Azo dyes for thermotransfer printing
Azo dyes useful for thermotransfer printing have the formula ##STR1##
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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:
R.sup.1 is hydrogen;
C.sub.1 -C.sub.15 -alkyl which may be substituted by phenyl or phenoxy;
cyclohexyl which may be substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy or halogen:
phenyl which may be substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 --C.sub.5 -alkoxy, sulfonamido or halogen;
thienyl which may be C.sub.1 --C.sub.5 -alkyl- or halogen-substituted, furanyl or pyridyl;
a radical of the formula II
[--W--O].sub.n --R.sup.4 II
where
W is identical or different C.sub.2 -C.sub.6 -alkylene,
n is from 1 to 6 and
R.sup.4 is C.sub.1 -C.sub.4 -alkyl or a phenyl or benzyl group which may both be substituted by C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy;
R.sup.2 and R.sup.3 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, C.sub.1 -C.sub.4 -alkylphenyl, C.sub.1 -C.sub.4 -alkoxyphenyl, halophenyl, benzyloxy, C.sub.1 -C.sub.4 -alkylbenzyloxy, C.sub.1 -C.sub.4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano; cyclohexyl which may be substituted by C.sub.1 14 C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkoxy or halogen;
phenyl which may be substituted by C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkoxy, benzyloxy or halogen; a radical of the abovementioned formula II; and
is the radical of a diazo component III
D--NH.sub.2 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:
R.sup.1' is C.sub.1 -C.sub.8 -alkyl which may be substituted by
phenyl or cyclohexyl;
phenyl which may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or chlorine;
thienyl;
a radical of the formula IIa ##STR4## where p is 0 or 1, q is from 1 to 4, and R.sup.4' is C.sub.1 -C.sub.4 -alkyl, phenyl or benzyl;
R.sup.2' and R.sup.3' are each C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.10 -alkoxy or C.sub.1 -C.sub.10 -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:
R.sup.5, R.sup.6 and R.sup.7 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--OR.sup.15, --CO--NR.sup.15 R.sup.16, --SO--OR.sup.15, --SO.sub.2 --OR.sup.15 or --SO.sub.2 --NR.sup.15 R.sup.16 in which
R.sup.15 and R.sup.16 are each alkyl or alkoxyalkyl which may each contain up to 10 carbon atoms, and
R.sup.16 may also be hydrogen;
R.sup.5 may also be oxadiazole substituted in the 3-position by C.sub.1 -C.sub.8 -alkoxy;
R.sup.6 may also be a radical of the formula --CO--R.sup.17 or --CO--OR.sup.17 where
R.sup.17 is phenyl which may be substituted by C.sub.1 -C.sub.8 -alkyl;
a radical of the formula IV ##STR16## where X is cyano, --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16 ;
R.sup.8 is hydrogen, chlorine, cyano or thiocyanato, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 10 carbon atoms; 2-(C.sub.1 -C.sub.2 -alkoxycarbonyl)ethylthio; 2-(pyrrolid-1-yl)ethyl; C.sub.5 -C.sub.6 -cycloalkyl or -cycloalkylthio; phenyl which may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, benzyloxy or phenylthio; Ar-C.sub.1 -C.sub.4 -alkythio; Ar-C.sub.1 -C.sub.4 -alkoxy or Ar-C.sub.1 -C.sub.4 -alkylthio;
thienyl or pyridyl which may each be substituted by C.sub.1 -C.sub.4 -alkyl;
a radical of the formula II;
a radical of the formula --CO--OR.sup.15, --CO--NR.sup.15 R.sup.16, --SO--OR.sup.15 or --SO.sub.2 --OR.sup.15 ;
R.sup.9 is hydrogen, chlorine, bromine, nitro, cyano, thiocyanato or phenyl; or a radical of the formula --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16 ;
R.sup.10 is hydrogen, chlorine, bromine, nitro, cyano or formyl; a radical of the formula --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16 ; or a radical of the formula IV
R.sup.11 and R.sup.12 are each hydrogen, chlorine, bromine, nitro or cyano; C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy; or a radical of the formula --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16 ;
R.sup.13 is hydrogen, chlorine, bromine or C.sub.1 -C.sub.4 -alkyl;
R.sup.14 is hydrogen or cyano; or a radical of the formula --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16 ;
R.sup.18 is cyano or formamido;
R.sup.19 is methyl or phenyl;
X is hydrogen, chlorine or nitro; and
Y is hydrogen or cyano.
Suitable alkyl R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12, R.sup.13, R.sup.15 or R.sup.16 is in particular methyl, ethyl, propyl, ispropyl or butyl, but also isobutyl, sec.-butyl or tert.-butyl.
R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.15 and R.sup.16 may each also be for example pentyl, isopentyl, neopentyl, tert.-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, mixed isooctyl isomer and cyclohexyl.
R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.15 and R.sup.16 may each also be for example nonyl, decyl, mixed isononyl isomer or mixed isodecyl isomer.
Other possible meanings for R.sup.1, R.sup.2 and R.sup.3 include undecyl, dodecyl, tridecyl, mixed isotridecyl isomer, tetradecyl and pentadecyl and for R.sup.2 and R.sup.3 additionally hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkyls R.sup.2 and R.sup.3 may each also be substituted by phenyl; specific examples, where Ph=phenyl, are:
--CH.sub.2 --Ph, --CH(CH.sub.3)--Ph, --(CH.sub.2).sub.2 --Ph,
--(CH.sub.2).sub.4 --CH(CH.sub.3)--Ph--3--CH.sub.3,
--(CH.sub.2).sub.3 --CH(C.sub.4 H.sub.9)--Ph--3--CH.sub.3,
--(CH.sub.2).sub.6 --Ph--4--O--CH.sub.3.
--CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.3 --Ph--3--O--C.sub.2 H.sub.5 and
--CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.3 --Ph--3--Cl.
It is also possible to use for example the following halo, hydroxyl and cyanoalkyl groups as R.sup.2 or R.sup.3 :
--(CH.sub.2).sub.5 --Cl, --CH(C.sub.4 H.sub.9)--(CH.sub.2).sub.3 --Cl or --(CH.sub.2).sub.4 --CF.sub.3 ;
--(CH.sub.2).sub.2 --CH(CH.sub.3)--OH. --(CH.sub.2).sub.2 --CH(C.sub.4 H.sub.9)--OH oder CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.9 --OH:
--(CH.sub.2).sub.2 --CN, --(CH.sub.2).sub.3 --CN, --CH.sub.2 --CH(CH.sub.3)--CH(C.sub.2 H.sub.5)--CN, --(CH.sub.2).sub.6 --CH(C.sub.2 H.sub.6)--CN and
--(CH.sub.2).sub.3 --CH(CH.sub.3)--(CH.sub.2).sub.2 --CH(CH.sub.3)--CN.
When R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.15 or R.sup.16 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 R.sup.4 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:
--(CH.sub.2).sub.2 --O--CH.sub.3, --(CH.sub.2).sub.2 --O--C.sub.2 H.sub.5, --(CH.sub.2).sub.2 --O--C.sub.3 H.sub.7, --(CH.sub.2).sub.2 --O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.2 --O--CH.sub.2 --CH(CH.sub.3)--CH.sub.3,
--(CH.sub.2).sub.2 --O--Ph, --(CH.sub.2).sub.2 --O--CH.sub.2 --Ph,
--[(CH.sub.2).sub.2 --O].sub.2 --CH.sub.3, --[(CH.sub.2).sub.2 --O].sub.2 --C.sub.2 H.sub.5, --[(CH.sub.2).sub.2 --O].sub.2 --Ph,
--[(CH.sub.2).sub.2 --O].sub.2 --Ph--4--O--C.sub.4 H.sub.9,
--[(CH.sub.2).sub.2 --O].sub.3 --C.sub.4 H.sub.9, --[(CH.sub.2).sub.2 --O].sub.3 --Ph, --[(CH.sub.2).sub.2 --O].sub.3 --Ph--3--C.sub.4 H.sub.9,
--[(CH.sub.2).sub.2 --O].sub.4 --CH.sub.3,
--(CH.sub.2).sub.3 --O--(CH .sub.2 ).sub.2 --O--CH.sub.3, --(CH .sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.2 H.sub.5,
--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--Ph, --(CH.sub.2).sub.3 --O--[(CH.sub.2).sub.2 --O].sub.2 --CH.sub.3 and
--(CH.sub.2).sub.3 --O--[(CH.sub.2).sub.2 --O].sub.2 --C.sub.2 H.sub.5.
Further preferred groups II are for example:
--(CH.sub.2).sub.3 --O--CH.sub.3, --(CH.sub.2).sub.3 --O--C.sub.2 H.sub.5, --(CH.sub.2).sub.3 --O--C.sub.3 H.sub.7, --(CH.sub.2).sub.3 --O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.3 --O--Ph, --[(CH.sub.2).sub.3 --O].sub.2 --CH.sub.3, --[(CH.sub.2).sub.3 --O--].sub.2 'C.sub.2 H.sub.5,
--CH.sub.2 --CH(CH.sub.3)--O--CH.sub.3, --CH.sub.2 --CH(CH.sub.3)--O--C.sub.2 H.sub.5, --CH.sub.2 --CH(CH.sub.3)--O--C.sub.3 H.sub.7,
--CH.sub.2 --CH(CH.sub.3)--O--C.sub.4 H.sub.9, --CH.sub.2 --CH(CH.sub.3)--O--Ph,
--(CH.sub.2).sub.4 --O--CXH.sub.3, --(CH.sub.2).sub.4 --O--C.sub.2 H.sub.5, --(CH.sub.2).sub.4 --O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.4 --O--CH.sub.2 --CH(C.sub.2 H.sub.5)--C.sub.4 H.sub.9, --(CH.sub.2).sub.4 --O--Ph,
--(CH.sub.2).sub.4 --O--CH.sub.2 --Ph--2--O--C.sub.2 H.sub.5, --(CH.sub.2).sub.4 --O--C.sub.6 H.sub.10 --2--C.sub.2 H.sub.5,
--[(CH.sub.2).sub.4 --O].sub.2 --CH.sub.3, --[(CH.sub.2).sub.4 --O].sub.2 --C.sub.2 H.sub.5, --[(CH.sub.2).sub.2 --CH(CH.sub.3)--O].sub.2 --C.sub.2 H.sub.5,
--(CH.sub.2).sub.5 --O--CH.sub.3, --(CH.sub.2).sub.5 --O--C.sub.2 H.sub.5, --(CH.sub.2).sub.5 --O--C.sub.3 H.sub.7, --(CH.sub.2).sub.5 --O--Ph,
--CH.sub.2).sub.2 --CH(C.sub.2 H.sub.5)--O--CH.sub.2 --Ph--3--O--C.sub.4 H.sub.9, --(CH.sub.2).sub.2 --CH(C.sub.2 H.sub.5)--O--CH.sub.2 --Ph--3--Cl,
--(CH.sub.2).sub.6 --O--C.sub.4 H.sub.9, --(CH.sub.2).sub.6 --O--Ph--4--O--C.sub.4 H.sub.9, --(CH.sub.2).sub.3 --CH(CH.sub.3)--CH(CH.sub.3)--CH.sub.2 --O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --O--CH.sub.3, --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --O--C.sub.2 H.sub.5,
--(CH.sub.2).sub.4 --O--(CH.sub.2).sub.3 --O--CH.sub.3 and --(CH.sub.2).sub.4 --O--(CH.sub.2).sub.3 --O--C.sub.2 H.sub.5.
Suitable alkoxyalkyl also includes for example:
--(CH.sub.2).sub.8 --O--CH.sub.3, --(CH.sub.2).sub.8 --O--C.sub.4 H.sub.9, --(CH.sub.2).sub.8 --O--CH.sub.2 --Ph--3--C.sub.2 H.sub.5,
--(CH.sub.2).sub.4 --CH(Cl)--(CH.sub.2).sub.3 --O--CH.sub.2 --Ph--3--CH.sub.3 and
--(CH.sub.2).sub.3 --CH(C.sub.4 H.sub.9)--O--CH.sub.2 --Ph--3--CH.sub.3.
Of the above-recited alkoxyalkyl groups, those which contain up to 8 carbon atoms are also suitable for use as R.sup.8 and those having up to 12 carbon atoms are also suitable for use as R.sup.15 and R.sup.16.
Preferred alkoxy R.sup.2, R.sup.3, R.sup.8, R.sup.11 or R.sup.12 is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec.-butoxy.
R.sup.8 and especially R.sup.2 and R.sup.3 may each also be for example pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, oxtyloxy or 2-ethylhexyloxy.
R.sup.2 and R.sup.3 may each in addition be for example nonyloxy or decyloxy but also undecyloxy, dodecyloxy, tridecyloxy, tetradecyioxy or pentadecyloxy.
R.sup.8 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 R.sup.2 or R.sup.3 is for example:
--CH.sub.2).sub.2 --O--CO--CXH.sub.3,
--(CH.sub.2).sub.3 --O--CO--(CH.sub.2).sub.7 --CH.sub.3,
--(CH.sub.2).sub.2 --O--CO--(CH.sub.2).sub.3 --PH-2--O--CH.sub.3,
--CH(CH.sub.2 --Ph--3--CH.sub.3)--O--CO--C.sub.4 H.sub.9 and
--(CH.sub.2).sub.4 --O--CO--(CH.sub.2).sub.4 --CH(C.sub.2 H.sub.5)--OH;
--(CH.sub.2).sub.2 --O--CO--O--CH.sub.3,
--(CH.sub.2).sub.3 --O--CO--O--(CH.sub.2)).sub.7 --CH.sub.3,
--CH(C.sub.2 H.sub.5)--CH.sub.2 --O--CO--O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.4 --O--CO--O--(CH.sub.2).sub.2 --CH(CH.sub.3)--O--Ph--3--CH.sub.3 and
--(CH.sub.2).sub.5 --O--CO--O--(CH.sub.2).sub.5 --CN;
--(CH.sub.2).sub.2 --CO--O--CH.sub.3,
--(CH.sub.2).sub.3 --CO--O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.3 --CH(CH.sub.3)--CH.sub.2 --CO--O--C.sub.4 H.sub.9,
--(CH.sub.2).sub.3 --CH(C.sub.4 H.sub.9)--CH.sub.2 --CO--O--C.sub.2 H.sub.5,
--(CH.sub.2).sub.2 --CO--O--(CH.sub.2).sub.5 --Ph,
--(CH.sub.2).sub.4 --CO--O--(CH.sub.2).sub.4 --Ph-4C.sub.4 H.sub.9,
--(CH.sub.2).sub.3 --CO--O--(CH.sub.2).sub.4 --O--Ph-3--O--CH.sub.3,
--(CH.sub.2).sub.2 --CH(CH.sub.2 OH)--(CH.sub.2).sub.2 --CO--O--C.sub.2 H.sub.5,
--CH(C.sub.2 H.sub.5)--CH.sub.2 --CO--O--CH.sub.2).sub.4 --OH and
--(CH.sub.2).sub.3 --CO--O--(CH.sub.2).sub.6 --CN.
Phenyl and cyclohexyl which may each be present as
R.sup.1, R.sup.2 or R.sup.3 are for example: --Ph, --Ph--3--CH.sub.3, --Ph--4--(CH.sub.2).sub.10 --CH.sub.3, --Ph--3--(CH.sub.2).sub.5 --CH(CH.sub.3)--CH.sub.3, Ph--4--O--C.sub.4 H.sub.9, --Ph--4--(CH.sub.2).sub.5 --CH(C.sub.2 H.sub.5)--CH.sub.3, --Ph--4--)--CH.sub.2 --Ph or --Ph--4--Cl and also in the case of R.sup.1 in particular --Ph--3--SO.sub.2 --N(CH.sub.3)--CH.sub.3 or Ph--3--SO.sub.2 --N--((CH.sub.2).sub.2 --O--CH.sub.3)--(CH.sub.2).sub.2 --O--CH.sub.3 ; --C.sub.6 H.sub.10 --4--CH.sub.3, --C.sub.6 H.sub.10 --4--C.sub.10 H.sub.21, --C.sub.6 H.sub.10 --3--O--C.sub.4 H.sub.9, --C.sub.6 H.sub.10 --3--O--(CH.sub.2).sub. 4 --CH(C.sub.2 H.sub.5)--CH.sub.3 or --C.sub.6 H.sub.10 --4--Cl.
Where R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12 or R.sup.14 is a group of the formula --CO--OR.sup.15 or --CO--NR.sup.15 R.sup.16, particularly suitable instanccs thereof are
--CO--O--CH.sup.3, --CO--O--C.sub.2 H.sub.5, --CO--O--C.sub.3 H.sub.7,
--CO--O--C.sub.4 H.sub.9, --CO--N(CH.sub.3)--CH.sub.3 and
--CO--N(C.sub.2 H.sub.5)--C.sub.2 H.sub.5, but also for example
--CO--O--C.sub.5 H.sub.11, --CO--O--C.sub.6 H.sub.13, --CO--n(C.sub.3 H.sub.7)--C.sub.3 H.sub.7 and --CO--n(C.sub.4 H.sub.9.
Groups of the formula --SO--OR.sup.15 or --SO.sub.2 --OR.sup.15, which may each be used as R.sup.5, R.sup.6, R.sup.7 or R.sup.8 are For example:
--SO--O--CH.sub.3, --SO--O--C.sub.2 H.sub.5, --SO--O--C.sub.3 H.sub.7,
--SO.sub.2 --O--CH.sub.3, --SO.sub.2 --O--C.sub.2 H.sub.5, --SO.sub.2 --O--C.sub.3 H.sub.7.
R.sup.5, R.sup.6 and R.sup.7 may each also be groups of the formula --SO.sub.2 --NR.sup.15 R.sup.16, in particular --SO.sub.2 --N(CH.sub.3)--CH.sub.3, --SO.sub.2 --N((CH.sub.2).sub.2 --O--CH.sub.3)--(CH.sub.2).sub.2 --O--CH.sub.3, but also for example --SO.sub.2 --N(C.sub.2 H.sub.5)--C.sub.2 H.sub.5 or --SO.sub.2 --N(C.sub.3 H.sub.7)--C.sub.3 H.sub.7.
R.sup.6 and R.sup.10 may each also be groups of the formula IV, such as --CH.dbd.C(CN)--CN, --CH.dbd.C(CN)--CO--O--CH.sub.3, --CH.dbd.C(CN)--CO--O--C.sub.2 H.sub.5. --CH.dbd.C(CN)--CO--O--C.sub.3 H.sub.7, --CH.dbd.--C(CN)--CO--O--C.sub.4 H.sub.9, --CH.dbd.C(CN)--N(CH.sub.3)--CH.sub.3 or --CH.dbd.C(CN)--N(C.sub.2 H.sub.5)--C.sub.2 H.sub.5.
Of the aforementioned radicals, R.sup.1 is particularly preferably C.sub.1 -C.sub.8 alkyl, especially methyl or isopropyl, cyclohexyl, phenyl, which may also be methoxy-, sulfonamido- or chlorine-substituted, or benzyl. Preferred R.sup.12 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 R.sup.2 or R.sup.3 is of up to 12 carbon atoms, especially methyl, ethyl or propyl, preferred cyanoalkyl and alkoxy R.sup.2 or R.sup.3 is of up to 10 carbon atoms. Particularly preferred R.sup.2 and R.sup.3 each has the formula Ila with methyl or ethyl as R.sup.4 '.
Of the above-recited diazo components D-NH.sub.2, the following are particularly preferred:
aniline derivatives IIIa having the above-defined meanings of R.sup.5, R.sup.6 and R.sup.7
aminothiophene derivatives IIIc having the following meanings for R.sup.8, R.sup.9 and R.sup.10 :
R.sup.8 is hydrogen or chlorine; alkyl, alkoxy or alkoxyalkyl, which may each contain up to 8 carbon atoms; phenyl which may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted, or benzyl; or a radical of the formula --CO--OR.sup.15 ;
R.sup.9 is cyano or a radical of the formula --CO--OR.sup.15 or else --CO--NR.sup.15 R.sup.16 ; and
R.sup.10 is cyano, nitro, formyl or a radical of the formula IV
aminothiazole derivatives IIIe having the following meanings for R.sup.8 and R.sup.10 :
R.sup.8 is hydrogen, chlorine, C.sub.1 14 C.sub.8 -alkyl, phenyl which may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted, benzyl, or a radical of the formula --CO--OR.sup.15 ; and
R.sup.10 is cyano, nitro, formyl or a radical of the formula --CO--OR.sup.15
aminoisothiazole derivatives IIIg having the following meanings for R.sup.8 and R.sup.9 :
R.sup.8 is chlorine, alkyl, alkoxy, alkylthio or alkoxyalkyl which may each contain up to 8 carbon atoms, phenyl which may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted, benzyl or benzyloxy, and
R.sup.9 is cyano, nitro or a radical of the formula --CO--OR.sup.15
aminothiadiazole derivatives IIIk and aminoisothiadiazole derivatives IIIl having the following meaning for R.sup.8 :
R.sup.8 is hydrogen, chlorine, cyano, thiocyanato, or alkyl, alkoxy, alkylthio or alkoxyalkyl, which may each contain up to 8 carbon atoms, 2-(C.sub.1 -C.sub.2 -alkoxycarbonyl)ethylthio, phenyl which may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted, benzyl, benzyloxy, or a radical of the formula --CO--OR.sup.15, --SO--OR.sup.15 or --SO.sub.2 --OR.sup.15.
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 .mu.m, preferably from 5 to 10 .mu.m.
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 T.sub.g are within the range from 50.degree. to 100.degree. 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.degree. C., so thai dye transfer takes not more than 15 msec.
EXAMPLESFirst, transfer sheets (donors) were produced from a polyester sheet from 6 to 10 .mu.m in thickness coated with an approximately 5 .mu.m 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 .mu.m in thickness which had been coated with a layer of plastic 8 .mu.m 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.degree.-80.degree. C. for 2 minutes. This operation was repeated three times with similar samples at a temperature within the range from 80.degree. to 120.degree. 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 .DELTA.E.sub..lambda. 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 .lambda..sub.max [nm]. The .lambda..sub.max 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.dbd.2:1, and VY=nylon.
If the abovementioned parameters R* [.degree.C.] and .DELTA.E, [kJ/mol] were measured, the values found are likewise stated.
TABLE 1
__________________________________________________________________________
##STR17## IIIa
Ex
R.sup.1
R.sup.2 R.sup.3
R.sup.5 R.sup.6
.lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau.
[kJ/mol]
__________________________________________________________________________
1 Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CN H 494 EC 104 42
2 Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
##STR18## NO.sub.2
544 MS 90 71
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
##STR19## IIIb
Ex.
R.sup.2 R.sup.3
R.sup.5
R.sup.6
R.sup.7
R.sup.11
R.sup.12
R.sup.12'
.lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau.
[kJ/mol]
__________________________________________________________________________
3 C.sub.2 H.sub.5
R.sup.2
Cl CN Cl OCH.sub.3
H OCH.sub.3
584 EC 96 84
4 (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H H Br H H 538 MS 97 76
5 (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H H Br Br H 492 EC 106 84
__________________________________________________________________________
3 TABLE 3
IIIc
##STR20##
Ex. R.sup.1 R.sup.2 R.sup.3 R.sup.8 R.sup.10 .lambda..sub.max [nm] B
T*[.degree.C.] .DELTA.E.sub..tau.
[kJ/mol] 6 Cyclohexyl C.sub.2 H.sub.5
R.sup.2 CH.sub.3 CN 550 MIX 90 65 7 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
CH.sub.3 COOCH.sub.3 545.sup.a -- -- -- 8 Cyclohexyl (CH.sub.2).sub.2
OCH.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 544.sup.a -- -- -- 9 Cyclohexyl
(CH.sub.2).sub.2 OCH.sub.3 R.sup. 2 Cl COH 580.sup.a MIX 90 88 VY
90 58 10 Cyclohexyl (CH.sub.2).sub.2
OCH.sub.3 R.sup.2 Cl CHC(CN)COO.sub.4
H.sub.9 625 VY 99 54 11 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3 C.sub.2
H.sub.5 CH.sub.3 CN 551 MIX 92 77 12 Cyclohexyl (CH.sub.2).sub.2
OCH.sub.3 C.sub.2 H.sub.5 Cl COH 572 MIX 92 66 VY 86 40 13
CH(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 547 EC 90 88 14 C
H(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 Cl COH 572 MIX 90 50 15
CH(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 547 -- -- -- 16 C
H(CH.sub.3)CH.sub.3 C.sub.2 H.sub.5 R.sup.2 COOC.sub.2
H.sub.5 COOC.sub.2 H.sub.5 542 VY 135 50 17 CH(C.sub.2 H.sub.5)C.sub.4
H.sub.9 C.sub.2 H.sub.5 R.sup.2 Cl CHC(CN)COOC.sub.4 H.sub.9 608 MIX
90** 59 18 Ph C.sub.2 H.sub.5 R.sup.2 H NO.sub.2 623 -- -- -- 19 Ph
C.sub.2 H.sub.5 R.sup.2 Cl Br 559 -- -- -- 20 Ph C.sub.2 H.sub.5 R.sup.2 C
l COH 602 -- -- -- 21 Ph C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOC.sub.2
H.sub.5 569 EC 132 64 22 Ph C.sub.2 H.sub.5 R.sup.2 OC.sub.2 H.sub.5
COH 598 -- -- -- 23 Ph C.sub.2 H.sub.5 R.sup.2 COOC.sub.2 H.sub.5
COOC.sub.2 H.sub.5 573 VY 100 52 24 Ph (CH.sub.2).sub.3 OCH.sub. 3
C.sub.2 H.sub.5 Cl COH 574 VY 81 23 25 Ph (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3
576.sup.a -- -- -- 26 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5 Cl COH 606.sup.a -- -- -- 27 Ph (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 CH.sub.3 CN 582.sup.a MIX 91
64 28 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Cl C
OH 633 MIX 91 60 29 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
(CH.sub.2).sub.3 OCH.sub.3 Cl CHC(CN)COOC.sub.4 H.sub.9 644 EC 130 76
30 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl COH
601 EC* 94 73 31 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 C.sub.2
H.sub.5 Cl CHC(CN)COOC.sub.4 H.sub.9 653 MIX 106
46 32 Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3
OCH.sub.3 Cl CHC(CN)COOC.sub.4 H.sub.9 648 MIX 122
67 33 Ph (CH.sub.2).sub.2 O[(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2
H.sub.5 CH.sub.3 CN 581.sup.a -- -- -- 34 Ph (CH.sub.2).sub.2
O[(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CN
583.sup.a -- -- -- 35 Ph CH.sub.2 [(CH.sub.2).sub.2 O] .sub.2 CH.sub.3
C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 575.sup.a -- -- -- 36 Ph
CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 C
COOH.sub.3 575.sup.a -- -- -- 37 Ph CH.sub.2 [(CH.sub.2).sub.2 O].sub.2
C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 575.sup.a --
-- -- 38 Ph-4-OCH.sub.3 C.sub.2 H.sub.5 R.sup.2 COOC.sub.2 H.sub.5
COOC.sub.2 H.sub.5 591 EC 120 50 39 Ph-3-SO.sub.2 N(CH.sub.3).sub.2
C.sub.2 H.sub.5 R.sup.2 Cl COH 595 -- -- -- 40 Ph-3-SO.sub.2
N(CH.sub.3).sub.2 (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 Cl COH 596 -- --
-- 41 Ph-3-SO.sub.2 N[(CH.sub.2).sub.2 OCH.sub.3 ].sub.2 C.sub.2 H.sub.5
R.sup.2 CH.sub.3 COOCH.sub.3 586-- -- -- 42 CH.sub.2 Ph (CH.sub.2).sub.2 O
C
H.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 540.sup.a VY 94 51 43 CH.sub.2 OPh
C.sub.2 H.sub.5 R.sup.2 CH.sub.3 CN 543.sup.a MIX 88 72 44 Thien-3-yl
C.sub.2 H.sub.5 R.sup.2 CH.sub.3 COOCH.sub.3 582.sup.a -- -- -- 45
Thien-2-yl C.sub.2 H.sub.5 R.sup.2 COOC.sub.4 H.sub.9 COOC.sub.4 H.sub.9
600 MIX 94 80 46 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5
CH.sub.3 COOC.sub.2
H.sub.5 597.sup.a -- -- -- 47 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2 CH.sub.3 CN 599 -- -- -- 48 Thien-2-yl (CH.sub.2).sub.2
OCH.sub.3 R.sup.2 CH.sub.3 COOCH.sub.3 589 -- -- -- 49 Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3 R.sup.2 Cl COH 631 -- -- -- 50 Thien-3-yl
(CH.sub.2).sub.3 OCH.sub.3 C.sub.2
H.sub.5 CH.sub.3 COOCH.sub.3 583.sup.a -- -- -- 51 Thien-2-yl (CH.sub.2)
.sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOC.sub.2 H.sub.5 598.sup.a
-- -- -- 52 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 Cl COH
638.sup.a -- -- -- 53 Thien-2-yl (CH.sub.2).sub.2
O(CH.sub.2)hd 2OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 COOCH.sub.3 599.sup.a
-- -- -- 54 Thien-2-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3
C.sub.2
H.sub.5 Cl COOH 639.sup.a -- -- -- 55 Thien-2-yl (CH.sub.2).sub.2
O(CH.sub.2)hd 2OCH.sub.3 C.sub.3 H.sub.7 Cl COOH 636 MIX 91 59 56
Thien-3-yl (CH.sub.2).sub.2 O(CH.sub.2)hd 2OCH.sub.3 C.sub.3 H.sub.7 Cl
COOH 619.sup.a -- -- -- 57 Furan-2-yl C.sub.2 H.sub.5 R.sup.2 CH.sub.3
CN 605.sup.a -- -- -- 58 Furan-2-yl C.sub.2 H.sub.5 R.sup.2 CH.sub.3
COOCH.sub.3 596.sup.a -- -- -- 59 Furan-2-yl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2 CH.sub.3 COOCH.sub.3 594.sup.a -- -- -- 60 Furan-2-yl (CH.sub.2).
sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Cl COH 635.sup. a --
-- -- 61 Pyrid-3-yl C.sub.2 H.sub.5 R.sup.2 Cl COH 599.sup.a -- --
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
*weight ratio of binder:dye 2:1
TABLE 3a
__________________________________________________________________________
IIIc
##STR21##
.DELTA.E.sub..
tau.
.lambda..sub.max
T* [kJ/
Ex.
R.sup.1 R.sup.2 R.sup.3
R.sup.8
R.sup.9 R.sup.10
[nm]
B .degree.C.]
mol]
__________________________________________________________________________
62 Ph CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
Cl COOCH.sub.3
COH 598.sup.a
-- -- --
63 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3
COO CH.sub.3
CN 577
VY 82
32
64 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Cl COOCH.sub.3
COH 611.sup.a
-- -- --
65 Ph (CH.sub.2).sub.3 OCH.sub.3
R.sup.2
CH.sub.3
COOC.sub.2 H.sub.5
CN 562.sup.a
-- -- --
66 Ph (CH.sub.2).sub.3 OCH.sub.3
C.sub.3 H.sub.7
CH.sub.3
COOC.sub.2 H.sub.5
CN 589.sup.a
-- -- --
67 Ph-4-OCH.sub.3
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2
CH.sub.3
COOC.sub.2 H.sub.5
CN 567
VY 107
59
68 Thien-2-yl
CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
CH.sub.3
COOC.sub.2 H.sub.5
CN 577
VY 105
45
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 4
__________________________________________________________________________
##STR22## IIIe
.DELTA.E.sub..
tau.
.lambda..sub.max
T* [kJ/
Ex. R.sup.1
R.sup.2 R.sup.3
R.sup.8 R.sup.10 [nm]
B [.degree.C.]
mol]
__________________________________________________________________________
69 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
H NO.sub.2 595.sup.a
-- -- --
70 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
Cl COH 581
-- -- --
71 Ph
(CH.sub.2).sub.2 CH.sub.3
R.sup.2
Cl CHC(CN) COOC.sub.4 H.sub.9
637
VY 130
52
72 Thien-
C.sub.2 H.sub.5 R.sup.2
Cl CHC(CN)COOC.sub.4 H.sub.9
631
VY 125
67
3-yl
73 Thien-
C.sub.2 H.sub.5 R.sup.2
COOCH.sub.3
CN 581
-- -- --
2-yl
74 Thien-
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H NO.sub.2 626
-- -- --
2-yl
75 Thien-
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
Cl COH 593
-- -- --
3-yl
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 5
__________________________________________________________________________
##STR23## IIIg
.DELTA.E.sub..
tau.
.lambda..sub.max
T* [kJ/
Ex.
R.sup.1 R.sup.2 R.sup.3
R.sup.8 R.sup.9
[nm]
B [.degree.C.]
mol]
__________________________________________________________________________
76 CH(CH.sub.3)CH.sub.3
C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 522
EC*
63 69
77 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
CH.sub.3 CN 520
MIX
85 97
526.sup.a
VY 75 34
78 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
Ph CN 529
VY 89 24
79 Cyclohexyl C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 528.sup.a
-- -- --
80 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 CN 521
VY 75 42
81 Cyclohexyl (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph CN 524
MIX
100
80
82 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3 CN 523
VY 72 38
83 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 520
VY 75 37
84 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Ph CN 529
VY 84 44
85 Cyclohexyl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
(CH.sub.2).sub.2 OCH.sub.3
CN 524
VY 72 33
86 Cyclohexyl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
R.sup.2
Thien-2-yl
CN 587.sup.a
-- -- --
87 Cyclohexyl CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.3 H.sub.7
Ph CN 531
VY 88 38
88 Ph C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 548
VY 89 53
89 Ph C.sub.2 H.sub.5 R.sup.2
Ph-4-SPh CN 556
EC 118
53
90 Ph-3-OCH.sub.3
C.sub.2 H.sub.5 R.sup.2
Thien-2-yl
CN 572
-- -- --
91 Ph-3-SO.sub.2 N(CH.sub.3).sub.2
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
(CH.sub.2).sub.3 OCH.sub.3
CN 548
EC*
89 32
92 CH.sub.2 OPh
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 CN 531.sup.a
-- -- --
93 Furan-2-yl C.sub.2 H.sub.5 R.sup.2
CH.sub.3 CN 578.sup.a
-- -- --
94 Furan-2-yl C.sub.2 H.sub.5 R.sup.2
(CH.sub.2).sub.2 OCH.sub.3
CN 578.sup.a
-- -- --
95 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
CH(CH.sub.3)CH.sub.3
CN 579.sup.a
-- -- --
96 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 581.sup.a
-- -- --
97 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3
C.sub.3 H.sub.7
C.sub.2 H.sub.5
CN 581.sup.a
-- -- --
98 Thien-3-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
CH.sub.3 CN 562.sup.a
-- -- --
99 Thien-2-yl CH.sub.2 [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN 582.sup.a
-- -- --
100
Thien-2-yl CH.sub.2 [CH.sub. 2).sub.2 O].sub.2 CH.sub.3
C.sub.3 H.sub.7
C.sub.2 H.sub.5
CN 580.sup.a
-- -- --
101
CH(CH.sub.3)CH.sub.3
C.sub.2 H.sub.5 R.sup.2
CH.sub.3 SCN 512
EC 87 99
102
Ph C.sub.2 H.sub.5 R.sup.2
CH.sub.3 SCN 540
-- -- --
103
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
CH.sub.3 SCN 538
EC 90 57
104
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2 CH.sub.3
SCN 562 EC 88 47
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
*weight ratio of binder:dye = 2:1
TABLE 6
__________________________________________________________________________
##STR24## IIIh
Ex.
R.sup.1 R.sup.2 R.sup.3
X X' .lambda..sub.max [nm]
__________________________________________________________________________
105
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H 573.sup.a
106
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl H 579.sup.a
107
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
H H 574.sup.a
108
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
NO.sub.2
H 629.sup.a
109
Ph-4-O CH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl N 594.sup.a
110
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
H H 594.sup.a
111
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Cl H 602.sup.a
112
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
H H 597.sup.a
113
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
Cl H 605.sup.a
114
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2
Cl H 606.sup.a
115
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5
H H 598.sup.a
116
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
Cl H 598.sup.a
117
Thien-2-yl
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
H Cl 606.sup.a
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 7
__________________________________________________________________________
##STR25## IIIi
Ex.
R.sup.1
R.sup.2 R.sup.3
Y .lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau. [kJ/mol]
__________________________________________________________________________
118
CH.sub.3
C.sub.2 H.sub.5 R.sup.2
CN 591 EC*
130 44
119
Ph C.sub.2 H.sub.5 R.sup.2
H 583 -- -- --
120
Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3
C.sub.3 H.sub.7
CN 622.sup.a
-- -- --
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide glacial acetic acid
*weight ratio of binder:dye = 2.1
TABLE 8
__________________________________________________________________________
##STR26## IIIk
Ex.
R.sup.1
R.sup.2 R.sup.3
R.sup.8
.lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau. [kJ/mol]
__________________________________________________________________________
121
PH C.sub.2 H.sub.5
R.sup.2
Ph 531 EC 94 68
122
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 533.sup.a
-- -- --
123
Cyclohexyl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 508.sup.a
-- -- --
124
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2
Ph 556.sup.a
-- -- --
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
TABLE 9
__________________________________________________________________________
##STR27## IIIl
Ex.
R.sup.1
R.sup.2 R.sup.3
R.sup.8 .lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau.
[kJ/mol]
__________________________________________________________________________
125
Ph C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
535 EC 110 72
126
Ph C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 CN
536 EC 103 47
127
Ph C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 533 -- -- --
128
Ph C.sub.2 H.sub.5
R.sup.2
CH.sub.3 524 -- -- --
129
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
535 MIX
87 71
130
Cyclohexyl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
519.sup.a
-- -- --
131
Cyclohexyl
C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 518.sup.a
-- -- --
132
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 COOCH.sub.3
558 VY 93 61
133
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
S(CH.sub.2).sub.2 CN
560 EC 105 42
134
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
SCH.sub.3 557 EC 126 62
__________________________________________________________________________
.sup.a solvent 9:1 dimethylformamide/glacial acetic acid
*weight ratio of binder:dye = 2:1
TABLE 10
__________________________________________________________________________
##STR28## IIIm
Ex.
R.sup.1
R.sup.2
R.sup.3
R.sup.18
R.sup.19
.lambda..sub.max [nm]
B T*[.degree.C.]
.DELTA.E.sub..tau. [kJ/mol]
__________________________________________________________________________
135
Ph C.sub.2 H.sub.5
R.sup.2
CN Ph 567 MIX
106 37
136
Thien-2-yl
C.sub.2 H.sub.5
R.sup.2
CONH.sub.2
CH.sub.3
573 -- -- --
__________________________________________________________________________
3 TABLE 11
##STR29##
IIIg
Ex. R.sup.1 R.sup.2 R.sup.3 R.sup.8 R.sup.9 Hue 137 P
h (CH.sub.2).sub.2
OCH.sub.3 R.sup.2 CH.sub.3 H red 138 Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2 CH.sub.3 Cl red 139 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2
CH.sub.3 Br red 140 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 CN
violet 141 Ph (CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH.sub.3 SCN violet 142 P
h (CH.sub.2).sub.2 OCH.sub.3 R.sup. 2 C.sub.2 H.sub.5 CN violet 143 Ph
(CH.sub.2).sub.2 OCH.sub.3 R.sup.2 CH(CH.sub.3)CH.sub.3 CN violet 144 Ph (
CH.sub.2).sub.2 OCH.sub.3 R.sup.2 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN
bluish red 145 Ph (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3
CH.sub.3 SCN violet 146 Ph (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 Ph CN violet 147 Ph (CH.sub.2).sub.2
OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN
violet 148 Ph (CH.sub.2).sub.2 OCH.sub.3 C.sub.2
H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 149 Ph (CH.sub.2).sub.3
OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3
CN violet 150 Ph (CH.sub.2).sub.3 OC.sub.2
H.sub.5 CH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 CN violet 151 Ph (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 (
CH.sub.2).sub.2 OCH.sub.3Ph CN violet 152 Ph (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3Ph CN violet 153
Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph CN
violet 154 Ph [(CH.sub.2).sub.2 O].sub.2
CH.sub.3 CH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 CN violet 155 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2
H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 156 Ph [(CH.sub.2).sub.2
O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 Ph CN violet
157 Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.3 CH.sub.3 Ph
CN violet 158 Ph-4-Cl (CH.sub.2).sub.2
OCH.sub.3 R.sup.2 (CH.sub.2).sub.2 OCH.sub.3 CN violet 159 Ph-4-Cl
[(CH.sub.2).sub.2 O].sub.2 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2
OCH.sub.3 CN violet 160 Ph-4-OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3
C.sub.2 H.sub.5 CH.sub.3 CN violet 161 Ph-4-OCH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN violet 162
Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 CH.sub.3 SCN violet 163
Thien-2-yl (CH.sub.2).sub.2 O CH.sub.3R.sup.2 CH.sub.3 CN reddish blue
164 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C.sub.2 H.sub.5 CN
reddish blue 165 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C.sub.3
H.sub.7 CN reddish blue 166 Thien-2-yl (CH.sub.2).sub.2 OCH.sub.3R.sup.2 C
H(CH.sub.3)CH.sub.3 CN reddish blue 167 Thien-2-yl (CH.sub.2).sub.3
OCH.sub.3R.sup.2 (CH.sub.2).sub.2 OCH.sub.3 CN navy 168 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3R.sup.2 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 CN
navy 169 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 CH.sub.3 SCN reddish blue 170 Thien-2-yl (CH.sub.2).sub.3
OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph CN reddish blue 171 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Ph SCN reddish
blue 172 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 CN navy 173 Thien-2-yl (CH.sub.2).sub.3
OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OC.sub.2 H.sub.5
CN navy 174 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2
OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 175 Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.2 OC.sub.2 H.sub.5 Thien-2-yl
CN blue 176 Thien-2-yl (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5
(CH.sub.2).sub.2 OCH.sub.3 CN navy 177 Thien-2-yl (CH.sub.2).sub.3
OC.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Thien-3-yl CN blue 178
Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5 (CH.sub.2).sub. 3 OCH.sub.3 (
CH.sub.2).sub.2 OCH.sub.3 CN navy 179 Thien-2-yl (CH.sub.2).sub.3
OC.sub.2 H.sub.5 (CH.sub.2).sub.2
OCH.sub.3
##STR30##
CN reddish blue 180 Thien-2-yl (CH.sub.2).sub.3 OC.sub.2 H.sub.5
(CH.sub.2).sub.2 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 181
Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5
CH.sub.3 SCN bluish violet 182 Thien-2-yl (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Ph CN reddish blue 183
Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5
(CH.sub.2).sub.2 OCH.sub.3 CN navy 184 Thien-2-yl (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.2 H.sub.5 Thien-2-yl CN blue 185
Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7
CH(CH.sub.3)CH.sub.3 CN navy 186 Thien-2-yl (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 Ph CN reddish blue 187
Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7
(CH.sub.2).sub.2 OCH.sub.3 CN navy 188 Thien-2-yl (CH.sub.2).sub.3
O(CH.sub.2).sub.2 OCH.sub.3 C.sub.3 H.sub.7 (CH.sub.2).sub.2 OC.sub.2
H.sub.5 CN navy 189 Thien-2-yl (CH.sub.2).sub.3 O(CH.sub.2).sub.2
OC.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.2 OCH.sub.3 CN navy 190
Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.2
O CH.sub.3 Thien-2-yl CN reddish blue 191 Thien-2-yl [(CH.sub.2).sub.2
O].sub.2 CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Thien-3-yl CN blue 192
Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3 (CH.sub.2).sub.3
OCH.sub.3 Ph CN reddish blue 193 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2
CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.2
OCH.sub.3 CN navy 194 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5 Thien-3-yl CN blue 195 Thien-2-yl [(CH.sub.2).sub.2
O].sub.2 CH.sub.3 C.sub.3 H.sub.7 (CH.sub.2).sub.2 OCH.sub.3 CN navy 196
Thien-2-yl [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3
OCH.sub.3 Ph CN reddish blue 197 Thien-2-yl [(CH.sub.2).sub.2 O].sub.2
C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.3 Pyrid-3-yl CN reddish blue
198 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 (CH.sub.2).sub.3
OCH.sub.3 Ph CN reddish blue 199 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3
CH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 Thien-2-yl CN reddish blue 200
Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 (CH.sub.2).sub.2
OCH.sub.3 Thien-3-yl CN reddish blue 201 Thien-2-yl [(CH.sub.2).sub.2
O].sub.3 CH.sub.3 C.sub.2 H.sub.5 Ph CN reddish blue 202 Thien-2-yl
[(CH.sub.2).sub.2 O].sub.3 CH.sub.3 C.sub.2 H.sub.5 Thien-2-yl CN blue
203 Thien-2-yl [(CH.sub.2).sub.2 O].sub.3 CH.sub.3 C.sub.2 H.sub.5
Thien-3-yl CN blue
TABLE 12
__________________________________________________________________________
##STR31## IIII
Ex.
R.sup.1 R.sup.2 R.sup.3 R.sup.8 Hue
__________________________________________________________________________
204
Ph (CH.sub.2).sub.2 OCH.sub.3
R.sup.2 SCH.sub.3 reddish violet
205
Ph (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SCH.sub.3 violet
206
Ph (CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
violet
207
Ph [(CH.sub.2).sub.2 O].sub.2 CH.sub.3
Ph SCH.sub.3 violet
208
Ph [(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
Ph SCH.sub.3 violet
209
Ph-4-OCH.sub.3
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SCH.sub.3 violet
210
Thien-2-yl
(CH.sub.2).sub.2 OCH.sub.3
R.sup.2 SCH.sub.3 reddish blue
211
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
R.sup.2 SCH.sub.3 reddish blue
212
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OCH.sub.3
SC.sub.2 H.sub.5 reddish blue
213
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 OC.sub.2 H.sub.5
SCH.sub.3 bluish violet
214
Thien-2-yl
(CH.sub.2).sub.3 OCH.sub.3
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
bluish violet
215
Thien-2-yl
(CH.sub.2).sub.3 OC.sub.2 H.sub.5
C.sub.2 H.sub.5
S(CH.sub.2).sub.2 COOCH.sub.3
bluish violet
216
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 CH.sub.3
C.sub.2 H.sub.5
SCH.sub.3 bluish violet
217
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
(CH.sub.2).sub.3 OCH.sub.3
SCH.sub.3 bluish violet
218
Thien-2-yl
[(CH.sub.2).sub.2 O].sub.2 C.sub.2 H.sub.5
C.sub.2 H.sub.5
SCH.sub.3 bluish
__________________________________________________________________________
violet
Claims
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: R.sup.1 is hydrogen;
- C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy or halogen;
- phenyl, phenyl substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy, sulfonamido or halogen;
- thienyl, thienyl substituted by C.sub.1 -C.sub.5 -alkyl or halogen; furanyl or pyridyl;
- a radical of the formula II
- W is identical or different C.sub.2 -C.sub.6 -alkylene,
- n is from 1 to 6 and
- R.sup.4 is C.sub.1 -C.sub.4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy;
- R.sup.2 and R.sup.3 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, C.sub.1 -C.sub.4 -alkylphenyl, C.sub.1 -C.sub.4 -alkoxyphenyl, halophenyl, benxyloxy, C.sub.1 -C.sub.4 -alkylbenzyloxy, C.sub.1 -C.sub.4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano;
- cyclohexyl, cyclohexyl substituted by C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkoxy or halogen;
- phenyl, phenyl substituted by C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkoxy, benzyloxy or halogen;
- a radical of the above-mentioned formula II; and
- D is the radical of a diazo component III.
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: R.sup.1 on is hydrogen;
- C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkyl substituted by phenyl or phenoxy; cyclohexyl, cyclohexyl substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy or halogen;
- phenyl, phenyl substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy, sulfonamido or halogen;
- thienyl, thienyl substituted by C.sub.1 -C.sub.5 -alkyl or halogen; furanyl or pyridyl;
- a radical of the formula II
- where
- W is identical or different C.sub.2 -C.sub.6 -alkylene,
- n is from 1 to 6 and
- R.sup.4 is C.sub.1 -C.sub.4 -alkyl, phenyl or benzyl; phenyl or benzyl substituted by C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy;
- R.sup.2 and R.sup.3 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, C.sub.1 -C.sub.4 -alkylphenyl, C.sub.1 -C.sub.4 -alkoxyphenyl, halophenyl, benzyloxy, C.sub.1 -C.sub.4 -alkylbenzyloxy, C.sub.1 -C.sub.4 -alkoxybenzyloxy, halogenzyloxy, halogen, hydroxyl or by cyano;
- cyclohexyl, cyclohexyl substituted by C.sub.1 -C.sub.15 -alkyl, C.sub.1 -C.sub.15 -alkoxy or halogen;
- phenyl, phenyl substituted by C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.5 -alkoxy, C.sub.1 -C.sub.15 -alkoxy, benzyloxy or halogen;
- a radical of the above-mentioned formula II; and
- D is the radical of a diazo component III
3. A process as claimed is claim 2, wherein the azo dye or dyes has the formula Ia ##STR34## where the substituents have the following meanings: R.sup.1 is C.sub.1 14 C.sub.8 -alkyl, C.sub.1 -C.sub.8 -alkyl substituted by phenyl or phenoxy;
- cyclohexyl;
- phenyl, phenyl substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or chlorine;
- thienyl;
- a radical of the formula IIa ##STR35## where p is 0 or 1, q is from 1 to 4, and
- R.sup.4' is C.sub.1 -C.sub.4 -alkyl, phenyl or benzyl;
- R.sup.2' and R.sup.3' are each C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.10 -alkoxy or C.sub.1 -C.sub.10 -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.
| 0192435 | August 1986 | EPX |
| 275381 | July 1988 | EPX |
| 239291 | November 1985 | JPX |
- Derwent Japanese Patents Report, vol. 79, No. 46, 14 Dec. 1979, London, GB, Seite 2 Canon K.K.: "Heat-Sensitive Sheet for Latent Image Production". Patent Abstracts of Japan, vol. 10, No. 109 (M-472) (2166), 23 Apr. 1986.
Type: Grant
Filed: Dec 14, 1993
Date of Patent: Mar 14, 1995
Assignee: BASF Aktiengesellschaft (Ludwigshafen)
Inventors: Volker Bach (Neustadt), Karl-Heinz Etzbach (Frankenthal), Sabine Gruettner (Mutterstadt), Gunther Lamm (Hassloch), Helmut Reichelt (Neustadt), Ruediger Sens (Mannheim)
Primary Examiner: B. Hamilton Hess
Law Firm: Oblon, Spivak, McClelland, Maier, & Neustadt
Application Number: 8/166,103
International Classification: B41M 5035; B41M 538;
