azo dyes useful for thermotransfer printing have the formula ##STR1##
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1. A process comprising printing a substrate by thermotransfer printing with a transfer dye which is an azo dye of the general formula I ##STR32## in which the substituents have the following meanings: R1 is hydrogen;
C1 -C15 -alkyl, C1 -C15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen; phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, sulfonamido or halogen; thienyl, thienyl substituted by C1 -C5 -alkyl or halogen; furanyl or pyridyl; a radical of the formula ii
[--W--O]n --R4 ii where W is identical or different C2 -C6 -alkylene, n is from 1 to 6 and R4 is C1 -C4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy; R2 and R3 are each hydrogen; alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms; alkyl, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms, substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benxyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano; cyclohexyl, cyclohexyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy or halogen; phenyl, phenyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy, benzyloxy or halogen; a radical of the above-mentioned formula ii; and D is the radical of a diazo component iii. D--NH2 iii wherein D is the radical of a diazo component iii of the aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series. 2. A process comprising transferring an azo dye or dyes by diffusiton from a transfer to a plastic-coated substrate by means of a thermal printing head, wherein said azo dye or dyes is or are of the formula I ##STR33## in which the substituents have the following meanings: R1 on is hydrogen;
C1 -C15 -alkyl, C1 -C15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen; phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, sulfonamido or halogen; thienyl, thienyl substituted by C1 -C5 -alkyl or halogen; furanyl or pyridyl; a radical of the formula ii
[--W--O]n --R4 ii where W is identical or different C2 -C6 -alkylene, n is from 1 to 6 and R4 is C1 -C4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy; R2 and R3 are each hydrogen; alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms; alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, each containing up to 15 carbon atoms, substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benzyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano; cyclohexyl, cyclohexyl substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy or halogen; phenyl, phenyl substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy, C1 -C15 -alkoxy, benzyloxy or halogen; a radical of the above-mentioned formula ii; and D is the radical of a diazo component iii D--NH2 iii wherein D is the radical of a diazo component iii of the aminothiophene, phenylazominothiophene, aminothiazole, phenylazominothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminoidazole, aminotriazole or aminopyrrole series. 3. A process as claimed is
cyclohexyl; phenyl, phenyl substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy or chlorine; thienyl; a radical of the formula IIa ##STR35## where p is 0 or 1, q is from 1 to 4, and R4' is C1 -C4 -alkyl, phenyl or benzyl; R2' and R3' are each C1 -C12 -alkyl, C1 -C10 -alkoxy or C1 -C10 -cyanoalklyl or a radical of the above-mentioned formula IIa; and D' is the radical of a diazo component iii of the aniline, phenylazoaniline. aminothiophene, phenylazoaminothiophene, aminothiazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazle, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series.
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The present invention relates to the use in thermo-transfer printing of azo dyes of the formula I ##STR2## where the substituents have the following meaning:
R1 is hydrogen;
C1 -C15 -alkyl which may be substituted by phenyl or phenoxy;
cyclohexyl which may be substituted by C1 -C5 -alkyl, C1 -C5 -alkoxy or halogen:
phenyl which may be substituted by C1 -C5 -alkyl, C1 --C5 -alkoxy, sulfonamido or halogen;
thienyl which may be C1 --C5 -alkyl- or halogen-substituted, furanyl or pyridyl;
a radical of the formula II
[--W--O]n --R4 II
where
W is identical or different C2 -C6 -alkylene,
n is from 1 to 6 and
R4 is C1 -C4 -alkyl or a phenyl or benzyl group which may both be substituted by C1 -C4 -alkyl or C1 -C4 -alkoxy;
R2 and R3 are each hydrogen;
alkyl, alkoxy, alkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkyl, hydroxyalkyl or cyanoalkyl, which may each contain up to 15 carbon atoms and be substituted by phenyl, C1 -C4 -alkylphenyl, C1 -C4 -alkoxyphenyl, halophenyl, benzyloxy, C1 -C4 -alkylbenzyloxy, C1 -C4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano; cyclohexyl which may be substituted by C1 14 C15 -alkyl, C1 -C15 -alkoxy or halogen;
phenyl which may be substituted by C1 -C15 -alkyl, C1 -C15 -alkoxy, benzyloxy or halogen; a radical of the abovementioned formula II; and
is the radical of a diazo component III
D--NH2 III
and specifically to a process for transferring these azo dyes by diffusion from a transfer to a plastic-coated substrate with the aid of a thermal printing head.
The technique of thermotransfer printing is common knowledge; suitable heat sources besides lasers and IR lamps are in particular thermal printing heads capable of emitting short heat pulses lasting fractions of a second.
In this preferred embodiment of thermotransfer printing, a transfer sheet which contains the transfer dye together with one or more binders, a support material and possibly further assistants such as release agents or crystallization inhibitors is heated from the back with the thermal printing head, causing the dye to migrate out of the transfer sheet and to diffuse into the surface coating of the substrate, for example into the plastic coat of a coated sheet of paper.
The essential advantage of this process is that the amount of dye to be transferred (and hence the color gradation) can be controlled in a specific manner via the amount of energy supplied to the thermal printing head.
Thermal transfer printing is in general carried out using the three subtractive primaries yellow, magenta and cyan (with or without black), and the dyes used must have the following properties to ensure optimal color recording: ready thermal transferability, little tendency to migrate within or out of the surface coating of the receiving medium at room temperature, high thermal and photochemical stability, and also resistance to moisture and chemicals, no tendency to crystallize on storage of the transfer sheet, a suitable hue for subtractive color the transfer sheet, a suitable hue for subtractive color mixing, a high molar absorption coefficient, and ready industrial availability.
It is very difficult to meet all these requirements at one and the same time. In particular, the magenta dyes used to date have not been fully satisfactory. This is also true for example of the azo dyes described, and recommended for thermal transfer, in U.S. Pat. No. 4,764,178, which resemble the azo dyes I and have coupling components based on aniline, tetrahydroquinoline, aminoquinoline or julolidine.
The azo dyes I themselves are known per se or obtainable by known methods, for example as described in earlier German Patent Application P 38 33 443.7, O. Annen et al., Rev. Prog. Coloration 17 (1987), 72-85, or M. A. Weaver and L. Shuttleworth, Dyes and Pigments 3 (1982), 81-121.
It is an object of the present invention to find suitable red and blue dyes for thermotransfer printing which come closer to the required property profile than the prior art dyes.
We have found that this object is achieved by the azo dyes I defined at the beginning.
We have also found a process for transferring azo dyes by diffusion from a transfer to a plastic-coated substrate with the aid of a thermal printing head, which comprises using for this purpose a transfer on which are situated one or more of the azo dyes I defined at the beginning.
We have further found preferred embodiments of this process, which comprise using dyes of the formula Ia ##STR3## where the substituents have the following meanings:
R1' is C1 -C8 -alkyl which may be substituted by
phenyl or cyclohexyl;
phenyl which may be substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy or chlorine;
thienyl;
a radical of the formula IIa ##STR4## where p is 0 or 1, q is from 1 to 4, and R4' is C1 -C4 -alkyl, phenyl or benzyl;
R2' and R3' are each C1 -C12 -alkyl, C1 -C10 -alkoxy or C1 -C10 -cyanoalkyl or a radical of the abovementioned formula Ila; and
D' is the radical of a diazo compound III of the aniline, phenylazoaniline, aminothiophene, phenylazoaminothiophene, aminothazole, phenylazoaminothiazole, aminoisothiazole, aminobenzisothiazole, aminothiadiazole, aminoisothiadiazole, aminooxazole, aminooxadiazole, aminodiazole, aminotriazole or aminopyrrole series.
Preferred diazo components III are:
aniline derivatives of the formula IIIa ##STR5## phenylazoaniline derivatives of the formula IIIb ##STR6## aminothiphene derivatives of the formula IIIc ##STR7## phenylazoaminothiophene derivatives of the formula IIId ##STR8##
Aminothiazole derivatives of the formula IIIe ##STR9## phenylazoaminothiazole derivatives of the formula IIIf ##STR10## aminoisothiazole derivatives of the formula IIIg ##STR11## aminobenzisothiazole derivatives of the formulae IIIh and IIIi ##STR12## aminothiadiazole derivatives of the formula IIIk ##STR13## aminothiadiazole derivatives of the formula IIIl ##STR14## aminopyrrole derivatives of the formula IIIm ##STR15##
Here the substituents have the following meanings:
R5, R6 and R7 are each hydrogen, chlorine, bromine, nitro or cyano; alkyl alkoxyalkyl, alkanoyloxalkyl or alkoxycarbonylalkyl, which may each contain up to 10 carbon atoms;
a radical of the formula II;
a radical of the formula --CO--OR15, --CO--NR15 R16, --SO--OR15, --SO2 --OR15 or --SO2 --NR15 R16 in which
R15 and R16 are each alkyl or alkoxyalkyl which may each contain up to 10 carbon atoms, and
R16 may also be hydrogen;
R5 may also be oxadiazole substituted in the 3-position by C1 -C8 -alkoxy;
R6 may also be a radical of the formula --CO--R17 or --CO--OR17 where
R17 is phenyl which may be substituted by C1 -C8 -alkyl;
a radical of the formula IV ##STR16## where X is cyano, --CO--OR15 or --CO--NR15 R16 ;
R8 is hydrogen, chlorine, cyano or thiocyanato, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 10 carbon atoms; 2-(C1 -C2 -alkoxycarbonyl)ethylthio; 2-(pyrrolid-1-yl)ethyl; C5 -C6 -cycloalkyl or -cycloalkylthio; phenyl which may be substituted by C1 -C4 -alkyl, C1 -C4 -alkoxy, benzyloxy or phenylthio; Ar-C1 -C4 -alkythio; Ar-C1 -C4 -alkoxy or Ar-C1 -C4 -alkylthio;
thienyl or pyridyl which may each be substituted by C1 -C4 -alkyl;
a radical of the formula II;
a radical of the formula --CO--OR15, --CO--NR15 R16, --SO--OR15 or --SO2 --OR15 ;
R9 is hydrogen, chlorine, bromine, nitro, cyano, thiocyanato or phenyl; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R10 is hydrogen, chlorine, bromine, nitro, cyano or formyl; a radical of the formula --CO--OR15 or --CO--NR15 R16 ; or a radical of the formula IV
R11 and R12 are each hydrogen, chlorine, bromine, nitro or cyano; C1 -C4 -alkyl or C1 -C4 -alkoxy; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R13 is hydrogen, chlorine, bromine or C1 -C4 -alkyl;
R14 is hydrogen or cyano; or a radical of the formula --CO--OR15 or --CO--NR15 R16 ;
R18 is cyano or formamido;
R19 is methyl or phenyl;
X is hydrogen, chlorine or nitro; and
Y is hydrogen or cyano.
Suitable alkyl R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R15 or R16 is in particular methyl, ethyl, propyl, ispropyl or butyl, but also isobutyl, sec.-butyl or tert.-butyl.
R1, R2, R3, R5, R6, R7, R8, R15 and R16 may each also be for example pentyl, isopentyl, neopentyl, tert.-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, mixed isooctyl isomer and cyclohexyl.
R1, R2, R3, R5, R6, R7, R8, R15 and R16 may each also be for example nonyl, decyl, mixed isononyl isomer or mixed isodecyl isomer.
Other possible meanings for R1, R2 and R3 include undecyl, dodecyl, tridecyl, mixed isotridecyl isomer, tetradecyl and pentadecyl and for R2 and R3 additionally hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkyls R2 and R3 may each also be substituted by phenyl; specific examples, where Ph=phenyl, are:
--CH2 --Ph, --CH(CH3)--Ph, --(CH2)2 --Ph,
--(CH2)4 --CH(CH3)--Ph--3--CH3,
--(CH2)3 --CH(C4 H9)--Ph--3--CH3,
--(CH2)6 --Ph--4--O--CH3.
--CH(C2 H5)--(CH2)3 --Ph--3--O--C2 H5 and
--CH(C2 H5)--(CH2)3 --Ph--3--Cl.
It is also possible to use for example the following halo, hydroxyl and cyanoalkyl groups as R2 or R3 :
--(CH2)5 --Cl, --CH(C4 H9)--(CH2)3 --Cl or --(CH2)4 --CF3 ;
--(CH2)2 --CH(CH3)--OH. --(CH2)2 --CH(C4 H9)--OH oder CH(C2 H5)--(CH2)9 --OH:
--(CH2)2 --CN, --(CH2)3 --CN, --CH2 --CH(CH3)--CH(C2 H5)--CN, --(CH2)6 --CH(C2 H6)--CN and
--(CH2)3 --CH(CH3)--(CH2)2 --CH(CH3)--CN.
When R1, R2, R3, R5, R6, R7, R15 or R16 is alkoxyalkyl of preferred formula II, suitable W is for example 1,2- and 1,3-propylene, 1,2-, 1,3-, 1,4- and 2,3-butylene, pentamethylene, hexamethylene and 2-methylpentamethylene, but in particular ethylene, and R4 is in particular methyl, ethyl, propyl, butyl and also benzyl and phenyl which may each be substituted by methyl(oxy), ethyl(oxy), propyl(oxy) or butyl(oxy). Particularly preferred II is for example:
--(CH2)2 --O--CH3, --(CH2)2 --O--C2 H5, --(CH2)2 --O--C3 H7, --(CH2)2 --O--C4 H9,
--(CH2)2 --O--CH2 --CH(CH3)--CH3,
--(CH2)2 --O--Ph, --(CH2)2 --O--CH2 --Ph,
--[(CH2)2 --O]2 --CH3, --[(CH2)2 --O]2 --C2 H5, --[(CH2)2 --O]2 --Ph,
--[(CH2)2 --O]2 --Ph--4--O--C4 H9,
--[(CH2)2 --O]3 --C4 H9, --[(CH2)2 --O]3 --Ph, --[(CH2)2 --O]3 --Ph--3--C4 H9,
--[(CH2)2 --O]4 --CH3,
--(CH2)3 --O--(CH 2 )2 --O--CH3, --(CH 2)3 --O--(CH2)2 --O--C2 H5,
--(CH2)3 --O--(CH2)2 --O--Ph, --(CH2)3 --O--[(CH2)2 --O]2 --CH3 and
--(CH2)3 --O--[(CH2)2 --O]2 --C2 H5.
Further preferred groups II are for example:
--(CH2)3 --O--CH3, --(CH2)3 --O--C2 H5, --(CH2)3 --O--C3 H7, --(CH2)3 --O--C4 H9,
--(CH2)3 --O--Ph, --[(CH2)3 --O]2 --CH3, --[(CH2)3 --O--]2 'C2 H5,
--CH2 --CH(CH3)--O--CH3, --CH2 --CH(CH3)--O--C2 H5, --CH2 --CH(CH3)--O--C3 H7,
--CH2 --CH(CH3)--O--C4 H9, --CH2 --CH(CH3)--O--Ph,
--(CH2)4 --O--CXH3, --(CH2)4 --O--C2 H5, --(CH2)4 --O--C4 H9,
--(CH2)4 --O--CH2 --CH(C2 H5)--C4 H9, --(CH2)4 --O--Ph,
--(CH2)4 --O--CH2 --Ph--2--O--C2 H5, --(CH2)4 --O--C6 H10 --2--C2 H5,
--[(CH2)4 --O]2 --CH3, --[(CH2)4 --O]2 --C2 H5, --[(CH2)2 --CH(CH3)--O]2 --C2 H5,
--(CH2)5 --O--CH3, --(CH2)5 --O--C2 H5, --(CH2)5 --O--C3 H7, --(CH2)5 --O--Ph,
--CH2)2 --CH(C2 H5)--O--CH2 --Ph--3--O--C4 H9, --(CH2)2 --CH(C2 H5)--O--CH2 --Ph--3--Cl,
--(CH2)6 --O--C4 H9, --(CH2)6 --O--Ph--4--O--C4 H9, --(CH2)3 --CH(CH3)--CH(CH3)--CH2 --O--C4 H9,
--(CH2)3 --O--(CH2)4 --O--CH3, --(CH2)3 --O--(CH2)4 --O--C2 H5,
--(CH2)4 --O--(CH2)3 --O--CH3 and --(CH2)4 --O--(CH2)3 --O--C2 H5.
Suitable alkoxyalkyl also includes for example:
--(CH2)8 --O--CH3, --(CH2)8 --O--C4 H9, --(CH2)8 --O--CH2 --Ph--3--C2 H5,
--(CH2)4 --CH(Cl)--(CH2)3 --O--CH2 --Ph--3--CH3 and
--(CH2)3 --CH(C4 H9)--O--CH2 --Ph--3--CH3.
Of the above-recited alkoxyalkyl groups, those which contain up to 8 carbon atoms are also suitable for use as R8 and those having up to 12 carbon atoms are also suitable for use as R15 and R16.
Preferred alkoxy R2, R3, R8, R11 or R12 is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec.-butoxy.
R8 and especially R2 and R3 may each also be for example pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, oxtyloxy or 2-ethylhexyloxy.
R2 and R3 may each in addition be for example nonyloxy or decyloxy but also undecyloxy, dodecyloxy, tridecyloxy, tetradecyioxy or pentadecyloxy.
R8 may also be alkylthio, such as preferably methylthio, ethylthio or 2-cyanoethylthio, but also propylthio, isopropylthio, butylthio, pentylthio, hexylthio, heptythio, octylthio, 2-ethylhexylthio, 2-ethoxycarbonylethylthio or in particular 2-methoxycarbonylthio.
Suitable alkanoyloxyalkyl, alkoxycarbonyloxyalkyl or alkoxycarbonylalkyl R2 or R3 is for example:
--CH2)2 --O--CO--CXH3,
--(CH2)3 --O--CO--(CH2)7 --CH3,
--(CH2)2 --O--CO--(CH2)3 --PH-2--O--CH3,
--CH(CH2 --Ph--3--CH3)--O--CO--C4 H9 and
--(CH2)4 --O--CO--(CH2)4 --CH(C2 H5)--OH;
--(CH2)2 --O--CO--O--CH3,
--(CH2)3 --O--CO--O--(CH2))7 --CH3,
--CH(C2 H5)--CH2 --O--CO--O--C4 H9,
--(CH2)4 --O--CO--O--(CH2)2 --CH(CH3)--O--Ph--3--CH3 and
--(CH2)5 --O--CO--O--(CH2)5 --CN;
--(CH2)2 --CO--O--CH3,
--(CH2)3 --CO--O--C4 H9,
--(CH2)3 --CH(CH3)--CH2 --CO--O--C4 H9,
--(CH2)3 --CH(C4 H9)--CH2 --CO--O--C2 H5,
--(CH2)2 --CO--O--(CH2)5 --Ph,
--(CH2)4 --CO--O--(CH2)4 --Ph-4C4 H9,
--(CH2)3 --CO--O--(CH2)4 --O--Ph-3--O--CH3,
--(CH2)2 --CH(CH2 OH)--(CH2)2 --CO--O--C2 H5,
--CH(C2 H5)--CH2 --CO--O--CH2)4 --OH and
--(CH2)3 --CO--O--(CH2)6 --CN.
Phenyl and cyclohexyl which may each be present as
R1, R2 or R3 are for example: --Ph, --Ph--3--CH3, --Ph--4--(CH2)10 --CH3, --Ph--3--(CH2)5 --CH(CH3)--CH3, Ph--4--O--C4 H9, --Ph--4--(CH2)5 --CH(C2 H5)--CH3, --Ph--4--)--CH2 --Ph or --Ph--4--Cl and also in the case of R1 in particular --Ph--3--SO2 --N(CH3)--CH3 or Ph--3--SO2 --N--((CH2)2 --O--CH3)--(CH2)2 --O--CH3 ; --C6 H10 --4--CH3, --C6 H10 --4--C10 H21, --C6 H10 --3--O--C4 H9, --C6 H10 --3--O--(CH2) 4 --CH(C2 H5)--CH3 or --C6 H10 --4--Cl.
Where R5, R6, R7, R8, R9, R10, R11, R12 or R14 is a group of the formula --CO--OR15 or --CO--NR15 R16, particularly suitable instanccs thereof are
--CO--O--CH3, --CO--O--C2 H5, --CO--O--C3 H7,
--CO--O--C4 H9, --CO--N(CH3)--CH3 and
--CO--N(C2 H5)--C2 H5, but also for example
--CO--O--C5 H11, --CO--O--C6 H13, --CO--n(C3 H7)--C3 H7 and --CO--n(C4 H9.
Groups of the formula --SO--OR15 or --SO2 --OR15, which may each be used as R5, R6, R7 or R8 are For example:
--SO--O--CH3, --SO--O--C2 H5, --SO--O--C3 H7,
--SO2 --O--CH3, --SO2 --O--C2 H5, --SO2 --O--C3 H7.
R5, R6 and R7 may each also be groups of the formula --SO2 --NR15 R16, in particular --SO2 --N(CH3)--CH3, --SO2 --N((CH2)2 --O--CH3)--(CH2)2 --O--CH3, but also for example --SO2 --N(C2 H5)--C2 H5 or --SO2 --N(C3 H7)--C3 H7.
R6 and R10 may each also be groups of the formula IV, such as --CH═C(CN)--CN, --CH═C(CN)--CO--O--CH3, --CH═C(CN)--CO--O--C2 H5. --CH═C(CN)--CO--O--C3 H7, --CH═--C(CN)--CO--O--C4 H9, --CH═C(CN)--N(CH3)--CH3 or --CH═C(CN)--N(C2 H5)--C2 H5.
Of the aforementioned radicals, R1 is particularly preferably C1 -C8 alkyl, especially methyl or isopropyl, cyclohexyl, phenyl, which may also be methoxy-, sulfonamido- or chlorine-substituted, or benzyl. Preferred R12 further includes 3-thienyl and especially 2-thienyl. 3-furanyl and especially 2-furanyl, and also 2-pyridyl, 4-pyridyl and especially 3-pyridyl.
Preferred alkyl R2 or R3 is of up to 12 carbon atoms, especially methyl, ethyl or propyl, preferred cyanoalkyl and alkoxy R2 or R3 is of up to 10 carbon atoms. Particularly preferred R2 and R3 each has the formula Ila with methyl or ethyl as R4 '.
Of the above-recited diazo components D-NH2, the following are particularly preferred:
aniline derivatives IIIa having the above-defined meanings of R5, R6 and R7
aminothiophene derivatives IIIc having the following meanings for R8, R9 and R10 :
R8 is hydrogen or chlorine; alkyl, alkoxy or alkoxyalkyl, which may each contain up to 8 carbon atoms; phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, or benzyl; or a radical of the formula --CO--OR15 ;
R9 is cyano or a radical of the formula --CO--OR15 or else --CO--NR15 R16 ; and
R10 is cyano, nitro, formyl or a radical of the formula IV
aminothiazole derivatives IIIe having the following meanings for R8 and R10 :
R8 is hydrogen, chlorine, C1 14 C8 -alkyl, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl, or a radical of the formula --CO--OR15 ; and
R10 is cyano, nitro, formyl or a radical of the formula --CO--OR15
aminoisothiazole derivatives IIIg having the following meanings for R8 and R9 :
R8 is chlorine, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 8 carbon atoms, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl or benzyloxy, and
R9 is cyano, nitro or a radical of the formula --CO--OR15
aminothiadiazole derivatives IIIk and aminoisothiadiazole derivatives IIIl having the following meaning for R8 :
R8 is hydrogen, chlorine, cyano, thiocyanato, or alkyl, alkoxy, alkylthio or alkoxyalkyl, which may each contain up to 8 carbon atoms, 2-(C1 -C2 -alkoxycarbonyl)ethylthio, phenyl which may be C1 -C4 -alkyl- or C1 -C4 -alkoxy-substituted, benzyl, benzyloxy, or a radical of the formula --CO--OR15, --SO--OR15 or --SO2 --OR15.
The dyes I to be used according to the present invention are notable for the following properties compared with prior art red and blue thermotransfer printing dyes having aniline-based coupling components: readier thermal transferability, improved migration properties in the receiving medium at room temperature, higher thermal stability, higher lightfastness, better resistance to moisture and chemicals. better solubility in printing ink preparation, higher color strength. and readier industrial accessability.
In addition, the azo dyes I exhibit a distinctly better purity of hue, in particular in mixtures of dyes, and produce improved black prints.
The transfer sheets required as dye donors for the thermotransfer printing process according to the present invention are prepared as follows. The azo dyes I are incorporated in an organic solvent, such as isobutanol, methyl ethyl ketone, methylene chloride, chlorobenzene, toluene, tetrahydrofuran or a mixture thereof, together with one or more binders and possibly further assistants such as release agents or crystallization inhibitors to form a printing ink in which the dyes are preferably present in a molecularly dispersed, i.e. dissolved, form. The printing ink is then applied to an inert support and dried.
Suitable binders for the use of the azo dyes I according to the present invention are all materials which are soluble in organic solvents and which are known to be suitable for thermotransfer printing, e.g. cellulose derivatives such as methylcellulose, hydroxypropylcellulose, cellulose acetate or cellulose acetobutyrate, but in particular ethylcellulose and ethylhydroxyethylcellulose, starch, alginates, alkyd resins and vinyl resins such as polyvinyl alcohol or polyvinylpyrrolidone but in particular polyvinyl acetate and polyvinyl butyrate. It is also possible to use polymers and copolymers of acrylates and derivatives thereof, such as polyacrylic acid, polymethyl methacrylate or styrene/acrylate copolymers, polyester resins, polyamide resins, polyurethane resins or natural resins such as gum arabic.
It is frequently advisable to use mixtures of these binders, for example mixtures of ethylcellulose and polyvinyl butyrate in a weight ratio of 2:1.
The weight ratio of binder to dye is in general from 8:1 to 1:1, preferably from 5:1 to 2:1.
Suitable assistants are for example release agents based on perfiuofinated alkylsulfonamidoalkyl esters or silicones as described in EP-A-127,092 and EP-A-192,435, and in particular organic additives which stop the transfer dyes from crystallizing out in the course of storage or heating of the inked ribbon, for example cholesterol or vanillin.
Inert support materials are for example tissue, blotting or parchment paper and films made of heat resistant plastics such as polyesters, polyamides or polyimides, which films may also be metal coated.
The inert support may additionally be coated on the side facing the thermal printing head with a lubricant in order that adhesion of the thermal printing head to the support material may be prevented. Suitable lubricants are for example silicones or polyurethanes as described in EP-A-216,483.
The thickness of the dye transfer is in general from 3 to 30 μm, preferably from 5 to 10 μm.
The substrate to be printed, e.g. paper, must in turn be coated with a plastic which receives the dye during the printing process. It is preferable to use for this purpose polymeric materials whose glass transition temperatures Tg are within the range from 50° to 100°C: e.g. polycarbonates and polyesters. Details may be found in EP-A-227,094, EP-A-133,012, EP-A-133,011, JP-A-199,997/1986 or JP-A-283,595/1986.
The process according to the present invention is carried out using a thermal printing head which is heatable to above 300°C, so thai dye transfer takes not more than 15 msec.
First, transfer sheets (donors) were produced from a polyester sheet from 6 to 10 μm in thickness coated with an approximately 5 μm thick transfer layer of a binder B which in each case contained about 0.25 g of azo dye I. The weight ratio of binder to dye was in each case 4:1, unless otherwise stated in the Tables below.
The substrate (receiver) to be printed was paper about 120 μm in thickness which had been coated with a layer of plastic 8 μm in thickness (Hitachi Color Video Print Paper).
Donor and receiver were placed on top of one another with the coated fronts next to each other, then wrapped in aluminum foil and heated between two hotplates at 70°-80°C for 2 minutes. This operation was repeated three times with similar samples at a temperature within the range from 80° to 120°C, the temperature being increased each time.
The amount of dye diffusing into the plastics layer of the receiver in the course of transfer is proportional to the optical density determined photometrically as absorbance A after each heating phase at the abovementioned temperatures.
The plot of the logarithm of the measured absorbances A against the corresponding reciprocal of the absolute temperature is a straight line from whose slope it is possible to calculate the activation energy ΔEλ for the transfer experiment: ##EQU1##
From the plot it is additionally possible to discern the temperature T* at which the absorbance attains the value 1, i.e. at which the transmitted light intensity is one tenth of the incident light intensity. The lower the temperature T*, the better the thermal transferability of the particular dye.
The Tables which follow list the azo dyes I which were studied in respect of their thermal transfer characteristics together with their absorption maxima λmax [nm]. The λmax values were measured in methylene chloride or the stated solvent.
In addition, they list the particular binder B used employing the following abbreviations: EC=ethylcellulose, PVB=polyvinyl butyrate, MIX=EC:PVB═2:1, and VY=nylon.
If the abovementioned parameters R* [°C.] and ΔE, [kJ/mol] were measured, the values found are likewise stated.
| TABLE 1 |
| __________________________________________________________________________ |
| ##STR17## IIIa |
| Ex |
| R1 |
| R2 R3 |
| R5 R6 |
| λmax [nm] |
| B T*[°C.] |
| ΔEτ |
| [kJ/mol] |
| __________________________________________________________________________ |
| 1 Ph (CH2)2 OCH3 |
| R2 |
| CN H 494 EC 104 42 |
| 2 Ph (CH2)2 OCH3 |
| R2 |
| ##STR18## NO2 |
| 544 MS 90 71 |
| __________________________________________________________________________ |
| TABLE 2 |
| __________________________________________________________________________ |
| ##STR19## IIIb |
| Ex. |
| R2 R3 |
| R5 |
| R6 |
| R7 |
| R11 |
| R12 |
| R12' |
| λmax [nm] |
| B T*[°C.] |
| ΔEτ |
| [kJ/mol] |
| __________________________________________________________________________ |
| 3 C2 H5 |
| R2 |
| Cl CN Cl OCH3 |
| H OCH3 |
| 584 EC 96 84 |
| 4 (CH2)2 OCH3 |
| R2 |
| H H H Br H H 538 MS 97 76 |
| 5 (CH2)2 OCH3 |
| R2 |
| H H H Br Br H 492 EC 106 84 |
| __________________________________________________________________________ |
| TABLE 3 |
| IIIc |
| ##STR20## |
| Ex. R1 R2 R3 R8 R10 λmax [nm] B |
| T*[°C.] ΔEτ |
| [kJ/mol] 6 Cyclohexyl C2 H5 |
| R2 CH3 CN 550 MIX 90 65 7 Cyclohexyl C2 H5 R2 |
| CH3 COOCH3 545a -- -- -- 8 Cyclohexyl (CH2)2 |
| OCH3 R2 CH3 COOCH3 544a -- -- -- 9 Cyclohexyl |
| (CH2)2 OCH3 R 2 Cl COH 580a MIX 90 88 VY |
| 90 58 10 Cyclohexyl (CH2)2 |
| OCH3 R2 Cl CHC(CN)COO4 |
| H9 625 VY 99 54 11 Cyclohexyl (CH2)2 OCH3 C2 |
| H5 CH3 CN 551 MIX 92 77 12 Cyclohexyl (CH2)2 |
| OCH3 C2 H5 Cl COH 572 MIX 92 66 VY 86 40 13 |
| CH(CH3)CH3 C2 H5 R2 CH3 CN 547 EC 90 88 14 C |
| H(CH3)CH3 C2 H5 R2 Cl COH 572 MIX 90 50 15 |
| CH(CH3)CH3 C2 H5 R2 CH3 CN 547 -- -- -- 16 C |
| H(CH3)CH3 C2 H5 R2 COOC2 |
| H5 COOC2 H5 542 VY 135 50 17 CH(C2 H5)C4 |
| H9 C2 H5 R2 Cl CHC(CN)COOC4 H9 608 MIX |
| 90** 59 18 Ph C2 H5 R2 H NO2 623 -- -- -- 19 Ph |
| C2 H5 R2 Cl Br 559 -- -- -- 20 Ph C2 H5 R2 C |
| l COH 602 -- -- -- 21 Ph C2 H5 R2 CH3 COOC2 |
| H5 569 EC 132 64 22 Ph C2 H5 R2 OC2 H5 |
| COH 598 -- -- -- 23 Ph C2 H5 R2 COOC2 H5 |
| COOC2 H5 573 VY 100 52 24 Ph (CH2)3 OCH 3 |
| C2 H5 Cl COH 574 VY 81 23 25 Ph (CH2)3 |
| O(CH2)2 OCH3 C2 H5 CH3 COOCH3 |
| 576a -- -- -- 26 Ph (CH2)3 O(CH2)2 OCH3 |
| C2 H5 Cl COH 606a -- -- -- 27 Ph (CH2)3 |
| O(CH2)2 OCH3 C3 H7 CH3 CN 582a MIX 91 |
| 64 28 Ph (CH2)3 O(CH2)2 OCH3 C3 H7 Cl C |
| OH 633 MIX 91 60 29 Ph [(CH2)2 O]2 C2 H5 |
| (CH2)3 OCH3 Cl CHC(CN)COOC4 H9 644 EC 130 76 |
| 30 Ph [(CH2)2 O]2 C2 H5 C2 H5 Cl COH |
| 601 EC* 94 73 31 Ph [(CH2)2 O]2 C2 H5 C2 |
| H5 Cl CHC(CN)COOC4 H9 653 MIX 106 |
| 46 32 Ph [(CH2)2 O]2 C2 H5 (CH2)3 |
| OCH3 Cl CHC(CN)COOC4 H9 648 MIX 122 |
| 67 33 Ph (CH2)2 O[(CH2)2 O]2 CH3 C2 |
| H5 CH3 CN 581a -- -- -- 34 Ph (CH2)2 |
| O[(CH2)2 O]2 CH3 C2 H5 CH3 CN |
| 583a -- -- -- 35 Ph CH2 [(CH2)2 O] 2 CH3 |
| C2 H5 CH3 COOC2 H5 575a -- -- -- 36 Ph |
| CH2 [(CH2)2 O]2 CH3 C2 H5 CH3 C |
| COOH3 575a -- -- -- 37 Ph CH2 [(CH2)2 O]2 |
| C2 H5 C2 H5 CH3 COOC2 H5 575a -- |
| -- -- 38 Ph-4-OCH3 C2 H5 R2 COOC2 H5 |
| COOC2 H5 591 EC 120 50 39 Ph-3-SO2 N(CH3)2 |
| C2 H5 R2 Cl COH 595 -- -- -- 40 Ph-3-SO2 |
| N(CH3)2 (CH2)2 OCH3 R2 Cl COH 596 -- -- |
| -- 41 Ph-3-SO2 N[(CH2)2 OCH3 ]2 C2 H5 |
| R2 CH3 COOCH3 586-- -- -- 42 CH2 Ph (CH2)2 O |
| C |
| H3 R2 CH3 COOCH3 540a VY 94 51 43 CH2 OPh |
| C2 H5 R2 CH3 CN 543a MIX 88 72 44 Thien-3-yl |
| C2 H5 R2 CH3 COOCH3 582a -- -- -- 45 |
| Thien-2-yl C2 H5 R2 COOC4 H9 COOC4 H9 |
| 600 MIX 94 80 46 Thien-2-yl (CH2)2 OCH3 C2 H5 |
| CH3 COOC2 |
| H5 597a -- -- -- 47 Thien-2-yl (CH2)2 OCH3 |
| R2 CH3 CN 599 -- -- -- 48 Thien-2-yl (CH2)2 |
| OCH3 R2 CH3 COOCH3 589 -- -- -- 49 Thien-2-yl |
| (CH2)2 OCH3 R2 Cl COH 631 -- -- -- 50 Thien-3-yl |
| (CH2)3 OCH3 C2 |
| H5 CH3 COOCH3 583a -- -- -- 51 Thien-2-yl (CH2) |
| 3 OCH3 C2 H5 CH3 COOC2 H5 598a |
| -- -- -- 52 Thien-2-yl (CH2)3 OCH3 C2 H5 Cl COH |
| 638a -- -- -- 53 Thien-2-yl (CH2)2 |
| O(CH2)hd 2OCH3 C2 H5 CH3 COOCH3 599a |
| -- -- -- 54 Thien-2-yl (CH2)2 O(CH2)hd 2OCH3 |
| C2 |
| H5 Cl COOH 639a -- -- -- 55 Thien-2-yl (CH2)2 |
| O(CH2)hd 2OCH3 C3 H7 Cl COOH 636 MIX 91 59 56 |
| Thien-3-yl (CH2)2 O(CH2)hd 2OCH3 C3 H7 Cl |
| COOH 619a -- -- -- 57 Furan-2-yl C2 H5 R2 CH3 |
| CN 605a -- -- -- 58 Furan-2-yl C2 H5 R2 CH3 |
| COOCH3 596a -- -- -- 59 Furan-2-yl (CH2)2 OCH3 |
| R2 CH3 COOCH3 594a -- -- -- 60 Furan-2-yl (CH2). |
| sub.3 O(CH2)2 OCH3 C3 H7 Cl COH 635 a -- |
| -- -- 61 Pyrid-3-yl C2 H5 R2 Cl COH 599a -- -- |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| *weight ratio of binder:dye 2:1 |
| TABLE 3a |
| __________________________________________________________________________ |
| IIIc |
| ##STR21## |
| ΔE. |
| tau. |
| λmax |
| T* [kJ/ |
| Ex. |
| R1 R2 R3 |
| R8 |
| R9 R10 |
| [nm] |
| B °C.] |
| mol] |
| __________________________________________________________________________ |
| 62 Ph CH2 [(CH2)2 O]2 CH3 |
| C2 H5 |
| Cl COOCH3 |
| COH 598a |
| -- -- -- |
| 63 Thien-2-yl |
| (CH2)3 OCH3 |
| C2 H5 |
| CH3 |
| COO CH3 |
| CN 577 |
| VY 82 |
| 32 |
| 64 Thien-2-yl |
| (CH2)3 OCH3 |
| C2 H5 |
| Cl COOCH3 |
| COH 611a |
| -- -- -- |
| 65 Ph (CH2)3 OCH3 |
| R2 |
| CH3 |
| COOC2 H5 |
| CN 562a |
| -- -- -- |
| 66 Ph (CH2)3 OCH3 |
| C3 H7 |
| CH3 |
| COOC2 H5 |
| CN 589a |
| -- -- -- |
| 67 Ph-4-OCH3 |
| (CH2)3 OCH3 |
| R2 |
| CH3 |
| COOC2 H5 |
| CN 567 |
| VY 107 |
| 59 |
| 68 Thien-2-yl |
| CH2 [(CH2)2 O]2 CH3 |
| C2 H5 |
| CH3 |
| COOC2 H5 |
| CN 577 |
| VY 105 |
| 45 |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| TABLE 4 |
| __________________________________________________________________________ |
| ##STR22## IIIe |
| ΔE. |
| tau. |
| λmax |
| T* [kJ/ |
| Ex. R1 |
| R2 R3 |
| R8 R10 [nm] |
| B [°C.] |
| mol] |
| __________________________________________________________________________ |
| 69 Ph |
| (CH2)2 CH3 |
| R2 |
| H NO2 595a |
| -- -- -- |
| 70 Ph |
| (CH2)2 CH3 |
| R2 |
| Cl COH 581 |
| -- -- -- |
| 71 Ph |
| (CH2)2 CH3 |
| R2 |
| Cl CHC(CN) COOC4 H9 |
| 637 |
| VY 130 |
| 52 |
| 72 Thien- |
| C2 H5 R2 |
| Cl CHC(CN)COOC4 H9 |
| 631 |
| VY 125 |
| 67 |
| 3-yl |
| 73 Thien- |
| C2 H5 R2 |
| COOCH3 |
| CN 581 |
| -- -- -- |
| 2-yl |
| 74 Thien- |
| (CH2)2 OCH3 |
| R2 |
| H NO2 626 |
| -- -- -- |
| 2-yl |
| 75 Thien- |
| (CH2)3 O(CH2)2 OCH3 |
| C3 H7 |
| Cl COH 593 |
| -- -- -- |
| 3-yl |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| TABLE 5 |
| __________________________________________________________________________ |
| ##STR23## IIIg |
| ΔE. |
| tau. |
| λmax |
| T* [kJ/ |
| Ex. |
| R1 R2 R3 |
| R8 R9 |
| [nm] |
| B [°C.] |
| mol] |
| __________________________________________________________________________ |
| 76 CH(CH3)CH3 |
| C2 H5 R2 |
| (CH2)2 OCH3 |
| CN 522 |
| EC* |
| 63 69 |
| 77 Cyclohexyl C2 H5 R2 |
| CH3 CN 520 |
| MIX |
| 85 97 |
| 526a |
| VY 75 34 |
| 78 Cyclohexyl C2 H5 R2 |
| Ph CN 529 |
| VY 89 24 |
| 79 Cyclohexyl C2 H5 R2 |
| (CH2)2 OCH3 |
| CN 528a |
| -- -- -- |
| 80 Cyclohexyl (CH2)2 OCH3 |
| R2 |
| CH3 CN 521 |
| VY 75 42 |
| 81 Cyclohexyl (CH2)2 OCH3 |
| R2 |
| Ph CN 524 |
| MIX |
| 100 |
| 80 |
| 82 Cyclohexyl (CH2)3 OCH3 |
| C2 H5 |
| CH3 CN 523 |
| VY 72 38 |
| 83 Cyclohexyl (CH2)3 OCH3 |
| C2 H5 |
| C2 H5 |
| CN 520 |
| VY 75 37 |
| 84 Cyclohexyl (CH2)3 OCH3 |
| C2 H5 |
| Ph CN 529 |
| VY 84 44 |
| 85 Cyclohexyl (CH2)3 OCH3 |
| C2 H5 |
| (CH2)2 OCH3 |
| CN 524 |
| VY 72 33 |
| 86 Cyclohexyl [(CH2)2 O]2 CH3 |
| R2 |
| Thien-2-yl |
| CN 587a |
| -- -- -- |
| 87 Cyclohexyl CH2 [(CH2)2 O]2 CH3 |
| C3 H7 |
| Ph CN 531 |
| VY 88 38 |
| 88 Ph C2 H5 R2 |
| (CH2)2 OCH3 |
| CN 548 |
| VY 89 53 |
| 89 Ph C2 H5 R2 |
| Ph-4-SPh CN 556 |
| EC 118 |
| 53 |
| 90 Ph-3-OCH3 |
| C2 H5 R2 |
| Thien-2-yl |
| CN 572 |
| -- -- -- |
| 91 Ph-3-SO2 N(CH3)2 |
| (CH2)2 OCH3 |
| R2 |
| (CH2)3 OCH3 |
| CN 548 |
| EC* |
| 89 32 |
| 92 CH2 OPh |
| (CH2)2 OCH3 |
| R2 |
| CH3 CN 531a |
| -- -- -- |
| 93 Furan-2-yl C2 H5 R2 |
| CH3 CN 578a |
| -- -- -- |
| 94 Furan-2-yl C2 H5 R2 |
| (CH2)2 OCH3 |
| CN 578a |
| -- -- -- |
| 95 Thien-2-yl (CH2)2 OCH3 |
| C2 H5 |
| CH(CH3)CH3 |
| CN 579a |
| -- -- -- |
| 96 Thien-2-yl (CH2)3 OCH3 |
| C2 H5 |
| C2 H5 |
| CN 581a |
| -- -- -- |
| 97 Thien-2-yl (CH2)3 OCH3 |
| C3 H7 |
| C2 H5 |
| CN 581a |
| -- -- -- |
| 98 Thien-3-yl (CH2)3 O(CH2)2 OCH3 |
| C2 H5 |
| CH3 CN 562a |
| -- -- -- |
| 99 Thien-2-yl CH2 [(CH2)2 O]2 CH3 |
| C2 H5 |
| C2 H5 |
| CN 582a |
| -- -- -- |
| 100 |
| Thien-2-yl CH2 [CH 2)2 O]2 CH3 |
| C3 H7 |
| C2 H5 |
| CN 580a |
| -- -- -- |
| 101 |
| CH(CH3)CH3 |
| C2 H5 R2 |
| CH3 SCN 512 |
| EC 87 99 |
| 102 |
| Ph C2 H5 R2 |
| CH3 SCN 540 |
| -- -- -- |
| 103 |
| Ph (CH2)2 OCH3 |
| R2 |
| CH3 SCN 538 |
| EC 90 57 |
| 104 |
| Thien-2-yl |
| C2 H5 |
| R2 CH3 |
| SCN 562 EC 88 47 |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| *weight ratio of binder:dye = 2:1 |
| TABLE 6 |
| __________________________________________________________________________ |
| ##STR24## IIIh |
| Ex. |
| R1 R2 R3 |
| X X' λmax [nm] |
| __________________________________________________________________________ |
| 105 |
| Ph (CH2)2 OCH3 |
| R2 |
| H H 573a |
| 106 |
| Ph (CH2)2 OCH3 |
| R2 |
| Cl H 579a |
| 107 |
| Ph (CH2)3 O(CH2)2 OCH3 |
| C2 H5 |
| H H 574a |
| 108 |
| Ph (CH2)3 O(CH2)2 OCH3 |
| C3 H7 |
| NO2 |
| H 629a |
| 109 |
| Ph-4-O CH3 |
| (CH2)2 OCH3 |
| R2 |
| Cl N 594a |
| 110 |
| Thien-2-yl |
| (CH2)2 OCH3 |
| R2 |
| H H 594a |
| 111 |
| Thien-2-yl |
| (CH2)2 OCH3 |
| R2 |
| Cl H 602a |
| 112 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| C2 H5 |
| H H 597a |
| 113 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| C2 H5 |
| Cl H 605a |
| 114 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| R2 |
| Cl H 606a |
| 115 |
| Thien-2-yl |
| (CH2)3 O(CH2)2 OCH3 |
| C2 H5 |
| H H 598a |
| 116 |
| Thien-2-yl |
| (CH2)3 O(CH2)2 OCH3 |
| C3 H7 |
| Cl H 598a |
| 117 |
| Thien-2-yl |
| (CH2)3 O(CH2)2 OCH3 |
| C3 H7 |
| H Cl 606a |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| TABLE 7 |
| __________________________________________________________________________ |
| ##STR25## IIIi |
| Ex. |
| R1 |
| R2 R3 |
| Y λmax [nm] |
| B T*[°C.] |
| ΔEτ [kJ/mol] |
| __________________________________________________________________________ |
| 118 |
| CH3 |
| C2 H5 R2 |
| CN 591 EC* |
| 130 44 |
| 119 |
| Ph C2 H5 R2 |
| H 583 -- -- -- |
| 120 |
| Ph (CH2)3 O(CH2)2 OCH3 |
| C3 H7 |
| CN 622a |
| -- -- -- |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide glacial acetic acid |
| *weight ratio of binder:dye = 2.1 |
| TABLE 8 |
| __________________________________________________________________________ |
| ##STR26## IIIk |
| Ex. |
| R1 |
| R2 R3 |
| R8 |
| λmax [nm] |
| B T*[°C.] |
| ΔEτ [kJ/mol] |
| __________________________________________________________________________ |
| 121 |
| PH C2 H5 |
| R2 |
| Ph 531 EC 94 68 |
| 122 |
| Ph (CH2)2 OCH3 |
| R2 |
| Ph 533a |
| -- -- -- |
| 123 |
| Cyclohexyl |
| (CH2)2 OCH3 |
| R2 |
| Ph 508a |
| -- -- -- |
| 124 |
| Thien-2-yl |
| (CH2)2 OCH3 |
| R2 |
| Ph 556a |
| -- -- -- |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| TABLE 9 |
| __________________________________________________________________________ |
| ##STR27## IIIl |
| Ex. |
| R1 |
| R2 R3 |
| R8 λmax [nm] |
| B T*[°C.] |
| ΔEτ |
| [kJ/mol] |
| __________________________________________________________________________ |
| 125 |
| Ph C2 H5 |
| R2 |
| S(CH2)2 COOCH3 |
| 535 EC 110 72 |
| 126 |
| Ph C2 H5 |
| R2 |
| S(CH2)2 CN |
| 536 EC 103 47 |
| 127 |
| Ph C2 H5 |
| R2 |
| SCH3 533 -- -- -- |
| 128 |
| Ph C2 H5 |
| R2 |
| CH3 524 -- -- -- |
| 129 |
| Ph (CH2)2 OCH3 |
| R2 |
| S(CH2)2 COOCH3 |
| 535 MIX |
| 87 71 |
| 130 |
| Cyclohexyl |
| C2 H5 |
| R2 |
| S(CH2)2 COOCH3 |
| 519a |
| -- -- -- |
| 131 |
| Cyclohexyl |
| C2 H5 |
| R2 |
| SCH3 518a |
| -- -- -- |
| 132 |
| Thien-2-yl |
| C2 H5 |
| R2 |
| S(CH2)2 COOCH3 |
| 558 VY 93 61 |
| 133 |
| Thien-2-yl |
| C2 H5 |
| R2 |
| S(CH2)2 CN |
| 560 EC 105 42 |
| 134 |
| Thien-2-yl |
| C2 H5 |
| R2 |
| SCH3 557 EC 126 62 |
| __________________________________________________________________________ |
| a solvent 9:1 dimethylformamide/glacial acetic acid |
| *weight ratio of binder:dye = 2:1 |
| TABLE 10 |
| __________________________________________________________________________ |
| ##STR28## IIIm |
| Ex. |
| R1 |
| R2 |
| R3 |
| R18 |
| R19 |
| λmax [nm] |
| B T*[°C.] |
| ΔEτ [kJ/mol] |
| __________________________________________________________________________ |
| 135 |
| Ph C2 H5 |
| R2 |
| CN Ph 567 MIX |
| 106 37 |
| 136 |
| Thien-2-yl |
| C2 H5 |
| R2 |
| CONH2 |
| CH3 |
| 573 -- -- -- |
| __________________________________________________________________________ |
| TABLE 11 |
| ##STR29## |
| IIIg |
| Ex. R1 R2 R3 R8 R9 Hue 137 P |
| h (CH2)2 |
| OCH3 R2 CH3 H red 138 Ph (CH2)2 OCH3 |
| R2 CH3 Cl red 139 Ph (CH2)2 OCH3 R2 |
| CH3 Br red 140 Ph (CH2)2 OCH3 R2 CH3 CN |
| violet 141 Ph (CH2)2 OCH3 R2 CH3 SCN violet 142 P |
| h (CH2)2 OCH3 R 2 C2 H5 CN violet 143 Ph |
| (CH2)2 OCH3 R2 CH(CH3)CH3 CN violet 144 Ph ( |
| CH2)2 OCH3 R2 (CH2)2 OC2 H5 CN |
| bluish red 145 Ph (CH2)2 OCH3 (CH2)2 OCH3 |
| CH3 SCN violet 146 Ph (CH2)2 OCH3 (CH2)2 |
| OCH3 Ph CN violet 147 Ph (CH2)2 |
| OCH3 (CH2)2 OCH3 (CH2)2 OCH3 CN |
| violet 148 Ph (CH2)2 OCH3 C2 |
| H5 (CH2)2 OCH3 CN violet 149 Ph (CH2)3 |
| OC2 H5 (CH2)2 OCH3 (CH2)2 OCH3 |
| CN violet 150 Ph (CH2)3 OC2 |
| H5 CH3 (CH2)2 |
| OCH3 CN violet 151 Ph (CH2)3 O(CH2)2 OCH3 ( |
| CH2)2 OCH3Ph CN violet 152 Ph (CH2)3 |
| O(CH2)2 OCH3 (CH2)3 OCH3Ph CN violet 153 |
| Ph [(CH2)2 O]2 CH3 (CH2)2 OCH3 Ph CN |
| violet 154 Ph [(CH2)2 O]2 |
| CH3 CH3 (CH2)2 |
| OCH3 CN violet 155 Ph [(CH2)2 O]2 CH3 C2 |
| H5 (CH2)2 OCH3 CN violet 156 Ph [(CH2)2 |
| O]2 C2 H5 (CH2)3 CH3 CH3 Ph CN violet |
| 157 Ph [(CH2)2 O]2 CH3 (CH2)3 CH3 Ph |
| CN violet 158 Ph-4-Cl (CH2)2 |
| OCH3 R2 (CH2)2 OCH3 CN violet 159 Ph-4-Cl |
| [(CH2)2 O]2 CH3 C2 H5 (CH2)2 |
| OCH3 CN violet 160 Ph-4-OCH3 (CH2)2 OCH3 |
| C2 H5 CH3 CN violet 161 Ph-4-OCH3 (CH2)2 |
| OCH3 C2 H5 (CH2)2 OCH3 CN violet 162 |
| Thien-2-yl (CH2)2 OCH3R2 CH3 SCN violet 163 |
| Thien-2-yl (CH2)2 O CH3R2 CH3 CN reddish blue |
| 164 Thien-2-yl (CH2)2 OCH3R2 C2 H5 CN |
| reddish blue 165 Thien-2-yl (CH2)2 OCH3R2 C3 |
| H7 CN reddish blue 166 Thien-2-yl (CH2)2 OCH3R2 C |
| H(CH3)CH3 CN reddish blue 167 Thien-2-yl (CH2)3 |
| OCH3R2 (CH2)2 OCH3 CN navy 168 Thien-2-yl |
| (CH2)3 OCH3R2 (CH2)2 OC2 H5 CN |
| navy 169 Thien-2-yl (CH2)3 OCH3 (CH2)2 |
| OCH3 CH3 SCN reddish blue 170 Thien-2-yl (CH2)3 |
| OCH3 (CH2)2 OCH3 Ph CN reddish blue 171 Thien-2-yl |
| (CH2)3 OCH3 (CH2)2 OCH3 Ph SCN reddish |
| blue 172 Thien-2-yl (CH2)3 OCH3 (CH2)2 |
| OCH3 (CH2)2 |
| OCH3 CN navy 173 Thien-2-yl (CH2)3 |
| OCH3 (CH2)2 OCH3 (CH2)2 OC2 H5 |
| CN navy 174 Thien-2-yl (CH2)3 OCH3 (CH2)2 |
| OC2 H5 (CH2)2 OCH3 CN navy 175 Thien-2-yl |
| (CH2)3 OCH3 (CH2)2 OC2 H5 Thien-2-yl |
| CN blue 176 Thien-2-yl (CH2)3 OCH3 C2 H5 |
| (CH2)2 OCH3 CN navy 177 Thien-2-yl (CH2)3 |
| OC2 H5 (CH2)3 OCH3 Thien-3-yl CN blue 178 |
| Thien-2-yl (CH2)3 OC2 H5 (CH2) 3 OCH3 ( |
| CH2)2 OCH3 CN navy 179 Thien-2-yl (CH2)3 |
| OC2 H5 (CH2)2 |
| OCH3 |
| ##STR30## |
| CN reddish blue 180 Thien-2-yl (CH2)3 OC2 H5 |
| (CH2)2 OC2 H5 (CH2)2 OCH3 CN navy 181 |
| Thien-2-yl (CH2)3 O(CH2)2 OCH3 C2 H5 |
| CH3 SCN bluish violet 182 Thien-2-yl (CH2)3 |
| O(CH2)2 OCH3 C2 H5 Ph CN reddish blue 183 |
| Thien-2-yl (CH2)3 O(CH2)2 OCH3 C2 H5 |
| (CH2)2 OCH3 CN navy 184 Thien-2-yl (CH2)3 |
| O(CH2)2 OCH3 C2 H5 Thien-2-yl CN blue 185 |
| Thien-2-yl (CH2)3 O(CH2)2 OCH3 C3 H7 |
| CH(CH3)CH3 CN navy 186 Thien-2-yl (CH2)3 |
| O(CH2)2 OCH3 C3 H7 Ph CN reddish blue 187 |
| Thien-2-yl (CH2)3 O(CH2)2 OCH3 C3 H7 |
| (CH2)2 OCH3 CN navy 188 Thien-2-yl (CH2)3 |
| O(CH2)2 OCH3 C3 H7 (CH2)2 OC2 |
| H5 CN navy 189 Thien-2-yl (CH2)3 O(CH2)2 |
| OC2 H5 C2 H5 (CH2)2 OCH3 CN navy 190 |
| Thien-2-yl [(CH2)2 O]2 CH3 (CH2)2 |
| O CH3 Thien-2-yl CN reddish blue 191 Thien-2-yl [(CH2)2 |
| O]2 CH3 (CH2)2 OCH3 Thien-3-yl CN blue 192 |
| Thien-2-yl [(CH2)2 O]2 CH3 (CH2)3 |
| OCH3 Ph CN reddish blue 193 Thien-2-yl [(CH2)2 O]2 |
| CH3 C2 H5 (CH2)2 |
| OCH3 CN navy 194 Thien-2-yl [(CH2)2 O]2 CH3 |
| C2 H5 Thien-3-yl CN blue 195 Thien-2-yl [(CH2)2 |
| O]2 CH3 C3 H7 (CH2)2 OCH3 CN navy 196 |
| Thien-2-yl [(CH2)2 O]2 C2 H5 (CH2)3 |
| OCH3 Ph CN reddish blue 197 Thien-2-yl [(CH2)2 O]2 |
| C2 H5 (CH2)3 OCH3 Pyrid-3-yl CN reddish blue |
| 198 Thien-2-yl [(CH2)2 O]3 CH3 (CH2)3 |
| OCH3 Ph CN reddish blue 199 Thien-2-yl [(CH2)2 O]3 |
| CH3 (CH2)2 OCH3 Thien-2-yl CN reddish blue 200 |
| Thien-2-yl [(CH2)2 O]3 CH3 (CH2)2 |
| OCH3 Thien-3-yl CN reddish blue 201 Thien-2-yl [(CH2)2 |
| O]3 CH3 C2 H5 Ph CN reddish blue 202 Thien-2-yl |
| [(CH2)2 O]3 CH3 C2 H5 Thien-2-yl CN blue |
| 203 Thien-2-yl [(CH2)2 O]3 CH3 C2 H5 |
| Thien-3-yl CN blue |
| TABLE 12 |
| __________________________________________________________________________ |
| ##STR31## IIII |
| Ex. |
| R1 R2 R3 R8 Hue |
| __________________________________________________________________________ |
| 204 |
| Ph (CH2)2 OCH3 |
| R2 SCH3 reddish violet |
| 205 |
| Ph (CH2)3 OCH3 |
| (CH2)2 OCH3 |
| SCH3 violet |
| 206 |
| Ph (CH2)3 OCH3 |
| C2 H5 |
| S(CH2)2 COOCH3 |
| violet |
| 207 |
| Ph [(CH2)2 O]2 CH3 |
| Ph SCH3 violet |
| 208 |
| Ph [(CH2)2 O]2 C2 H5 |
| Ph SCH3 violet |
| 209 |
| Ph-4-OCH3 |
| (CH2)3 OCH3 |
| (CH2)2 OCH3 |
| SCH3 violet |
| 210 |
| Thien-2-yl |
| (CH2)2 OCH3 |
| R2 SCH3 reddish blue |
| 211 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| R2 SCH3 reddish blue |
| 212 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| (CH2)2 OCH3 |
| SC2 H5 reddish blue |
| 213 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| (CH2)2 OC2 H5 |
| SCH3 bluish violet |
| 214 |
| Thien-2-yl |
| (CH2)3 OCH3 |
| C2 H5 |
| S(CH2)2 COOCH3 |
| bluish violet |
| 215 |
| Thien-2-yl |
| (CH2)3 OC2 H5 |
| C2 H5 |
| S(CH2)2 COOCH3 |
| bluish violet |
| 216 |
| Thien-2-yl |
| [(CH2)2 O]2 CH3 |
| C2 H5 |
| SCH3 bluish violet |
| 217 |
| Thien-2-yl |
| [(CH2)2 O]2 C2 H5 |
| (CH2)3 OCH3 |
| SCH3 bluish violet |
| 218 |
| Thien-2-yl |
| [(CH2)2 O]2 C2 H5 |
| C2 H5 |
| SCH3 bluish |
| __________________________________________________________________________ |
| violet |
Bach, Volker, Etzbach, Karl-Heinz, Lamm, Gunther, Sens, Ruediger, Reichelt, Helmut, Gruettner, Sabine
| Patent | Priority | Assignee | Title |
| 8258300, | Sep 29 2008 | King Abdulaziz University | Azo dyes |
| Patent | Priority | Assignee | Title |
| 4933226, | Dec 11 1989 | Eastman Kodak Company; EASTMAN KODAK COMPANY, A CORP OF NJ | Thermal print element comprising a magenta 3-aryl-2-arylazo-5-aminothiazole or aminothiophene dye stabilized with a cyan indoaniline dye |
| 5101035, | Aug 26 1989 | BASF Aktiengesellschaft | Merocyanine-like thiazole dyes and thermal transfer thereof |
| EP192435, | |||
| EP275381, | |||
| JP239291, |
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