromogenic part.
• the color formation is caused by component (C).
• the desired colors e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated.
• components (A) and (B) together with one or more conventional color formers e.g.
• 3,3- (bis-aminophenyl -) phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides, (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialkylamino-2- dibenzylaminofluoranes, 6-dialkylamino-3-methyl-2-arylaminofluoranes, 3,6-bisalkoxyfluoranes, 3,6-bisdiarylaminofluoranes, leucoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothia
• the compounds of formula (1) contain, as part of their structure, the basic structure of, for example, a lactone, lactam, sulton, sultam or phthalan, and these basic structures are subject to - before, during or after the reaction of component (A) the condensation component (B) - upon contact with the color developer (component (C)) a ring opening or bond cleavage, as they are also suspected by the previously common recording materials.
• component (A) contain, as part of their structure, the basic structure of, for example, a lactone, lactam, sulton, sultam or phthalan, and these basic structures are subject to - before, during or after the reaction of component (A) the condensation component (B) - upon contact with the color developer (component (C)) a ring opening or bond cleavage, as they are also suspected by the previously common recording materials.
• the heteroaromatic radical X is expediently bonded to the central (meso) carbon atom of the polycyclic compound via a carbon atom of the hetero ring.
• X means, for example, a thienyl, acridinyl, benzofuranyl, benzothienyl, naphthothienyl or phenothiazinyl radical, but advantageously a pyrrolyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, dihydroquinolchinyl or tetrahydrovinyl radical.
• the mono- or polynuclear heteroaromatic radical can be ring-substituted one or more times.
• the C substituents are e.g. Halogen, hydroxy, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkoxycarbonyl, acyl with 1 to 8 carbon atoms, preferably lower alkylcarbonyl, amino, lower alkylamino, lower alkylcarbonylamino or di-lower alkylamino, C5-C6-cycloalkyl, benzyl or phenyl in question, while N-substituents for example C1-C12-alkyl, C2-C12-alkenyl, C5-C10-cycloalkyl, C1-C8-acyl, phenyl, benzyl, phenethyl or phenisopropyl, each of which, for example can be substituted by cyano, halogen, nitro,
• the alkyl and alkenyl radicals can be straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylbutyl, sec-butyl, t-butyl, amyl, isopentyl, n-hexyl, 2-ethylhexyl, isooctyl, n-octyl, 1,1 , 3,3-tetramethylbutyl, nonyl, isononyl, 3-ethylheptyl, decyl or n-dodecyl or vinyl, allyl, 2-methylallyl, 2-ethylallyl, 2-butenyl or octenyl.
• acyl is especially formyl, lower alkyl carbonyl, e.g. Acetyl or propionyl, or benzoyl. Further acyl residues can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl. Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
• Lower alkyl, lower alkoxy and lower alkylthio are groups or group components which have 1 to 6, in particular 1 to 3, carbon atoms.
• Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or hexyl or methoxy, ethoxy, isopropoxy, isobutoxy, tert-butoxy or amyloxy or methylthio , Ethylthio, propylthio or butylthio.
• Halogen means for example fluorine, bromine or preferably chlorine.
• Preferred heteroaromatic radicals are substituted 2- or 3-pyrrolyl or especially 3-indolyl radicals, such as e.g. N-C1-C8-alkyl-pyrrol-2-yl-, N-phenylpyrrol-3-yl-, N-C1-C8-alkyl-2-methylindol-3-yl-, N-C2-C4-alkanoyl-2 -methylindol-3-yl, 2-phenylindol-3-yl or N-C1-C8-alkyl-2-phenylindol-3-yl radicals.
• 3-indolyl radicals such as e.g. N-C1-C8-alkyl-pyrrol-2-yl-, N-phenylpyrrol-3-yl-, N-C1-C8-alkyl-2-methylindol-3-yl-, N-C2-C4-alkanoyl-2 -methylindol-3-yl, 2-
• X can be an aromatic radical which is unsubstituted or substituted by halogen, cyano, lower alkyl, C5-C6-cycloalkyl, C1-C8-acyl, -NR1R2, -OR3 or -SR3 Naphthylrest mean.
• X preferably represents a substituted phenyl radical of the formula represents.
• R1, R2 and R3, independently of one another, are each hydrogen, unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or unsubstituted or by halogen, Trifluoromethyl, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX′X ⁇ or 4-NX′X ⁇ -phenylamino ring-substituted phenalkyl or phenyl, in which X ′ and X ⁇ , independently of one another, represent hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R1 and R2 together with the nitrogen atom connecting them form a five- or six-membered, preferably saturated, heterocyclic radical.
• V denotes hydrogen, halogen, lower alkyl, C1-C12-alkoxy, C1-C12-acyloxy, benzyl, phenyl, benzyloxy, phenyloxy , Benzyl or benzyloxy substituted by halogen, cyano, lower alkyl or lower alkoxy, or the group -NT1T2.
• T1 and T2 independently of one another, each represent hydrogen, lower alkyl, C5-C10 cycloalkyl, unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy, or acyl having 1 to 8 carbon atoms and T1 also unsubstituted or by halogen, cyano, lower alkyl or lower alkoxy substituted phenyl.
• m is 1 or 2.
• -NR1R2 and -OR3 are preferably in the para position to the junction.
• a V is preferably in the ortho position to the connection point.
• R, R1, R2 and R3 represent, for example, the substituents listed above for alkyl radicals.
• alkyl radicals in R1, R2 and R3 substituted it is mainly Cyanoalkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl each preferably with a total of 2 to 8 carbon atoms, such as 2-cyanoethyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2,3-dihydroxypropyl, 2-hydroxy-3- chloropropyl, 3-methoxypropyl, 4-methoxybutyl or 4-propoxybutyl.
• cycloalkyl in the meaning of R, R1, R2, R3, T1 and T2 are cyclopentyl, cycloheptyl or preferably cyclohexyl.
• the cycloalkyl radicals can contain one or more C1-C4 alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
• R, R1, R2 and R3 can be phenethyl, phenylisopropyl or especially benzyl.
• Preferred substituents in the phenalkyl and phenyl group of the R radicals are e.g. Halogen, cyano, methyl, triluormethyl, methoxy or carbomethoxy.
• araliphatic or aromatic radicals are methylbenzyl, 2,4- or 2,5-dimethylbenzyl, chlorobenzyl, dichlorobenzyl, cyanobenzyl, tolyl, xylyl, chlorophenyl, methoxyphenyl, 2,6-dimethylphenyl, trifluoromethylphenyl or carbomethoxyphenyl.
• the acyloxy radical in V is, for example, formyloxy, lower alkylcarbonyloxy, e.g. Acetyloxy or propionyloxy, or benzoyloxy.
• V can be a straight-chain or branched group, e.g. Methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, amyloxy, 1,1,3,3-tetramethylbutoxy, n-hexyloxy, n-octyloxy or dodecyloxy.
• the pair of substituents (R1 and R2) together with the common nitrogen atom represent a heterocyclic radical
• this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino, piperazino, N-alkylpiperazino, such as e.g. N-methylpiperazino, N-phenylpiperazino or N-alkylimidazolino.
• Preferred saturated heterocyclic radicals for -NR1R2 are pyrrolidino, piperidino or morpholino.
• R1 and R2 are preferably cyclohexyl, benzyl, phenethyl, cyano-lower alkyl, for example ⁇ -cyanoethyl or primarily lower alkyl, such as methyl, ethyl or n-butyl.
• -NR1R2 is also preferably pyrrolidinyl.
• R3 is preferably lower alkyl or benzyl.
• V can advantageously be hydrogen, halogen, lower alkyl, e.g. Methyl, benzyloxy, C1-C8 alkoxy, primarily lower alkoxy, e.g. Methoxy, ethoxy, isopropoxy or tert-butoxy, or the group -NT1T2, where one of the radicals T1 and T2 is preferably C1-C8 acyl or lower alkyl and the other is hydrogen or lower alkyl.
• the acyl radical in this case is especially lower alkylcarbonyl, e.g. Acetyl or propionyl.
• V is preferably acetylamino, dimethylamino, diethylamino, benzyloxy or especially lower alkoxy and especially ethoxy or hydrogen.
• Substituents in the sense of Y are easily removable substituents on the central (meso) carbon atom, which thereby turn into an anion.
• substituents can be halogen atoms, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether groups, such as alkoxy, heteroaryloxy, aryloxy, cycloalkoxy and aralkoxy, or in particular acyloxy groups, for example of the formula (1c) R ′ - (NH-) n-1 -Q′-O-
• R ' is an organic radical, preferably unsubstituted or substituted C1-C22-alkyl, aryl, cycloalkyl, aralkyl or heteroaryl, Q'-CO- or -SO2- and n is 1 or 2, preferably 1.
• acyloxy groups include acetyloxy, propionyloxy, chloroacetyloxy, benzoyloxy, methylsulfonyloxy, ethylsulfonyloxy, chloroethylsulfonyloxy, trifluoromethylsulfonyloxy, 2-chloroethylsulfonylacetyloxy, phenylsulfonyloxy, tolylsulfonyloxy or phenylaminocarbonyl.
• Y is preferably an acyloxy group of the formula R ⁇ -CO-O-, where R ⁇ is lower alkyl or phenyl.
• Q1 preferably represents an oxygen atom, while Q2 preferably represents -SO2- or especially -CO. If represents, then R is preferably hydrogen, methyl or phenyl.
• A is preferably a benzene ring which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl, amino, lower alkylamino, di-lower alkylamino or lower alkylcarbonylamino.
• A is in particular a nitrogen-containing heterocycle with an aromatic character, such as a pyridine or pyrazine ring.
• Ring A can also contain a fused aromatic ring, preferably a benzene ring and thus represents for example a naphthalene, quinoline or quinoxaline ring.
• the preferred 6-membered aromatic or heterocyclic radicals represented by A are the 2,3-pyridino-, 3,4-pyridino-, 2,3-pyrazino-, 2,3-quinoxalino-, 1,2-naphthalino-, 2 , 3-Naphthalino- or 1,2-benzo radical which is unsubstituted or substituted by halogen, such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or an amino group optionally substituted as defined above, the unsubstituted or by halogen, especially 1,2-benzo radical substituted by 4 chlorine atoms is particularly preferred.
• halogen such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or an amino group optionally substituted as defined above
• Particularly important components (A) for the color reactant system according to the invention correspond to the formula in which A 1 is a benzene or pyridine ring optionally substituted by halogen, cyano, lower alkyl, lower alkoxy or di-lower alkylamino, Y1 halogen, acyloxy and especially lower alkylcarbonyloxy or benzoyloxy and X1 is a 3-indolyl radical of the formula a substituted phenyl radical of the formula where W1 is hydrogen, unsubstituted or substituted by cyano or lower alkoxy C1-C8-alkyl, acetyl, propionyl or benzyl, W2 is hydrogen, lower alkyl, especially methyl, or phenyl, R4, R5 and R6 independently of one another, each unsubstituted or substituted by hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, C5-C6-cycloalkyl
• the lactone compounds in which X1 is a 3-indolyl radical of the formula (2a) in which W1 is C1-C8-alkyl, W2 is methyl or phenyl and Y1 are lower alkylcarbonyloxy, in particular acetyloxy, are preferred.
• Lactone compounds of the formula are of particular interest in which the ring D is unsubstituted or substituted by 4 chlorine atoms, Y2 benzoyloxy or in particular acetyloxy, W3 C1-C8-alkyl, such as ethyl, n-butyl or n-octyl mean.
• Lactone compounds of the formula are also particularly preferred wherein D and Y2 have the meaning given in formula (3) and R7, R8 and R9 each represent lower alkyl, especially ethyl or n-butyl.
• Compounds of formula (1) which have an acyloxy group as removable substituents Y can be prepared by using a keto acid or carbinol compound (lactol) of the formula wherein A, Q1, Q2 and X have the meaning given, reacted with an acylating agent.
• Suitable acylating agents are reactive functional derivatives of aliphatic, cycloaliphatic or aromatic carboxylic acids or sulfonic acids, especially carboxylic acid halides or anhydrides such as e.g. Acetyl bromide, acetyl chloride, benzoyl chloride and especially acetic anhydride.
• carboxylic acid halides or anhydrides such as e.g. Acetyl bromide, acetyl chloride, benzoyl chloride and especially acetic anhydride.
• Mixed anhydrides i.e. Anhydrides of two different acids can be used.
• Compounds of formula (1) which contain halogen as removable substituents Y are prepared by the hydroxyl group of the carbinol compound of formula (i) replaced by a halogen atom with a halogenating agent, for example by means of thionyl chloride, phosgene, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride in dimethylformamide, dichlorobenzene, benzene, toluene or ethylene dichloride.
• the halogenating agent can also be used in excess without a solvent.
• ether groups By reacting compounds of the formula (1) in which Y is halogen or acyloxy with aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic hydroxy compounds, ether groups can be introduced as further removable substituents Y.
• Suitable alkylating agents are alkyl halides, e.g. Methyl or ethyl iodide, ethyl chloride or dialkyl sulfates, such as dimethyl sulfate or diethyl sulfate.
• Particularly suitable aralkylating agents are benzyl chloride or the corresponding substitution products, e.g. 4-chlorobenzyl chloride, preferably in a non-polar organic solvent such as e.g. Benzene, toluene or xylene can be used.
• condensation components are all those customary in azochemistry and from the relevant literature, such as MR. Swiss, artificial org. Dyes and their intermediates, Springer-Verlag 1964, p. 420 ff.
• condensation components of the benzene series for example: condensation components of the benzene series, the naphthalene series, the open-chain methylene-active compounds and the heterocyclic series.
• condensation components are N-substituted aminophenylethylene compounds, N-substituted aminophenylstyrene compounds, acylacetarylamides, monovalent or polyvalent phenols, phenol ethers (phenetols), 3-aminophenol ethers, anilines, naphthylamines, thionaphthenes, diarylamines, aminoanilines, anilinsulfoniaryoleoleilaminilanesilonilaminilanesilaneilineilonilethaneilineililaminolethaneilineilaneilineilineilanilethililethanilethanilethaneilaneilineilineilanilethaneilineilineilanilethilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanile
• Particularly preferred condensation components are anilines, such as cresidines, phenetidines or N, N-di-lower alkylanilines, 2-lower alkyls, 3-lower alkyls or 2-phenyl indoles, which can each be N-substituted by C1-C8-alkyl and 5-pyrazolones.
• Further preferred coupling components are 3-lower alkyl-6-lower alkoxy- or -6-di-lower alkylaminoindoles, which can also each be N-substituted by C1-C8-alkyl.
• condensation components are 2-amino-4-methoxytoluene, 3-amino-4-methoxytoluene, N, N-dimethylaniline, 4-isopropylaniline, N, N-diethylaniline, N, N-dibenzylaniline, 3-n-butoxy -N, N-di-n-butylaniline, 2-methyl-5-acetyloxy-N, N-diethylaniline, 4-ethoxydiphenylamine, 4-aminodiphenylamine, 3-ethoxy-N, N-dimethylaniline, N, N'-diphenyl-p-phenylenediamine, m-phenetidine, 3-ethoxy -N, N-diethylaniline, 1,3-bis-dimethylaminobenzene, 4-aminotoluene-2-sulfonic acid anilide, 4-aminotoluene-2-sulfonic acid-N-ethy
• Preferred components (B) are also phthalide and especially fluoran compounds which have at least one primary amino group or an amino group monosubstituted by lower alkyl, cyclohexyl or benzyl. These phthalide and fluoran compounds are described for example in FR-A-1 553 291, GB-A-1 211 393, DE-A-2 138 179, DE-A-2 422 899 and EP-A-138 177.
• components (B) are: 2-amino-6-diethylaminofluoran, 2-amino-6-dibutylaminofluoran, 2-amino-3-chloro-6-diethylaminofluoran, 2-methylamino-6-dimethylaminofluoran, 2-ethylamino-6-diethylaminofluoran, 2-methylamino-6-diethylaminofluoran, 2-n-butylamino-6-diethylaminofluoran, 2-n-octylamino-6-diethylaminofluoran, 2-sec butylamino-6-diethylaminofluoran, 2-benzylamino-6-diethylaminofluoran, 2,3-dimethyl-6-ethylaminofluoran, 2,3,7-trimethyl-6-ethylaminofluoran, 2,3,7-trimethyl-6-ethylamino-5 ′ (6 ′) -
• Both polycyclic components (A) and the condensation components (B) can be used alone or as mixtures in the form of a combination of two or more of them in the recording material.
• Inorganic or organic color developers known for recording materials and capable of attracting electrons can be used as component (C).
• Typical examples of inorganic developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite
• activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• Preferred inorganic color developers are Lewis acids, e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
• Lewis acids e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
• solid carboxylic acids advantageously aliphatic dicarboxylic acids, such as tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid, as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride can be used with styrene, ethylene or vinyl methyl ether.
• Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be substituted by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals such as ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, aryl radicals, acyl radicals such as arylsulfonyl, or alkoxycarbonyl radicals or aralkoxycarbonyl radicals such as benzyloxycarbonyl.
• phenols suitable as component (C) are 4-tert-butylphenol, 4-phenylphenol, methylene-bis (p-phenylphenol), 4-hydroxydiphenyl ether, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxybenzoic acid methyl ester or benzyl ester , 2,4-dihydroxybenzoic acid methyl ester, 4-hydroxydiphenyl sulfone, 4'-hydroxy-4-methyl-diphenyl sulfone, 4'-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-acetophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxydiphenyl, 2,4-dihydroxydiphenyl sulfone, 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4-bis- (4
• Particularly preferred components (C) are active clay or zinc salicylates, such as zinc 3,5-bis ( ⁇ -methylbenzyl) salicylate.
• Both components (A) and (B) and in particular component (C) can additionally also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as retention agents, silica gel or UV absorbers, such as, for example 2- (2'-Hydroxyphenyl) benzotriazoles, 2-hydroxyphenyltriazines, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used.
• auxiliaries such as retention agents, silica gel or UV absorbers, such as, for example 2- (2'-Hydroxyphenyl) benzotriazoles, 2-hydroxyphenyltriazines, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used.
• pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, magnesium carbonate, clays such as kaolin, and organic pigments, for example urea-formaldehyde condensates (BET surface area 2-75 m2 / g) or melamine-formaldehyde condensation products.
• the ratio of component (C) to components (A) and (B) depends on the type of the three components, the type of color change and of course also on the desired color concentration. Satisfactory results are achieved if the color-developing component (C) in amounts of 0.1 part by weight, expediently at least 0.5 part to 100 parts by weight, preferably 1 to 20 parts by weight, per part of the components (A ) and (B) can be used together.
• both component (A) and component (B) are preferably dissolved together or separately in an organic solvent and the solutions obtained are expediently encapsulated by processes such as e.g. in the U.S. 2 712 507, 2 800 457, 3 016 308, 3 429 827, 4 100 103 and 3 578 605 or in British Patents 989 264, 1 156 725, 1 301 052 or 1 355 124.
• Microcapsules formed by interfacial polymerization such as e.g. Capsules made from polyester, polycarbonate, polysulfonamide, polysulfonate, but especially from polyamide, polyurea or polyurethane. In some cases it is sufficient that only component (A) is encapsulated. Encapsulation is usually required to prevent early color formation. The latter can also be achieved by incorporating components (A) and (B) into foam, sponge or honeycomb structures.
• suitable solvents are preferably non-solvent solvents, for example halogenated benzene, diphenyls or paraffin, such as, for example, chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters such as dibutyl adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl adipate, trichloroethyl phosphate, trioctyl phosphate, tricresyl phosphate; aromatic ethers such as benzylphenyl ether, hydrocarbon oils such as paraffin oil or kerosene, aromatic hydrocarbons, for example derivatives of benzene, diphenyl, naphthalene or terphenyl, dibenzyltoluene, partially hydrogenated terphenyl alkylated with isopropyl, isobutyl
• microcapsules containing the components (A) and (B) are applied to the surface of a support base in the production of the recording materials according to the invention and are preferably bonded thereon with a binder in an amount ensuring sufficient adhesion to the support base.
• this binder is primarily paper coating agents such as e.g. Gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, carboxymethyl cellulose, dextrin, starch, starch derivatives or polymer latices and mixtures of these substances.
• Latices are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers. Carboxylated latices are preferably used.
• 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 substrate can also be a plastic film.
• the support base is generally coated with a coating slip containing binder and coloring reaction components (A) and (B).
• the coating composition forming the coating can be either in the form of an aqueous or non-aqueous system, i.e. be used in an organic solvent system or in a hotmelt waking system.
• spacers are preferably incorporated into the capsule coating slip to protect them.
• Cellulose powder and / or insoluble wheat starch are used as spacers. Mixtures of cellulose powder and starch are also used.
• the capsule mass which contains components (A) and (B) can be mixed with other capsules which contain conventional color formers. Similar results are achieved if the components (A) and (B) are encapsulated together with one or more of the conventional color formers.
• the color developer used as component (C) is not coated on the surface of the paper, but rather is built into the material body during the production of the carrier material.
• the color developer is thus distributed through the entire thickness of the carrier material or through part of the same.
• the color developer is preferably added to a suspension of sulfite cellulose, whereupon this stock suspension is used, using a conventional sizing agent and a conventional retention agent, e.g. a polyacrylamide such as Separan PG5 is processed into a paper sheet containing the color developer.
• microcapsules containing components (A) and (B) can either be applied to one or both sides of this paper sheet containing color developer in the form of a capsule layer.
• a sheet coated only on one side can then be written on or printed from the coated side. If a sheet is coated on both sides with the color-forming capsules, this sheet can be used both as a writing surface and as a transfer sheet in order to produce a copy of the desired image on an underlying sheet.
• components (A) and (B) can also be used in accordance with a transfer copying system in which the components are dispersed or dissolved in an oil-like solvent, encapsulated individually or together, and applied as a coating to the back of a transfer sheet. Components (A) and (B) are then transferred to the color developer-containing sheet by destroying the capsules. The desired markings are formed at the points at which the microcapsules are destroyed and components (A) and (B) are transferred.
• the IR spectrum shows the acetate-CO band at 1770 cm ⁇ 1, and the lactone-CO band at 1790 cm ⁇ 1.
• Procedure B If the procedure described in procedure A is followed, but 25 ml of propionic anhydride are used instead of acetic anhydride and the temperature is kept at 110 ° C. for 3 hours, 3.8 g of the lactol ester of the formula are obtained after recrystallization from toluene with a melting point of 197-198 ° C.
• Instructions D The procedure described in Instructions A, but using 24.6 g of 3- (1'-methyl-2'-phenylindol-3'-yl) -3-hydroxy-4,5,6 instead of the phthalide described there , 7-tetrachlorophthalide, 14.3 g of the lactol ester of the formula are obtained after recrystallization from toluene with a melting point of 220-221 ° C (Z).
• Instructions F 4.8 g of the lactol ester of the formula (5) according to Instructions A are stirred under reflux in 100 ml of methanol for 1 hour. After cooling and filtering off, 4 g of a phthalide compound of the formula are obtained After recrystallization from toluene and methanol, the product melts at 184-185 ° C.
• Instructions G If the procedure is as described in Instructions F, but 50 ml of benzyl alcohol are used instead of methanol, a phthalide compound of the formula is obtained Mp 183-184 ° C.
• Procedure H Proceeding as described in Procedure C, but using 30 ml of propionic anhydride instead of acetic anhydride, keeping the reaction temperature at 75-78 ° C. for 2 1/2 hours and diluting with 10 ml of propionic anhydride before filtration, this is obtained after drying 18.8 g of the lactol ester of the formula with a melting point of 154-155.5 ° C (Z).
• Instructions L 45.2 g of benzoic anhydride are melted at 50.degree. At this temperature, 8.9 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide (or that of the corresponding keto acid tautomeric form) are carried ) on, heated to 100 ° C and maintains this temperature for 3 hours. The mixture is cooled to 50 ° C., 25 ml of methyl ethyl ketone and 10 ml of petroleum ether are added and the mixture is left to crystallize at 20 ° C. for 2 hours. After filtration and drying, 2.9 g of the compound are obtained of the formula which precipitates after recrystallization from methyl ethyl ketone in pure form with a melting point of 129-131 ° C.
• Example 1 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 2-phenylindole are in 97 , 7 g of diisopropylnaphthalene dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation.
• the capsule mass is mixed with starch solution and cellulose flour and applied to a recording paper of 50 g / m2 in which 5 g / m2 of the zinc salicylate according to EP-A-181289 Example 1 are incorporated in the paper body.
• the application weight atro is 7 g / m2.
• Example 1 The 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide used in Example 1 is prepared according to regulation A.
• Example 2 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 1-n-octyl- 2-methylindole are dissolved in 97.7 g of 1-phenyl-1-xylylethane and microencapsulated in a known manner with gelatin and carboxymethylcellulose by coacervation.
• the capsule mass is mixed with starch solution and cellulose powder and applied to a recording paper of 50 g / m2 in which 5 g / m2 zinc 3,5-di- ⁇ -methylbenzylsalicylate are distributed, which have been incorporated into the paper mass.
• the application weight atro is 7 g / m2. Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness forms.
• Example 3 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 1.3 g of 1-n-octyl-2-methylindole are in 96.1 g of isopropyldiphenyl dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation.
• the capsule mass is mixed with starch solution and cellulose flour and applied to a recording paper of 50 g / m2, in which 5 g / m2 of active clay are distributed, which were incorporated in the manufacture of the paper.
• the application weight atro is 7 g / m2.
• Example 4 3.4 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 96.6 g of diisopropylnaphthalene and known Microencapsulated with gelatin and carboxymethyl cellulose by coacervation. 1.1 g of 2-phenylindole are dissolved in 98.9 g of diisopropylnaphthalene and likewise subjected to the encapsulation process. The microcapsules obtained are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and cellulose flour.
• the latter is applied to 50 g / m2 acceptor paper containing 5 g / m2 of activated clay that has been incorporated into the mass.
• the application weight atro is 7 g / m2. Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.
• Example 5 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 97.4 g of diisopropylnaphthalene and in a known manner with gelatin and carboxymethyl cellulose microencapsulated by coacervation. 1.3 g of 1-n-octyl-2-methylindole are dissolved in 98.7 g of diisopropylnaphthalene and also subjected to the encapsulation process.
• microcapsules produced are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and carboxymethyl cellulose.
• the latter is applied to an acceptor paper of 50 g / m2, which contains 5 g / m2 of zinc 3,5-di- ⁇ -methylbenzylsalicylate, which is added to the mass during manufacture of the paper is installed.
• the application weight atro is 7 g / m2. Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.
• Example 6 4.9 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 95.1 g of 1-phenyl-1 -xylylethane dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation. 1.8 g of 1-n-octyl-2-methylindole are dissolved in 98.2 g of 1-phenyl-1-xylylethane and likewise subjected to the encapsulation process.
• microcapsules produced are mixed together in a ratio of 1: 1, whereupon the capsule mixture is processed into a coating slip by adding an acrylic acid ester copolymer and cellulose flour.
• the latter is applied to an acceptor paper of 50 g / m 2, which contains 5 g / m 2 of a zinc salicylate according to EP-A-181289, example 1, which was incorporated in the manufacture of the paper.
• the application weight atro is 7 g / m2. Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.
• Example 7 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 97.4 g of diisopropylnaphthalene and in a known manner with gelatin and carboxymethyl cellulose microencapsulated by coacervation. 1.3 g of 1-n-octyl-2-methylindole are dissolved in 98.7 g of diisopropylnaphthalene and also subjected to the encapsulation process.
• microcapsules produced are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and carboxymethyl cellulose.
• the latter is applied to the back of a base paper of 50 g / m2 so that the applied mass corresponds to 7 g / m2 dry weight.
• an acceptor paper is prepared in which 5 g / m2 of zinc 3,5-di- ⁇ -methylbenzyl salicylate is present, which is incorporated into the mass during the manufacture of the paper.
• the two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.
• Example 8 3.4 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 96.6 g of diisopropylnaphthalene and known Way with gelatin and Carboxymethyl cellulose microencapsulated by coacervation. 1.1 g of 2-phenylindole are dissolved in 98.9 g of diisopropylnaphthalene and likewise subjected to the encapsulation process. The microcapsules obtained are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and cellulose flour.
• the latter is applied to the back of a base paper of 50 g / m2 so that the applied mass corresponds to 7 g / m2 dry weight.
• an acceptor paper is prepared in which 5 g / m2 of active clay is present, which is built into the paper pulp during the manufacture of the paper.
• the two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.
• Example 9 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 1.3 g of 1-n-octyl-2-methylindole are in 96.1 g of isopropyldiphenyl dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation. The capsule mass is mixed with starch solution and cellulose flour and applied to the back of a backing paper so that the application weight is 7 g / m2.
• an acceptor paper is prepared in which 5 g / m2 of zinc 3,5-di- ⁇ -methylbenzyl salicylate is present, which is built into the mass during the manufacture of the paper.
• the two sheets of paper are placed next to each other.
• pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.
• Example 10 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 1-n-octyl- 2-methylindole are dissolved in 97.7 g of 1-phenyl-1-xylylethane and microencapsulated in a known manner with gelatin and carboxymethylcellulose by coacervation. The capsule mass is mixed with starch solution and cellulose powder and applied to the back of a paper carrier so that the mass applied corresponds to 7 g / m2 dry weight.
• an acceptor paper is prepared in which 5 g / m2 of a zinc salicylate according to EP-A-181 289 Example 1 are distributed, which are added to the paper pulp during the Production of the paper can be added.
• the two sheets of paper are placed next to each other.
• pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Indole Compounds (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Plural Heterocyclic Compounds (AREA)
• Color Printing (AREA)

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• 1991
  • 1991-05-14 EP EP91810370A patent/EP0463987A1/fr not_active Withdrawn
  • 1991-05-23 JP JP3117765A patent/JPH04232089A/ja not_active Withdrawn

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