CA1283660C - Dyes for sublimation heat-sensitive transfer recording - Google Patents

Abstract

Abstract of Disclosure A dye for heat-sensitive transfer recording which is of the general formula:

wherein -B represents , , , , , , , , or , -Z1 and -Z2 each represents hydrogen, alkyl optionally substituted by fluorine, alkoxy, halogen or -NHB, K represents , , , , , , , , or

Description

~213;~

TITLE OF THE INVENTION

DYES FOR SUBLIMATION ~EAT-SEWSITIVE TRANSFER RECORDING

BACRGROUND OF THE INVENTION

Field of the Invention This invention relates to dyes for use in sublimation heat-sensitive transfer recording.

' Description of th Prior Art Heretofore, techniques for color recording facsimile printers, ; copying machines, television images etc. have been sought, and color recording techniques by electron photography, ink-jet process, heat-sensitive transfer etc. have been under .
study The heat-sensitive transfer recording process is considered more advantageous as compared with other processes since the maintenance and operation of the device are easier and the device and expendable supplies are less expensive.

The heat-sensitive transfer process is roughly classified into two processes, that is, a molten heat-sensitive transfer recording process which comprises heating a transfer sheet having a heat-melting ink layer formed on a base film by a ~33~

heat-sensitive head to melt said ink thereby transfer record ing onto a recording body, and a sublimation heat-sensitive trans~er recording process which comprises heating a transfer sheet having an ink layer containing a sublimable dye formed on a base film to sublime the dye thereby transfer recording onto a recording body.

And, said sublimation heat-sensitive transfer recording process is believed suitable for full color recording since it is possible to control the amount of the dye to be sublimed and transferred by controlling the energy applied to the heat-sensitive head and hence gradation expression is easy.

In general, full color recording is conducted by using tricolor dyes, that is, a cyan color dye, a magenta dye and a yellow color dye, and sometlmes, four color dyes, that is, these three plus a black color dye, but in order to obtain full color recording having good color reproducibility, the follo~l-ing requirements must be satisfied: the respective dyes easily sublime under the operational conditions of the heat-sensitive recording head, do not undergo thermal decomposition under the operational conditions of the heat-sensitive recording head, have preferred hues for color reproduction, have great molecu-lar absorption coefficients, are stable against light, mois-ture, chemicals etc., are easily synthesized, have excellent adaptability to inks, etc.

. ~ , .

However, no conventional cyan dye has satisEied the above requirements.
Accordingly, this invention aims to provide cyan color dyes which fulfill such requirements that they easily sublime under the operational conditions of the heat-sensitive recording head, do not ~ndergo thermal decomposition under the operational conditions of the heat-sensitive recording head, are stable against light, are easily synthesized, are readily and uniformly dissolved or dispersed to prepare an ink of a high concentration, etc.
: The present invention provides in a dye for heat-sensitive transfer recording which is oE the general formula [I]:

N~B

O = ~=~ = N - K
..--- [I]

\z2 wherein -B represents O O O O
-C-Rl , -C-~ -C ~ , -CO-R

-CNH-Rl, -co-Rl, -CNH-Rl, -S-Rl, -CN~ 2 , -CN~ 2 or 33~

-SN , _zl and -Z each represents hydrogen, alkyl optionally Il \R2 substituted by fluorine, alkoxy, halogen or -NHB, K represents X ~ l6 R l6 Y Y ~NHR6 N~ S02 ~ --~N ~O ~ ~

` ~ X R3 ~ 6 - ~ ~ X ~ X

-R1, -R2, _R6 and -R7 each represents hydrogen, C1 - C8 substitut-ed or unsubstituted alkyl, substituted or unsubstituted vinyl, allyl or aryl, -R3, -R4 and -R5 each represents hydrogen or methyl, -X represents hydrogen, alkyl optionally substituted by fluorine, alkoxy, formylaminol alkylcarbonylamino optionally substituted by fluorine, arylcarbonylamino or halogen, and -Y represents hydrogen, alkyl optionally substituted by fluorine, alkoxy or halogen.

The optionally fluorine-substituted alkyl as zl and Z
is a lower alkyl, such as, methyl and ethyl.
The alkoxy as a substituent of the optionally substituted ' ~;283~
- 4a - 70691-3 alkyl as zl and z2 is a lower alkoxy such as methoxy and ethoxy.
The possible substituents of the substituted Cl - C8 alkyl as -R , -R , _R6 and -R include lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy and phenoxy.
The possible substituents of the substituted vinyl as -Rl, -R2, _R6 and -R7 include methyl and halogen, such as bromine.
The aryl as -Rl, -R2, _R6 and -R is for example phenyl.
The optionally fluorine-substituted alkyl as -X is a lower alkyl optionally substituted by fluorine such as methyl and trifluoromethyl.
The alkoxy as -X is a lower alkoxy group such as methoxy.
The optionally fluorine substituted alkylcarbonylamino as -X is a lower alkylcarbonylamino optionally substituted by fluorine such as formylamino, acetylamino, propionylamino and trifluoroacetylamino.
The arylcarbonylamino as -X is for example phenylcarbonyl (= benzoyl)amino.
The optionally fluorine-substituted alkyl for -Y is a lower alkyl group optionally substituted by fluorine such as methyl and trifluoromethyl.
The alkoxy for -Y is a lower alkoxy group such as methoxy.
The descriptions of the eleven paragraphs immediately above are also applied to corresponding symbols where present in formulae [II] through [IX] mentioned hereinunder.

6~
- 4b - 70~91-3 The present invention also provtdes a method of sublimation heat~sensitive transfer recording, which method comprises heating a transfer sheet having an ink layer containing a sublimable dye coated on a base film to sublime the dye thereby transfer recording onto a recording body, whereln the said dye is of the formula lI]-The present invention further provides a sublimationheat-sensitive transfer recording sheet, which comprises an ink layer containing a heat-sensitive sublimable dye coated on a base film, wherein the said dye ls o~ the formula ~I].
The present invention still further provides a process for producing a subllmation heat-sensitive transfer recording sheet, which process comprises: a) dissolving a heat-sensitive sublimable dye in a medium or dispersing the dye in a f:Lne particle form in a medium together with a binder to prepare an ~ ink, and b) coating the ink on a base film and drying the coating, :
~ wherein the said sublimable dye is of the formula II].
D

~L2:~33~

Of the dyes for heat-sensitive transfer recording of the above general formula ~I] of this invention, those of the general formulae ~II] ~ [IX] shown below are preferred dyes for heat-sensitive transfer recording.

NHCOR8 yl ( i ) o=b=N~N~R10 ......................... ~II]

:: Xl wherein -Xl represents hydrogen, methyl, methoxy, formylamino, acetylamino, propionylamino, chlorine, bromine, iodine or fluorine, _yl represents hydrogen, methoxy, ethoxy, chlorine, bromine, iodine, fluorine or methyl, and -R8, -R9 and -R10 each represents hydrogen, Cl - C8 substituted or unsubstituted ~; alkyl, allyl or aryl;

: NHBl y (ii) O= ~ =N ~ -N/ .....
Z3 z4 X

wherein -X, -Y, -R9 and -R10 are as defined above, -Bl repre-O O O S
sents 11 ~3 -C-~, _co_Rll, _cNH-Rll, -CO-Rll, 3~

S o o S o Il 11 11 11 11 , Rll 11 , Rll 11 , R
-CNH-R , -S-R ,~CN~ 12' CN ~R12 11 ~ R12 O O

-Z3 and -Z4 each represents hydrogen, alkyl optionally substi-tuted by fluorine, alkoxy or halogen, and -Rll and -R12 each represents Cl - C8 substituted or unsubstituted alkyl or aryl.

In the above general formula [III], examples of the substitu-ents for the substituted alkyl include alkoxy, hydroxy, aryl etc. Of the dyes of the above general formula [III], espe-cially preferred are those wherein -X, -Y, -Z3 and -Z4 are each hydrogen, methyl, methoxy, ethoxy, chlorine, bromine or trifluoromethylr -R9 and -RlO are each hydrogen, hydroxyalkyl, aralkyl or Cl - C6 alkyl, _B1 is II O-R11 -IINHR11 S O 11 ~ Rll 11 ~ Rll 11 ~ Rll _CNHRll, -S-Rll , -CN , -CN or SN~ Rl2' O O

and -Rll and -Rl~ are each Cl - C4 alkyl.

(iii) O= ~ =N ~ N~ lO . [IV]

z5z6 X

wherein -X -Y, -R8, -R9 and -R10 are as defined above, and -Z5 and _z6 each represents hydrogen~ or alkyl optionally substituted by fluorine, alkoxy or halogenO
In the above general formula [IV], examples of the sub-stituents for the substituted alkyl represented by -R8, -R9 and -R10 include alkoxy, alkoxyalkoxy, aryl, aryloxy, tetrahydro-furyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, hydroxy, cyano, halogen etc. Of the dyes of the above general formula [IV], especially preferred are those wherein -X and -Y are each hydrogen, methyl, methoxy, ethoxy, chlorine, bromine or tri-fluoromethyl, -Z5 and _z6 are each methyl, methoxy, ethoxy, chlorine, bromine or trifluoromethyl, -R8 is Cl - C6 alkyl, tri-fluoromethyl, perfluoroethyl or perfluoropropyl, and -R9 and -R10 are each hydrogen, hydroxyalkyl, aralkyl or Cl - C6 alkyl.

~:~ NHB

(iv) 0 = ~ ~= N - K ..... [V~

Z Z

wherein _zl and _z2 are as defined above, _s2 represents O O O O O S
~C-R13, -C- ~ It ~ _IO_R13, -cNH-Rl3~ ~CO_R13, ~8~6~;~

Il 13 1l 13 _¦¦ R13 1l ~R13 ll ~ R13 -CNH-R , -S-R , \R14 \R14 or 11 \R14 ' _Kl represents ~ ~ R4 ~ ~ ~/ ~ , X ¦ R5 X N ' :~ R R15 X ~ 2 ~ N O ~ WHR15 ~ NHR15 ; l ~ or - ~ - N ~ _R13, -R14 and -R

each represents hydrogen, or Cl - C8 substituted or unsubstituted : alkyl.
In the above general formula [V], examples of the sub-stituents for the substituted alkyl represented by -R13, -R14 and _~15 include halogen, vinyl, alkoxy etc. Of the dyes of the above general for~ula [V~, especially preferred are those O O O S
wherein ~B2 is -C-R13, -Co-R13~ -CNH-R13, -CNH-R13, -s-Rl3~ -CN ~ , -CN \ 1 or -SW ~ , _zl and _z2 O O

36~1) are each hydrogen, methyl, trifluoromethyl, methoxy, chlorine, O o o S
bromine, 11 11 11 11 -NHC-Rl 3, -NHco-Rl3, -NHCNH--R13, -NHCNH-R13 11 ~ R13 11 , R13 11 ~ R13 -NHS-R13, -NHCN , -NHCN or -NHSN
Il ~ R14 ~ R14 11 ~ R14 O O

_Kl is ~ 5 , ~ N~_~502 , ~ O or 4~--NHR15 ~ , -R13, -R14 and -R15 are each Cl - C6 alkyl, `: ~
: R
trifluoromethyl, perfluoroethyl or perfluoropropyl, -R3, -R4 :~ and -R5 are each hydrogen or methyl, and -X and -Y are each hydrogen, methyl, trifluoromethyl, methoxy, ethoxy, chlorine or bromine NHB2 y (v) O ~ ~ ~R16 .................................. [VI]

wherein -B2, -X and -Y are as defined above, -B3 is as defined for -B2, and -R16 and -R17 are each hydrogen or Cl - Cg _ g _ ~L-2E~3~

substituted or unsubstituted alkyl. In the above general formula ~VI], examples of the substituents for the substituted alkyl represented by -R13, -R14, -R16 and -R~-7 include halogen, alkoxy, vinyl, hydroxy, aryl etc. Of the dyes of the above general formula [VI], especially preferred are those wherein -X and -Y are each hydrogen, methyl, methoxy, ethoxy, chlorine, bromine or trifluoromethyl, -R16 and -R17 are each hydrogen, hydroxyalkyl, aralkyl or Cl C6 alkyl, -B2 and -B3 O O o S O
are each 1 ll 13 ll 13 ll 13 ll 13 -C-R 3, -CO-R , -CNH-R , -CNH-R , -S-R

-CN~ , -CN or -SN and -R13 and -R14 are R14 ~ R14 il R14 each Cl - C4 alkyl or halogenated alkyl.

NH-~_R18 yl ~vi) O= ~ =N ~ -N ..... ~VII]
z7 z8 X1 wherein _Xl, _yl~ -R9 and -R10 are as defined above, and -Z7 and _Z8 each represents hydrogen, alkyl optionally substituted by fluorine, alkoxy, halogen or -NH-A-R13 wherein -R18 repre-sents substituted or unsubstituted vinyl, and -A- represents -CO- or -COO-.

~283~

NH-A-Rl9 yl (vii) o = ~ =N ~ N~ ............................. ~VIII]

. z9 zlO Xl wherein _Xl, _yl and -A are as defined above, -Z9 and _zlO
each represents hydrogen, methyl, trifluoromethyl, methoxy, ethoxy, chlorine, bromine or -NH-A-Rl9 wherein -Rl9 represents hydrogen, Cl - C8 straight~chain or branched-chain alkyl, allyl, vinyl, methylvinyl, C3 - Cg alkoxyalkyl, aralkyl, cyclohexyl, thienyl, trifluoromethyl or aryl, and -R20 and -R2l each represents hydrogen, Cl - C8 straight-chain or branched-chain alkyl, C3 - C8 alkoxyalkyl, C2 - C4 hydroxy-alkyl, Cl - C8 halogenated alkyl, ~-cyanoethyl, alkenyl, methylalkenyl or tetrahydrofurfuryl.

N~-A_R22 y2 (viiil ~ ~ R23 .................................. [IX]
zll z12 x2 wherein -A- is defined above, -x2, _y2, _zll and _z12 each represents hydrogen, methyl, methoxy or chlorine, and -R22, -R23 and -R24 each represents Cl - C8 straight-chain or branched-chain alkyl or alkenyl.

~ ~8~

Further, the dyes for heat-sensitive transfer recording of this invention may be used in combination.

3~

The dyes for heat-sensitive transfer recording of the above general formula [I] of this invention may be produced by, for exampler the following process:-That is, a phenol of the following general formula [a]:

NHB

HO - ~ .... [a]

wherein -B, _zl and _z2 are as defined above and an aniline of the following general formula [b]:

H2N - K --- [b]

gl 2836Ç;S~

wherein -K is as defined above are heated in the presence of silver nitrate, thereby a dye for heat-sensitive transfer recording of the above general formula [I] of this invention may be produced.

For applying the dyes for heat-sensitive transfer recording of the above general formula ~I] of thls invention in the sublimation heat-sensitive transfer recording process, the dye may be dissolved, or dispersed in a fine particle form, in a medium together with a binder to prepare an ink, then said ink is coated on a base film and dried, thereby a transfer sheet i5 prepared.

As the binder for the preparation of the ink, there may be used water-soluble resins such as cellulosic type, acrylic acid type, starch type etc.; resins soluble in organic solvents, such as acrylic resins, methacrylic resins, poly-styrene, polycarbonates, polysulfones, polyether sulfones, ethyl cellulose etc.; and the like. ~n the case of the resin soluble in organic solvents, it may be used not only as a solution in an organic solvent but also in the form of an aqueous dispersion.

Examples of the medium for the preparation of the ink include, in addition to water, organic solvents, for example, alcohols such as methyl alcohol, isopropyl alcohol, isobutyl alcohol 33~

etc.; cellosolves such as methyl cellosolve, ethyl cello-solve etc.; aromatics such as toluene, xylene, chlorobenzene etc.; esters such as ethyl acetate, butyl acetate etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.; chlorine type solvents such as methylene chloride, chloroform, trichloroethylene etc.;
ethers such as tetrahydrofuran, dioxane etc., N,N-dimethyl-formamide, N-methylpyrrolidone etc.

As the base film for coating the ink for the preparation of the transfer sheet, tissue paper such as condenser paper, glassine paper etc. and a film of a plastic having good heat resistance, e.g. polyesters, polyamides, polyimides etc. are suitable, and the thickness of said base film is suitably in the range of 3 - 50 ~m.

As the method for coating the ink on the base film, it may be conducted by using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater etc., and the thickness of the ink coated layer after drying may suitably be in the range of 0.1 - 5 ~m (Yuji Harazaki, published from Maki Shoten in 1979, 'ICoating Method").

Since the dyes for heat-sensitive transfer recording of the above general formula [I] of this invention have a brilliant cyan color, they are suitable for obtaining full color ~2~3~

recording having good color reproducibility by combining with appropriate magenta and yellow color dyes, and ~urther since they easily sublime and have great molecular absorption coefficients, it is possible to obtain recording having a high color density at a high speed without imposing much burden on the heat-sensitive head~ Further, since they are stable against heat, light, mois-ture, chemicals etc., they do not undergo thermal decomposition during transfer recording and also the obtained recording has excellent storage stability. Furthermore, since the dyes of this invention are good in solubility in organic solvents and dispers-ibility in water, it is easy to prepare a uniformly dissolved or dispersed ink of a high concentration, and by using such an ink, a transfer sheet on which the dye has been uniformly coated at a high concentration may be obtained. Therefore, by using such a transfer sheet, recordins having excellent uniformity and color density may be obtained.

,. . ,.~
~' l~B3660 This invention is more particularly described by the : -Eollowing examples, but it should be noted that this invention be not restricted by these examples.

(i) Preparation of an Ink ' ; CH3 Above dye 10 g Polysulfone resin* 10 g Chlorobenzene 80 g Total 100 g * UDEL, P-1700 (trade mark) produced by Nissan Chemicals Industries, Ltd.

The mixture of the above composition was treated by a paint conditioner for 10 minutes to prepare an ink. The dye and the resin had been completely dissolved and thus it was possible :: 8 ~
--~ ......

~33~

to obtain an ink in a uniform solution.

(ii) Preparation of a Transfer Sheet The aforesaid ink was coated on a polyimide film (15 ~m thick) using a bar coater (produced by RK Print Coat Instrurnents Co~, No. 1) and dried in air, to obtain a transfer sheet.

(iii) Transfer Recording The ink coated surface of the aforesaid transfer sheet was overlapped with a recording body, and recording was effected using a heat-sensitive head under the following conditions thereby it was possible to ob-tain uniform brilliant cyan color recording having a high color density of 1.40.

Recording Conditions Linear density of main scanning and minor scanning: 4 dots/mm Recording electric power: 0.6 W/dot Heating time of the head: 10 m sec.

The recording body was produced by coating a liquid prepared by mixing 10 g of an aqueous dispersion of 34% by weight of a saturated polyester (produced by Toyo Spinning Co., Ltd., VYLONAL MD-1200, trade mark) and 1 g of silica (produced by Nippon Silica Industry Co., Ltd., Nipsil E220A, trade mark~) on a wood free paper sheet (200 ~m thick) using a bar coater (produced by RK Print Coat Instrurnents Co., No. 3) and there-after drying.

The color density was measured by using a densitometer Model RD-514 manufactured by Macbeth Co., U.S.A. (filter: latten No. 25).

A light fastness test was conducted on the obtained recording using a carbon arc fade-o-meter (manufactured by Suga Tester Co., Ltd.) at a black panel temperature of 63 ~ 2C to find that there was hardly decoloration or change in color after exposure to light for 40 hours.

The dye used in this example was produced as follows:

3.0 g of acetamidophenol of the following structural formula:

HO - ~

and 4.3 g of a compound of the following structural formula:
.
H2N ~ N~ . HCl were added to 150 ml of ethanol, stirred at room temperature, and then a solution of 3.4 g of silver nitrate in 15 ml of water was added dropwise. Thexeafter, 15 ml of a 28~ ammonia water was added thereto, further a solution of 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction ~33~iO

was effected at 30 - 40C for 3 hours. After completion of the reaction, it was extracted with chloroform, the solvent was distilled off, and the residue was purified by column chromatography, to obtain 5.2 g (yield 80~ based on the theoretical yield) of a purified product of an indoaniline type dye of the following structural formula:

~ b ~ ~C2H5 The dye thus obtained had a melting point of 128 - 130C and a maximum absorption wavelength (chloroform) of 656 nm.

::
Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in : Example 1 was replaced by the dyes set forth in Table 1 respectively, thereby brilliant cyan color recording having the color density set forth in Table 1 was obtained in each case.

-~83~0 Table No. Structural For~ula of the oye r ~sorption (Chloroform) Recording (nm) . . ,~ _ 2-1 b N ~ N `C2H5 1.40 636 _.............. ,~... ,~

2-2 ~ ~ ~ CH3 1.40 626 _ __ -.~ _ : NHCOCH3 2-3 O ~ N ~ N~ C3H7(n) 1.40 637 . _ ~ , _ 2-4 ~ b ~ C 6' ( ) ~ 1.40 ~ 638 . ,, , ,,. , , ~ ,_ b ~ ~ C H ( ) ~ 1.35 ~ 639 ~836g~[) 2- 6 ~ C6H13(n) 1.35 639 _ NHCOC2Hs ..
2- 7 b N ~ N~ C2H5 1.40 636 .

2- 8 ~ ~ ~ ,C3~l7(n~ 1.4G ~ 637 .... _~ _ _ __ NHCOC2H5 C H ( n) 2- 9= b =N ~ -N~ 4 9 1.40 638 . ~ C4Hg(n) 2-lG b ~ C2H5 1.4G 636 ~_ _. . .. ~
NHCOC4Hg(n) 2-11 b ~ ~ C2H5 1.40 636 _ _ 36~

NHCOC2H5 _ 2-12 = b =N ~ -N\ 1.40 656 _ . .
NHCOC3H7(n) 2-13 = b =N ~ -N~ 1.40 656 NHCOC4Hg(n) : 2-14 o=b=N~ N 1.40 656 _ _ NHCOC2H5 ~ C3 7 (n) 2-15 b ~ \ C3H7~n)1.40 657 .,~ . . _ __ :~ NHCOC2Hs 2~16 O ~ =N ~ -N~ C4H9(n) 1.35 658 ~ ~C4Hg~n) .

7 ~> ~ ~ C2H- I 1 ' ~X~3~

2-18 b CH3 1.35 632 2-19 b N~ N~ C2H5 1.40 632 F
_ . ~

2-20 N ~ Cl~ 1.30 660 . ......... _~.

2-21 ~ ~C2H5 1.30 658 NHCHO
. _....... .
~; NHCOCH3 2-22 = b =N ~ N~ C2H5 1.30 660 - . . . .

2-23 b N ~ N~ C2H5 1.35 632 , .

~X1~3366~

_ NHCOCH3 OCH3 2-24 b N ~ N~ C H 1.35 661 2-25 = b =N ~ N~ 1.35 657 2-26 ~ ~ ~ C2H5 1.35 658 ; _ _~ , __ NHCOCH3 Cl 2-27 = b =N ~ ~N~ 2 5 1.25 656 ; NHCOCH3 2-28 ~ ~ ~ C2H 1.25 675 ,C2}~5 ~ 1.40 630 .. ~ .

~.21336GO

2-30 b ~ ~ C 2 H 5 1.35 630 NHCOCH3 Br 2-31 b ~ ~ C 2H 5 1.35 630 _ .

, C2H40CH3 2-32 CE3 1.35 652 _ ~ _ _ 2-33 b ~ ~ C 2H40C2H5 1 . 35 633 2-34 O= ~ =N ~ -N 1.35 652 _ _ _ `c~E4oH 1.35 ~ 633 _ .

2-36 b N ~ N~ C2H4OCH3 1.30 626 ~=:/ c 2H40CH3 .__ _ _ .__ 2-37 = b =N ~ -N 1.30 651 ~=/ ~ C2H4oc2H4ocH3 ~ , _ : NHCOCH3 2~38 b N ~ N C2H5 1.25 620 ~ .

:~ 2-39= b =N ~ -N~ 1.30 625 ~/ ~ C 2H 4 Cl _ . .

~ , CH2CH=CH2 2-40 O= ~ =N~ N 1.40 633 ~=/ ~ C2H5 . . ._ ~r__.______________ _ 2-41 = b =N ~ -N~ 2 ~ 6 5 2 ~LZ~ 0 -~ , CH2CH=CH2 2-42O=~ ~=N~--N 1. 40 623 \=~ =/ CH2CH=CH2 _ ._ 2--43 b ~ ` C2Hs 1 ......... ~, 6 _. _ NHCOC2H4oc2H5 C H .
2- 4 4 =b ~3 ~ C 2H 5 1 . 3 5 6 3 6 __ __ . __ _ , _ 2--45 Ob=N~--N 1. 30 636 _ , _ I

2-4 6 o~b=N~--N 1 . 3 0 6 3 2 ,, __ _ NHCOCH2CH=CH2 2-47 Ob=N~--N 1. 40 633 ` C2H5 _ __ ~X1~3~

. . ~ , NHCOCH2- ~
2-48 b ~ ~ C2H5 1.30635 . _ _ _ _ _ _ 2-49= b =N ~ ~ CH2- ~ 1.30626 _ __ _ 2-50 b ~ C3H7(i) 1.40636 _.._ _ 2-51 b ~ ~ C2~5 1.30636 ~: ~ . .

~_ , C2H5 2-52O=~ ~=N ~ -N 1.30 630 ~ \=/ ~ C2H40COCH3 _ _ _ _, , .
: NHCOCH3 2-53 = b =N ~ -N' C2H5 1.30630 ~2H4COOCH3 36~

, ~ , . 2-54 b=N~ N~ C2H5 1~30 630 ... , _ ~

2-55 = b =N ~ N~ C2H5 1.30 631 2-56 O ~ =N ~ N~ C2H5 1.30 633 ~ C2H4C6H13(n) : . _ 2-57 O= ~ N ~ N~ C2H5 1.30 633 ~ CH2CHC2H5 ! OH
._ _ ¦ 2-58 ~ O ~N ~ N~ C21~5 1.20 ¦ 657 ._ . _ _ _ _ NHCO ~
2-59 = b =N ~ N 1 2 0 ~7D

lZ83G6[) ~ NHCOCH3 2-60 = b =N ~ -N ~ 1.20 620 . _ _ _ 2~61 b ~ ~ C2H5 1.40 634 _ , _ , 2-62 b ~ ~ CH3 1.40 625 . , __ _ _ _ _.__ NHCOC3F7 ~ C ~H 5 2-63 b ~ N~ C H5 1.40 653 . . . _ : NHCOC2F5 2-64 = b =N ~ N~ 1.40 653 _ _ ~ ~ ~ , C2H5 1.40 634 .

v - 31 -~L~8~i60 I .
NHCOC~3 2-66 ~ ~ ~ C2H5 1.40 634 _ _ 2-67 b ~ ~ C 2E 5 1.40 653 : CH3 .

2-63 = b -N ~ -N~ C2Hs 1.35 635 ~ _ . _ __ _ ~ 2-69 O b=N~ - N ~ 1.35 636 ., -- , ._ :~' ~ NHCOC3F7 .: ~ r-~ , C4Hg(n) . 2-70 O=~ >=N~ N 1.30 656 ~ ~ ~=~ ~ ~ C4Hg(n) CH3 __ _ , ~ ____,, ,, NHcoc3F7 4H3(n) ¦ 1,35 ¦ 635 , ~36~C~

NHCOC3H7(1) C 2 55 ~ .
2-72 b N ~ ~ \ C2~5 1.40 ~ 636 _ _ _ , NHCOC3H7~i) c2~5 ~ 1.40 ~ 656 ~283G6~

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the proce-dures described in Example 1 except that the dye used in Example l was replaced by a dye of the following structural formula:

b ~ \C2H5 thereby it was possible to obtain uniform brilliant cyan color recording having a high color density of 1.40.

A light fastness test was conducted on the obtained recording according to the procedures described in Example 1 to find that there was hardly decoloration or change in color after exposure to light for 40 hours. Further, the transfer sheet and the recording were both stable against heat and moisture, and were excellent in dark place storability.

The dye used in this example was produced as follows:

150 ml of ethanol was added to 3.7 g of 2-methylsulfonyl-aminophenol of the following structural formula:

HO - ~

i61) and 5.24 g of a compound of the following structural formula:

H2N ~ 3 , C2H5 H2S04 stirred at room temperature, and then a solution of 3.4 g of silver nitrate in 15 ml of water was added dropwise. 15 ml of a 28% ammonia water was added thereto, further a solution of 10.5 g of silver nitrate in 10 ml of water was added drop-wise, and the reaction was effected at 30 - 40C for 3 hours.
After completion of the reaction, it was extracted with chloroform, the solvent was distilled off, and the residue was purified by column chromatography using chloroform to obtain 5.27 g (yield 76% based on the theoretical yield) of a puri-fied product of an indoaniline type dye of the following structural formula:

= b = N ~ -N

The dye thus obtained had a melting point of 135 - 137C and a maximum absorption wavelength (chloroform) of 640 nm.

83~

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by the dyes set forth in Table 2 respectively, thereby brilliant cyan color recording having the color density set forth in Table 2 was obtained in each case.

The results of a light fastness test on the obtained record-ing and a dark place storability test on the transfer sheet and the recording were both good.

Table 2 _ _ : Color Maximum No. Structural Formula of the Dye of the Wavelength Recording (Chloroform) ~ ~ . _ __ 4-1 b N ~ N~ C H 1.40 660 : CH3 _ _ _ 4-2 C33 1.35 645 _ 4-3 b ~ ~ C3H7(n)~ 1.40 662 : C~3 .
~: _ 4-4 b ~ C4Hg(n) 1.35 663 CH3 : _ 4-5 b ~ N~ C5Hll(n) 1.35 664 5Hll(n) _ CH3 3~
_ ~

4- 6 ~ =b N~ ~ C6H13 (n) ¦ 1 30 ~ 6 _ _.

4- 7 b N~ N~ CH3 1.35 626 . _ _ _ 4- 8 ob ~ ~ C3 H7 ( n) 1 . 4 0 64 0 __ _. .

4- 9 b=N~_ ~ 2 5 1.40 641 4-10 ¦b ~ 9 C H ( ¦ 1,35 642 . .__. . .

4-11 b ~ ` C2H5 1 30 606 CH 3 .

--, CH 3 _ _ _ 4 -12)=~ 2 CH 3 C H 1 . 3 0 6 3 6 ,O=~=N~3--N
CH 3 .

NHS02N ~
4-13\~\ ~\ , CH3 1. 30 620 O=~=~)=N~.--N
e ~ CH 3 _ _ ~HSO2N \ CH

4-14o=b=N~--N~ 1. 30 655 __ ~ .

~ ,_ C2H5 4-15 O=~=N~--N~ 1 . 4 0 64 9 . ~ _ NHS02N ~
4-16 o=b=N4~--N ` 1 . 30 639 CH 3 _ _ , C 2H 5 _ .

NHS02N ~
4-17 ~. ~--~ ~ C2H5 1.30 635 O=~ )=N--(/ \>--N
\=/ \=/ ~ C2H5 _ _ _ _ , C2H5 NHS02N ~
4-18 ~ ~ ~ CH3 1.30 619 _ _ _ _ , C2H5 NHS02N ~
4-19 b ~ , C2H5 ~ .4 , C2H5 4-20-- b - N~ - N 1 . 3 0 638 CH3 __ __ ___ C3H7~n) ~ C3H7(n) C H
4-21= b =W ~ -N 1.25 ~-~

_. ~ _ C4Hg(n) NHSO2N ~C4Hg(n) 2~ r-~ ~ C2H5 1.25 652 : 4-2O=~ >=N~ -N
\=/ ~ ~ C2H5 NHCOOC2Hs 4-23 b ~ , C 2H 5 1.35 656 . CH3 ~2~336~

NHCOOC2H5 ~ CH
4 - 2 4 CH3 1 . 3 5 6 4 0 . ~

4--2 5Nboc 2 3 5 1 . 4 0 6 3 6 ._ .. . . . _.

4--26 b~ ~ ~ CEI3 1.35 620 ~ _~_ _ l 4--2 7 ¦ -- ~ N ~ 2 ~ 1 . 3 5 ¦ 6 5 6 . , .

4 :28 b ~ , c2 5 1.35 636 __ ~
NHCOOC4H 9 ( n) 4--2 9 G=b--N~--N

-- - - - - ~
NHCOOC4Hg(n) 4-30 b N~ N ~ C H 1.30 633 _ . __ _ _ _ _ 4-31 b ~ ~C2H5 1.35 634 ,~ ,~. . __ __.
NHCONHC2Hs .

: 4-32 b ~ ~ C2H5 1.35 653 ;:: NHCONHC2Hs 4-33 b N ~ ~ C2H5 1.35 633 .
.
NHCONHC3H7(n) 4~34b N ~ N ~ 2 5 1.30 633 ,: _ _ ~ _ NHCONHC3H7(n) 4-35O ~ N ~ N ~ C2H5 1.30 653 ~283~

NHcsNHc2H5 .
4-36 b ~ , C2H5 1.30 653 _ CH3 4~37 = b =N ~ N 1.30 654 _ ~ CH3 NHCON ~

4-38 O ~ ~ , C2H5 1.30 633 ~ .
NHCoN~ C2H5 4~39 b N ~ N~ C2H5 1.30 632 . _ ~ . .
NHCON~ C4Hg(n) 4-40 ~ ~ ~ C2Hs 1.25 631 4-41 ~ ~ ~ C H 1.30 631 _, . ...

3~6~

_ NHCSN~ C2H5 4-42 b ~ , C 2H 5 1.30 632 ~ . . ___ C4Hg(n) C4Hg~n) 4-43 O- ~ N ~ N~ C2H5 1.25 632 ...__._ .

4-44 0=~ - N~ N~ C2H5 1.30 642 ~ . , _ 4-4 5 O=~=N~ - N 1.30 638 . _ , .

4-46 0= ~ - N 1.30 638 . ~ CH
NHS2N\ CH
: ~ ~ ~ ~ C2~33 ~ l 30 ~ 637 ~Z8;3~60 , C 2 H 5 4-48 ~ ~ , C2H5 1.30 637 . CH3 4-49 O= ~ =N ~ N~ C2H5 1.30 636 \=<C2H5 4-50 ~ ~ ~ C2H5 1.30 636 _ _ : NHCSNHC2H5 ~ C2H5 4-51 ~ ~ C2H5 1.25 636 . _ NHCOOc2H5 ~ C2H5 4-52 ~ ~ ~ C2H5 1.20 658 _ ........ ._ .

4-53 O= ~ N ~ -N

:

~Z~33~6~

... __ 4-54 o= ~2=N~ N C2H5 1.25 64~

., . . _ _ ___ 4 - 5 5 O=~=N~--N ~ 1 ~ 2 5 6 41 __ . _ 4- 56 O ~ ~ C2H5 1 . 2 5 641 _ ,. _ 4-57 O=~=N~--N 1. 25 642 _ ~ _.

4--58 b ~ ~ C2H5 1. 30 630 : Cl .. . ~.. _ NHCOOc2H 5 ~ b ~ ~ c H~ 1. 30 630 ~LX83~i6~

---r-b=N ~ ~ C2H5 4-60 CH3 1.25 667 _ . _ I

4-61 ob =N ~ -N~ 1.35 650 4-62 O ~ N ~ N C2H5 1.35 648 . ~ _ 4-63 b N ~ -N~ C2H5 1.30 646 . _ _ . . _ ~
i~ NHCSNHC2H5 4-64 b N ~ N~ C2 5 1.30 643 i- CF3 . ~ C 2H 5 _ NHSO 2N ~

5 ~ ~ ,C255 ~ 1.30 644 3366~

..... _ _ _ _ , 4-66 ~ O~=N~ N C235 1.30 643 .

NHS02C~3 4-67 b ~ ~ C2H5 1.25 664 ...._ 4-68 ~ ~ \ C2H5 1~25 663 _ NHCOH
: :: _ )~ ~ ~ C2HS
4-69O= ~ =N ~ -N ~.1.25 662 `: ,. _ .

4-70 ~ ~ ~ C2H5 1.20 660 NHCO ~
. ... ~ . _ NHCO_ ~
L ~ c23s ~ 1.20 ~ 642 -~2~33~

NHCO~ ~
4-72 ~ ~ ~ C2H5 1.25 636 '_. _ N'E~COOC2H5 4-73 O ~ =N ~ N~ C2~15 1.20 634 C2H4--~

_ 4-74 O= ~ N ~ N~ C2H5 1.20 635 ~ C 2H 4--(~

. ...

~ NHS02CH3 ; 4-75 O ~ =N ~ -N ~ ~ l.lS 650 __ ~ _ 4-76 O= ~ N ~ N~ C2H5 1.30 634 ~ C2H40H

4-77 O= ~ N ~ N~ C2H5 1.35 632 .. .. ~ - -: ..

-~ ~

~;2133~

. _ .
NHS02--~
4-78 ~ ~ ~ C2H5 1.25 643 : . _ .
NHCOO- ~
4-79 b N ~ N~ C2H5 1.20 638 ~ _ ..... _ _ :
: NHCONH- ~
4-80~ ~ ~ C2H5 1.15 636 _. .__.___ ._ . ._ NHS02cH3 ~ ~ CH2cH=cH2 4-81O=~ ~=N ~ -N 1.35 630 \=/ \=J ~ CH2CH=CH2 _ .

~ b= r~ S~ 1-20 ~ 634 NHCOOC2H5 Cl 4-83 = b =N ~ -N 1.25 594 ~33~

. _ .
NHCOOC2H5 ~H3 4-84 b N ~ N~ C2H5 1.30 635 ~ , CH2CH=CH2 4-85 O=~ ~=N ~ -N 1.30 624 =/ \~/ ~ CH2CH=CH2 ~ C2H5 _ NHS02N~ C2H5 ; 4-86 = b =N ~ Nf CH2CH=CH2 1.25 626 :: ~ CH2CH--CH2 ___ ~ . . ~ . .

~ ~ CH2CH=CH2 4~87 O- ~ -N ~ -N 1.30 624 ~ CH2CH=CH2 _ ~ ~ CH2CEI=CH2 4-88 O=( )=N ~ -N 1.30 650 \=/ >=/ ~ CH2cH=cH2 _ . _______ . 4-89 b N ~ N~ C2H5 1.25 665 . OCH3 ~33660 _ 4-90 ~ ~ \ C2H5 1.35 646 . ~
: NHSO2CH3 4-91O= ~ =N ~ -N~ C2H5 1.35 643 CF2C~3 __ NHCOC2H4OcH3 4-92 ~ r~~ ~ C2H5 1.20 619 O= ~ =N ~ -N
_ _ _ _ 4-93~ C2H4OCH3 C H 1.20 633 O= ~ =N ~ -N

336~0 Preparation of the inkl preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example l except that the dye used in Example l was replaced by a dye of the following structural formula:

O = ~ =N ~ N/C2H5 ; CH3 thereby it was possible to obtain uniform brilliant cyan color recording having a high color density of 1.40.

A light fastness test was conducted on the obtained recording according to the procedures described in Example 1, to find that there was hardly decoloration or change in color after exposure to light for 40 hours. Further, the transfer sheet and the recording were both stable against heat and moisture, and were excellent in dark place storability.

The dye used in this example was produced as follows:

150 mI of ethanol was added to 3.28 g of 5-methyl-2-acetamido-phenol of the following structural formula:

12~336~0 HO - ~

and 5.24 g of a sulfate salt of a compound of the following structural formula:

H2N~ C2H5 stirred at room temperature, and then a solution of 3.4 g of silver nltrate in 15 ml of water was added dropwise. 15 ml of a 28~ ammonia water was added thereto, further a solution ~ of 10.5 g of silver nitrate in 10 ml of water was added drop-1~ wise, and the reaction was effected at 30 - 40C for 3 hours.
`~:
After completion of the reaction, it was extracted with chloro-form, the solvent was distilled off, and the residue was purified by column chromatography using chloroform to obtain 5.6 g~Iyield 82% based on the theoretical yield) of a purified product o~ an indoaniline type dye of the following structural formula:

N~COCH3 ~ \C2H5 ,., ~2~3~

The maximum absorption wavelength of the above dye was 637 nm (chloroform).

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by the dyes set forth in Table 3 respectively, thexeby brilliant cyan color recording having the color density set forth in Table 3 was obtained in each case.

The results of a light fastness test on the obtained recording and a dark place storability test on the transfer sheet and the recording were both good.

, ... .
........ .

lZ8~G$0 Table 3 Color ~b90rption No. Structural Formula of the Dye f th Wavelength o e (Chloroform) Recordlng (nm) 6-1 O ~ - N~ N ~ C 2H 5 1 . 35 658 6-2 ~ CH3 1.35 ~ 628 ___. __ 6-3 ~ ~ ~ C3H7(n) L.35 639 ~ _ : NHCOCH3 6-4 ~ ~ / C4Hg(n) 1.35 640 6-5 ~ ~ CsHll(n) 1.30 641 CH3 _ ~2~

6- 6 O= ~ =N ~ -N~ C6H13(n) 1.30 641 \ C6~13(n) C~3 6- 7 ~ ~ ~ C2H5 1.35 638 _ ~ ~ C3H7(n) 6- 8 o=~=N~ ~ C3H7(n) 1.35 639 _ _ _ NHCOC2H5 C4Hg (n) 6- 9 ~ ~ ~ C4Hg(n) 1.35 640 { _ _ _ _ . _ _ ~ _ NHCOC3H7(n) 6-10 ~ ~ ~ C2Hs 1.35 638 __ ~ : - , NHCOC4Hg(n) 6-11 ~ ~ ~ C2H5 1.35 638 6gi~) _ NECOC2H5 ~ C2H5 6-12O ~ N ~ N ~C H5 1.30 657 Cl CH3 _ _ .. _ __ NHCOC3H7(n) 6-13 ~ ~ ~ C2Hs 1.30 657 Cl CH3 __ _ NHCOC4Hg(n) 6-14 O ~ =N ~ -N 1.30 657 \~ >~::/ ~ C2H5 Cl CH3 _ _ ~
~: NHCOC2H5 ~ r-~ ~ C3H7(n) : 6-15O~ ~=N-~ N 1.30 . 658 C3H7(n) :~ Cl CH3 __ _ NHCOC2Hs 6-16 O ~ ~ ~ C4Hg(n) 1.25 659 ___ _ _ _ 6-17 ~ ~ C2H
;

-33~

_______ NHCOCH3 6-18 O= ~ --N ~ -N 1.25 633 6-19 ~ ~ , C2H5 1.30 633 Cl F
._. .

6-20O ~ =N ~ N~ C2H5 1.20 661 Cl NHCOCH3 :' _ _ _ _ _ `~: NHCOCH3 6-21O= ~ =W ~ N~ C2H5 ~ 1.20 659 \ C2H5 Cl NHCHO
' _ _ _. _ 6-22O= ~ =N ~ -N~ 1.20 661. Cl NHCOC2H5 ,, ,,,,, _ _ . ..

6-23O ~ N ~ N~ C2H5 1.30 633 ~8~0 . _ 6-24 ~ N ~ ~ C2H5 1.20 662 _ _ 6-25 ~ ~ ~ C2H5 1.15 678 Cl CH3 CH3 _ __ _ __ _ : 6-26 ~ ~ ~ C2H5 1.15 678 Cl CH3 OCH3 _ _ _ . _ NHCOCH3 Cl ; 6-27 O ~ =N ~ N~ C2H5 1.15 657 Br NHCOCH3 ~ _ _ 6-28 ~ ~ N~ C2H5 1.15 676 Br NHCOCH3 _ ~
: NHCOCH3 F
6-29 O ~ ~ ~ C2H5 1.25 631 .

. . .

- - -6-30 O ~ =N ~ \ 1.25 631 ~` _ NHCOCH3 Br 6-31 O= ~ =N ~ -N - 1.25 629 _ _ 6-32 O= ~ N ~ N~ C2H4OCH3 1.25 651 ~_ C2H5 ,: _ __ _._ _ __ 6-33 O= ~ -N ~ N~ C2H5 1.25 634 ~=~ \ C2H40C2H5 CH2CF3 , _ : 6-34 ~ ~ ~ C2Hs 1.30 654 6-35 O= ~ =N ~ -N~ C2Hs 1.30 635 ~C2H40H

~ 61 --'12~

6-36 ~ ~ N~ C2H40CH3 1.25 628 ~ )=/ C2H4ocH3 : CH3 CH3 .

6-37 O ~ =N ~ N~ C2H5 1.25 653 ~=~ ~ C2H40c2H4ocH3 6-38 O ~ =N ~ N~ C2H5 1.20 622 \~ ~=/ ~ C2H4cN

~ __ , - -- _ ~ 6-39 ~ ~ , C2H5 1.25 627 ; CH3 CH3 :: ~ - _ _ )---~ ~ CH2CH=CH2 6-40O=~ ~=N 4/~ -N 1.30 635 \=~ )=/ C 2H 5 ; CH3 CH3 6~41 ~ ~ ~CH2- ~ 1.25 654 ~Z~6 __ 6-42 0= ~ =N ~/~ N~ CH2CH=CH2 1.30 625 =~ ~ CH2CH=CH2 CH3 C~3 NHCOC2H40cH3 6-43 0= ~ - N~ - N~ 1.25 638 NHCOc2H40c2H5 6-44 ~ ~ C2H5 1.25 638 _ .~ .

6-45 ~ ~ ~ C2H5 1.25 638 _ . CH3 .

NHCOC~H4CN .
6-46 0= ~ =N ~ N~ C2H5 1.25 634 CH3 ~ C2H5 _ NHCOCH~CH=CH2 6--47 o=~=N4~--N~ 6 3 -~8;~

: NHCO-CH~- ~
6-48 o=~ =N~ - N\ 1.25 636 _ .

:~ 6-49 ~ ~ ~ N~ C2H5 1.25 628 _ _ . _. _ 6-50 ~ ~\ C2H5 1.35 638 _ _ .

~6-51 ~ ~ Cj~34- ~ ~1.25 ~ 638 _. __ _ _ : 6-52 O= ~ =N ~ -N 1.25 631 C2H4OCOcH3 _ _ _ . _ _ .

6-53 O= ~ =N ~ N~ C2H5 1.25 632 8366~

- ~

6-54 O= ~ -N ~ N~ C2H5 1.25 632 CH3 C2H4Ocooc2H5 _ 6-55 ~ ~ C2H4O- ~ 1.25 633 6-56 O= ~ =N ~ -N~ C2Hs l.Z0 653 Cl CH3 \ C2H4OC6Hl3(n) _~ _ .

\~ ~ C2H5 6-57 O~ ~=N- ~ N~ 1.20 654 Cl CH3 CH2cHc2H5 6-58 O=~ C~

__ . ____ NHCO- ~
6-59 ~ ~ ~ C2H5 1.10 690 Br CH3 .

~LZ8~6~

NHCOCH3 _ 6-6 0 Cl OC 33 1 . 10 6 4 0 -L~ c23s 1.35 636 \C~3 1,3s ~Z~

NHCOC3~7 C2H5 6--63 (~ ~ \ C2H5 1.35 655 :~ _ _ _ 6-6~'3~/C~3 1.35 ~ 626 6--6 5 O~--N~--N 6 3 6 6~

NHCOCF3 . _ _ 6-66 b ~ ~ C2H5 1.35 655 _ _, , ., ....... ~.~, _ _ 6-67 ~ ~ ~ C2H5 1.35 648 ____ -) \ ~ C2H5 6-68 O= ~ =N ~ -N 1~20 660 CH3 NECOCF3 _ 6-69 O ~ =N ~ N C2H5 - 1.10 647 .~ CH3 NHCO ~
_ _ _ , .

6-70 O ~ N ~ N~ C2HS 1.30 646 CH3 ..

33~S~

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by a dye of the fo:Llowing structural formula:

NHCOC~3 CH3 ~ CH3 thereby it was possible to obtain uniform brilliant cyan color recording having a high color density. The color density of the obtained recording was 1.25.

~:;
A light fastness test was conducted on the obtained recording according to the procedures described in Example 1, to find that there was hardly decoloration or change in color after exposure to light for 40 hours. Further, the transfer sheet and the obtained recording were both stable against heat and moisture, a~d were excellent in dark place storability.

The dye used in this example was produced as follows:

3.0 g of 2-acetamidophenol of the following structural formula:

~Z~ 6~

NHCOC~3 HO - ~

and 5.1 g of a compound of the following structural formula:

H2N ~ ~ , 3 HCl ,~ were added to 200 ml of methanol, stirred at room temperature, and then a solution of 3.4 g of silver nitrate ln 15 ml of water was added dropwise. 15 ml of a 28% ammonia water was added thereto, further a solution of 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction was . ~ :
effected at 30 - 40C for 3 hours. After completion of the reaction, it was extracted with chloroform, the solvent was distilled off, and the residue was purified by column chromato-graphy using chloroform to obtain 5.3 g ~yield 73% based on the theoretical yield) of a purified product of an indoaniline type dye of the following structural formula:

.

i60 The maximum absorption wavelength of the above dye was 652 nm (chloroform).

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by the dyes set forth in Table 4 respectively~ thereby brilliant cyan color recording having the color density set forth in Table 4 was obtained in each case.

The results of a light fastness test on the obtained record-ing and a dark place storability test on the transfer sheet and the recording were both good.

-~28~G60 Table 4 _ _ _ Maximum Color Absorption No. Structural Formula of the Dye Recordlng (nm) . _ _ _ _ 8-1 O= ~ =N- ~ l.25 646 CE2CH=CH2 ¦ 8-2 ~ C33 ~ 1.20 ~ 648 _ N SO2C~3 O=~ ~=N--~r~~~
8-3 ~ NJ l.20 646 .~ _ ~ _ O= ~ =N~
8-4 ~C2~5 1.25 650 __ _ _ .~ NHS02N~ C2H5 2C~=c~l2 ~133~

8 - 6 C 5 3 1 1 .15 6 7 2 285 3 1.20 653 NHCOOc2H 5 CH 3 8-- 8 C2H 5 1 . 2 0 6 5 3 . _ _ \I~ C~ 1.10 653 NHcsNHc2H5 CH3 8--1 0 ~CH 3 1.1 0 6 S 3 8-11 ~ ~C83 ~ 1.25 655 L ; ~ H33 1.10 653 _ , CH3 NHCSN ~ CH3 CH3 8-13 b ~ ~ CH3 1.10 653 __ , CH3 .
NHS02N ~ CH3 CH3 8-14 = b =N- ~ H3 1.10 654 .~ 2H 5 ~ .

8-15 CH3 1 3 l.lS 657 , ~ C2H5 8~16 O= ~ =N- ~ CH3 1.10 657 H3COCHN l2H5CH3 8--17 o= b =N ~--N~_~

_ NH502CH3 _ 8-18 O ~ =N ~ -N~_~SO21.30 621 8-19 N b OC2H5 1.30 621 _ .
NHCONHC2~5 8-20 - b =N ~ -N~_~SO2 1.25 621 _ ~ .

~ 8-21 = b -N ~ -N S2 1.25 622 _ _ 8~22 ~ =N ~ -~ `302 ~ 1.30 636 _ : _ 8-23 ~ I ~l S~/

- - --~ 8-24 . ~ ~3~ 2 1.30 637 . _ 8-25 b ~ ~ , 1.30 623 ~: ~ 8-26 b ~ ~ ~ 1.30 624 ,., _ ~ ' .
. NHCOOC2H5 8-27 = b =N ~ -N O 1.30 624 ~ ~ _ _ 8-28 O ~ =N ~ -N O 1.25 624 ~ . '_ , 8-29 b ~ ~ , 1.25 625 83~6 - - - - -8-30NHCOCH3 1.30 ~ 638 1.30 L

1 b ~ 1 3 0 ~) ~ C2HS 1.15 660 8--3 4CH 3~ 1 . 1 0 6 6 2 ._ _ _ C2HS ~.10 ¦ 661 i65) 8-36 b ~ ;` c2Hs 1.10 ~ 659 . __ .
9-37 NAC~N~C,U 1.10 661 , ~ 1.15 661 NHCON ~ C~I3 8 ~ 1.10 661 NHS02N~ CH3 8-40 ~ ~ ~ C2H5 1.10 661 _ _ .

~ ~ ~ 1.15 663 ~283~6~) . _ _ . .

~,=n~ > ~ 1.lS ~ 66 5 8 - 4 3 O =b=N~ ~ 1 . 2 0 6 5 6 _ .

8-44 C b N--~O ~ 1. 20 __ ._ ___ _ _ ~ _ C2as l.lS 658 ~N IC2H5 ~ 1.05 ~ 680 -- ~)'N~ 1.05 ~ 660 ~Z~ i6 .
NE~S02CH3 L~ L = ~ o s ~ 1 ~

. 8-49 O= b -N ~ 1.15 620 _ .

8-50O ~ =N ~ N~ C2H5 1.1 5 634 _ . _ 1.30 ~ 630 : 8-52 CH3 1.20 642 _ _ _ . __ 8-53b ~ ~ , 1.20 643 OCH3 _ .

. - 79 -~,2~36~

8-54 O~=N~n O l . 20 618 . .

8- 5 5 Br l . 2 0 618 _ _.

8-56 ~NBCOc3p7 l . 30 625 _ ~
NHCO--l S 3 CH
8 - 57 C2H 5 1 . 10 6 5 7 _ . _ .
: NHCO~ CH3 8 - 5 3 ~ 5 1 . 10 6 5 6 .
2~HCSO-C2H4OCH3 CH 3 ~\~ 1l~ )<CB3 ~ l.05 652 ~2~3366~

, . _ _ _. ~ _ 8-60 ~ 1.25 645 _ _ _ 8-61 O ~ =N ~ -N~_~O 1.20. 646 ` __ __ 8-62 O ~ = ~ -N~_~O 1.15 640 NHCO ~
___ _ _ _ _ 8-63 b ~ ~ , 1.25 628 .' ~

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by a dye of the following structural formula:

~ ~ ~ C2H5 thereby it was possible to obtain uniform brilliant cyan color recording having a high color density of 1.30.

A light fastness test was conducted on the obtained record-ing according to the procedures described in Example 1 to find that there was hardly decoloration or change in color after exposure to light for 40 hours. Further, the transfer sheet and the recording were both stable against heat and moisture, and were excellent in dark place storability.

The dye used in this example was produced as follows:

300 ml of ethanol was added to 4.1 g of 2,5-bis-acetamido-phenol of the following structural formula:

~a~o HO ~

.
and 5.3 g of a compound of the following structural formula:

H2N ~ -N~ H2SO4 \ C2H5 stirred at room temperature, and then a solution of 3.4 g of silver nitrate in 15 ml of water was added dropwise. 15 ml of a 28% ammonia water was added thereto, further a solution of 10.5 g of silver nitrate in 10 ml of water was added drop-wise, and the reaction was effected at 30 - 40C for 3 hours.
After completion of the reaction, it was extracted with chloroform, the solvent was dlstllled off, and the residue was purified by column chromatography using chloroform to obtain 5.7 g (yield 78% based on the theoretical yield) of a purified product of an indoanilLne type dye of the following structural formula:

o Q N ~ N~ C2H5 - : ".. ~ , .. , -~;2 836Çi0 The mass spectrum of the above dye was m/e = 368, and its maximum absorption wavelength was 634 nm (chloroform).

Prepa.ration of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by the dyes set forth in Table 5 respectively, thereby brilliant cyan color recording having the color density set forth in Table 5 was obtained in each case.

The results of a light fastness test on the obtained record-ing and a dark place storability test on the transfer sheet and the recording were both good.

.

.

~Z~33~61D

Table 5 ___ _ ~ _ . _ .

No. Structural Formula of the Dye Density Marimv Recording (Chloroform) __ _ .

10- 1 ~ ~ ~ C2H5 1.30 654 _ : ~ r-~ ~ C3H7( n) ; 10- 2 O=~ >=N~ N 1.30 655 ; ~ ~ ~ C3H7 (n~

__. _ _ _ 10- 3 ~ ~ CH3 1~ 25640 .~ ._ _ _ 10- 4 O= ~ =N ~ -N~ 1.25 656 : 10- 5 O= ~ =N ~ N~ C 5Hll( n) 1. 20 657 ~ ~ ~ CsHll(n) _ _ 10 - 6 ~ ~~ C 6H13 ( n ) 1 .15 6 5 8 ._ _ _ :~ NHCOCH3 10- 7O= ~ =N ~ -N~ 1. 2 5 6 2 0 _ __ 10 - 8 ~ ~ C3H7( n ) 1 . 30 635 NHCOC~3 10 - 9 ~ ~ ~ C4 H g ( n ) 1 . 2 5 6 3 6 10-10 ~ ~ ~ CsHll ( n) 1 . 2 5 637 } _ _ __ _ C4H3(~) ~ 1.30 ~ 635 10-12 ~ ~ 1.30 644 H3COCHN CF3 , _ . .__ .................. __ 10-13 ~ CH3 CH 1.25 630 __ _ .

10-14 ~ ~ , C2H5 1.15 630 : H3COCHN
_ _ . _ _. .. . __.

lQ-15 ~ ~ 2 4 ~ 1.10 650 _ _ _ ._ . __ 10-16 O ~ =N ~ -N~ l.lS 634 H3COCHN _ 10-17 ~ ~ ~C2H4OH 1.10 654 .

~Z836~i~
.

;: 10-18 ~ ~ ~ C2H5 1.30 638 _ : NHSO2CH3 10-19 O- ~ =N ~ N~ 1.25 622 . H3CO2SHN

:: 10-20 ~ ~ ~ C2H5 1.30 658 ~ H3CO~SHN CH3 ~ _ _ __ , _ _ ,; NHS02CH3 10-21 O= ~ =N ~ -U~ 1.25 642 /: : ~3Co2sHN CH3 ~: ~ _ ~ _ _ . NHCOOCH3 . ~=\ ~, C2H5 10-22 o=~=N~~ C2H5 . 1.25 638 _,, ~

10-23 ~ ~ ~ ~ C235 ~ --- ~

10-24 Q ~ NC2H5 1.25 638 _ __ _ 10-25 ~ ~ \ C2H5 1.25 658 10-26 ~ ~ ~c2H5 1.30 638 _ _ _ 10-27 ~ ~\ C2H5 1.30 658 F3COCHN CH3 __ ___ _ _ _ 10-23 ~ ~~ C2~5 1.25 639 :` _ 10-29 ~ N ~ N~ C2H5 1.25 659 - - -10-30 O= ~ =N ~ ~ C2~5 1.20 657 \=.~ )=/ C 2 H 5 _ _ NHCONHCH3 ~ C2H5 10-31 O ~ =N ~ -N~ 1.20 637 ~ . .

` 10-32 O= ~ =N ~ N~ C2H5 1.20 637 ~ ~ C2H5 _ . _ 10-33 O= ~ =N ~ -N~ 1.20 658 _. _ _ N ~ NHc2H5 .~ 10-34 O=~ t=N ~ -N 1.20 658 \~, )=/ ~ C2H5 N ~SNHC2H5 10-35 O=~ ~=N- ~ N 1.20 637 \~< =/ C 2H 5 _ NHCSNHCH3 10-36 O= ~ =N ~ -N~ 1.20 658 10-37 ~ ~ 2 5 1.15 657 3 _ _ NHCON~ CH3 O ~ N~ 1.15 636 NHCON ~C2H5 10-39H C ~NOCHN 1.15 636 -NHSO2N ~CH3 C2 5 10-40 O= ~ =N ~ -N~ 1.10 656 -- H3C~ O2SHN CH3 _ _ o~ -N~ ¦ 1.10 636 ~3~

_ , C 2H 5 CL~

1~ 0=~)~

10-44 O- ~ -N ~ -N 1.15 657 : - H3C~ NSCHN CH3 10-45 ~ ~ ~ C2H5 1.30 . 635 __ _ 10-46 Q ~ N~ C2H5 1.30 655 . H3CO2SHN CH3 10-47 O ~ N ~ N~ C2H5 1.30 634 ~..2~3~ii~

10-48 O= ~ =N~ N~ C2H5 1.30 654 \=~ ~=/ C2H5 . _ _ _ _I

10-49 O ~ N ~ N~ C2H5 1.30 658 __ _ _ .

10-50 ~ ~ ~ C2H5 1.30 638 10-51 ~ ~ \ C2H5 1025 635 H3CD~b1~
_. _ 10-52 O ~ N ~ -N~ C2H5 1.30 635 . _ . _ 10-53 ~ ~ ~ C2H5 1.25 636 `~
- -10-54 ~ ~ ~ C2H5 1.25 636 _ ~ . ~ _ . 10-55 O ~ N ~ N~ C2H5 1.25 636 _ _ _ : 10-56 ~ ~ ~ C2H5 1.25 656 _ . ~

~\ ,~ ~ C2~I5 10-57 ~ 1.20 656 3 ~NOCHN H3 e __ _ _ _ 10 - S8 O ~ =N ~ -N 1.20 657 ,NSCHN CH3 _ 10-59 O= ~ =N ~ -N~ 1.20 635 .

~ N02SHN .
. .

~8~
_ _ 10-60 O= ~ =N ~ -N ~ 1.30 636 : H3COCHN
_ _ :~ ~HCOOCH3 10-61 ~ ~ ~ C2H5 1.25 638 . . I

10-62 ~ ~ ~ C2H5 1.25 638 : 10-63 O- ~ =N ~ -N ~ 1.20 638 H C,NOCHN
_ ._ _ 10-64 O; ~ -N ~ N~ 1.20 638 _ ._ _ _ _ ._ _ I

10~65 O= ~ =N ~ -N~ 1.20 638 ,N02S~N

: -- -~=~ ~ , CH2CH=CH2 10-66O=~ ~=N~ N 1.30 620 ,=< ~.=/ ~ CH2CH=CH2 ~ ___ 10-67 ~ ~ ~ C2H5 1.15 672 ~ _ _ 10-68 ~ ~ ~ C2H5 1.15 670 . _ _ __ _ _ 10-69 O= ~ =N ~ N~ C2H5 1.20 628 .~ \=~ ~=/ ~ C2H5 ~ H3COCHN Cl _ __~ ~_ _ ..

10-70 O= ~ =N ~ W~ C2H5 1.15 628 , " C2H5 H3COCHN Br _ _ NHCOCH3 Cl 10-71 ~ ~ N~ C2H5 1.20 627 ~ ~33Ei~

NHCOCH3 Br =
10 - 72 O~ =N~ - N ~ 1.15 627 _. _ : NHCOCH 3 OC 2H 5 10 -73 ~ ~ ~ C 2H5 1.15 671 .~ _ 10 -74 ~ ~ ~ C 2H4 - ~ 1.10 635 H 3COzSHN
_ _ _ _ NHS02CH3 ~ C2H5 10 - 75 O= ~ =N ~ -N 1. 15 638 H3C02SHN ~_ _ . __ _ 10 - 76 ~ ~ ~ C 2H 4 ~ 1.10 653 _ _ 10 -77 ~ ~ ~ C H40H 1.10 657 ~ -10-78 ~ ~ N~ C2H5 1.20 663 _ _ _ 10-79 ~ ~ ~ C2H5 1.20 665 _ _ . 10-80 ~ ~ \ C2H5 1.20 663 : H3COCHN NHCOCF3 _ _._ _ _ , NHCOCH3 10-81 O ~ N ~ N~ C2H5 1.10 658 : H3COCHN NHCO- ~
. ~ . _ _ _. _ _ _ ~ ~ C2H40CH3 10-82 O=~ >=N~ -N 1.10 648 . ~ ~=~ ~ C2H4OCH3 _ _ _ NHCOI~s .!J
10-83 ~ ~ ~ CH2CF3 1.15 620 _ H3COOEIN

~2~3~

_ .
NHCO~
10 - 8 4 Q ~ \ C 2H 5 1 . 1 5 6 3 5 _ , _ _ NHCSOc2H40clI3 10- 8 5 ~ ~ ~ C2H4Cl 1 . 10 616 _ H 3COCHN

~ ~ .

- _ 99 _ 3~

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example 1 except that the dye used in Example 1 was replaced by a dye of the ~ollow.ing structural formula:

NHcocH=cH2 =b--N ~--N ~

thereby it was possible to obtain uniform brilliant cyan color recording having a high color density of 1.40.

Further, a light fastness test was conducted on the obtained recording according to the procedures described in Example 1 to find that there was hardly decoloration or change in color after exposure to light for 40 hours.

The dye used in this example was produced as follows:

301 g of a phenol compound of the following structural formula:

NHCOCH=CH 2 HO~

~21~366~

and 4.3 g of a compound of the following structural formula:

H2N ~ -N\ HCl were added to 150 ml of ethanol, stirred at room temperature, ; and then a solution of 3.4 g of silver nitrate in 15 ml of water was added dropwise. Thereafter, 15 ml of a 28% ammonia water was added thereto, further a solution of 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction ~ was effected at 30 - 40C for 3 hours. After completion of : the reaction, it was extracted with chloroform, the solvent was distilled off, and then the residue was purified by column : chromatography using chloroform, to obtain a purified product of an indoaniline compound of the following structural ormula:

NHCOCH=CH2 ~ b ~ ~ C2H5 The maximum absorption wavelength (chloroform) of this product was 659 nm.

~ Z836~

The indoaniline compounds set forth in Table 6 below were produced according to the procedures described in Example 11.
The maximum absorption wavelength (chloroform) of each ob-tained indoaniline compound is shown in Table 6.

Preparation of the ink, preparation of the transfer sheet and transfer recording were carried out according to the pro-cedures described in Example l except that the dye used in Example l was replaced by the indoaniline compounds set forth in Table 6 as the dyes respectively, thereby it was possible to obtain uniorm brilliant cyan color recording having the color density set forth in Table 6 in each casea A light fastness test was conducted on the obtained record-ing according to the procedures described in Example 1 to find that there was hardly decoloration or change in color.

~B36~

Table 6 No . S tructural Formula of -he Dye De ~3 it, Maximum o t e (Chloroform) Recordlng (nm) __ __ _ _ _ NHCOCH=CH2 12- 1 b N ~ N~ C H5 1.40 639 : ~ _ ~:~ . NHCOCH=CH2 H
;~ 12- 2 ~ N ~ N~ C 3 1.40 629 ~``
.: ~ , . . .
. NHCOCH=CH2 12- 3 = b -N ~ N~ C3H7(n) 1.40 640 C3H7(n) :

NHCOCH=CH2 :
1-- 4 =b _~ ~ C4Hg ( n) 1 . 4 0 6 41 .
NHCOCH=CH2 12- 5 b ~ C5~11(n) 1.35 642 1~ . ~ r ' .

NHCOCH=CH2 ¦12- 6 ~ C6H13(n) 1.35 642 _ _ NHcocH=cH2 12- 7 b ~ , CH2CH=CH2 1.40 623 ~ CH2CH=CH2 NHCOC(CH3)-CH2 12- 8 ~ ~ ~ C2H5 1.40 NHCOCH=CHCH3 12- 9 b ~ ~C2H5 1.40 639 .
~ :~
NHCOOCH=CH2 12-10 b N ~ N~ C2H5 1.40 633 NHCOC(CH3)=cH2 12-11 O ~ =N ~ -N 1 4D 5;9 . - 104 --NHCOCH=CHCH3 12-12 o=b=N~ N~ 1.40 659 _ .
NHCOOCH=CH2 12-13 o=b =N ~ -N 1.40 653 C~3 NHCOCH=CH2 12-14 b ~ ~ CH2CH=~H2 1.40 643 ~ ~ CH2CH=CH2 NHCOCH=CH2 , C2H
12-15 = b =N ~ -N~ 1.35 635 _ _ _ NHCOCH=CH2 12-16 b N ~ N~ C2H5 1.35 635 _ _ NHCOCH=CH2 12-17 = b =N ~ -N~ 1.35 635 _ ., ., ` .

o NHCOCH=CH2 12-18 b ~ N' C2H5 1.30 663 NHCOCH=CH2 12-19 b N ~ N~ C2H5 1.30 661 NHCHO
_ I
_ NHCOCH=CH2 12-20 b ~ ~C2H5 1.30 663 12-21 b N ~ ~ C2~5 1.35 635 _ NHCOcH=cH2 OCH3 12-22 = b =N ~ N 1.35 664 NHcOcH=CH2 CH `
12-23 = b =N ~ -N ~ 1.35 660 .- :. : ,., 6~

NHcocH=cH2 CH3 12-24- b=N~ N\ 1.35 661 _ _ _ _ 12-25NHCOcH=cH2 cl 1.30 659 ~.__ _ . .. .
NHCOCH=CH2 OCH3 12 26 O ~ -N ~ -N~ 1.30 678 __ .__ _ _ _.
:
NHCOCH=CH2 F
~12-27~ ~ b -N ~ -N ~ ~ 1 35 633 _~
NHCOC~=CH2 I C 2}3 5 12-28b ~ ~C2H5 1.35 633 __ __. .
NHCOCH=CH2 Br 12-29o=b=N~ N 1.35 633 .

~z~
-NHCOCH=CH 2 ~=, , C2H40CH3 12-30 0~=N~ - N ~ 1.35 655 _ _ _ . _ _~
NHCOCH=CH2 C2H5 12 - 31 b ~ \ C2H40C2H5 1.35 636 NHCOCH=CH 2 12 - 32 =b=N - ~N~ C2H5 1~35 655 _ _ NHCOCH=CH 2 12-33 b=N~ N~ C2H40CH3 1.30 629 _ .
NHCOCH=CH2 C2H5 12-34 0=b=N~ - N~ 1.30 654 ~/ \ C2H4oc2H4ocH3 _ _ .

NHCOCH=CH2 2 - 3; ~ J~ =N~ - N~ 1.30 ~ 624 'I~8;~

_ ~

NHCOCH=CH 2 12-- 36 b ~ , C2H5 1.30 628 _ NHCOCH=CH2 ~ ~ CH 2CH=CH2 12 - 37 O~=N~N ~ 1 O 35 636 _ ~
NHCO CH =CH 2 C 2H 5 12 - 38 o=b=N~ ~ CH2 - ~ 1.35 655 NHCOCH=CH 2 12 - 39 o=b=N~ ~ CH2 - ~ 1.30 629 _ NHCOCH=CH 2 12-40 b ~ C3H7 ( i ) ~ 1.40 639 .. _ __ NHCOCH=CH 2 C 2~ 5 12-41 ~ ~ ~ C2~4~ 1.30 639 8366q~

-NHCOCH=CH2 12-42 o=b=N~N~ C2H5 1.30 633 _ NHCOCH=CH2 C2H5 12 - 43 o=b=N~ - N 1.30 633 ~ C2H4COOCH3 _ _ NHCOCH=CH 2 12 - 44 o=b=N~ - N 1.30 633 ~ C2H40COOC2H5 ~. ~ '_ _ NHCOCH=CH2 12 45 O - ~=N~ N ~ C2H5 1.30 634 ~ C2H4--~
.
.
NHCOCH=CH 2 12 - 46 o=b=N~ - N ~ 1.30 636 ~ C2H4C6H13 (n) NHcocH=cH2 C 2H 5 12 - 47 O=b=N~ - N~ 1.30 636 ~ CH2CHC2H5 OH

~z~33~

_ ._ 12-48 N~COC8-c 2 1.20 623 _ _.

NHCOCH=CH2 12-49 O= ~ --N ~ -N~ 1.40 640 _ NHCOCH=~H2 12-50 ~ ~ , C2H5 1.40 661 _ . _ _ ..

12-Sl O= ~ -N ~ -N~ 1~40 631 _ _ _, NHCOC~=CH2 12-52 O ~ ~ , C2H5 1.30 660 Cl CH3 , NHCOCH=CH2 OCH3 12-53 O-- ~ =N ~ -N~ 1.30 665 836~

NHcocH=cH2 CH3 12 - 54 O ~ N~N ~ C 2H 5 1.25 681 Cl CH3 OCH3 _ _ NHCOCH=CH 2 cl 12-55 O - - ~=N~N~ C2H5 1.20 660 Br NHCOCH 3 NHCOCH=CH2 F
12 - 56 O~ - N~N~ C2H5 1.35 634 NHCOCH=CH 2 I
12 - 57 ~ N~W ~ C 2H 5 1.20 634 ; NHcocE=cH 2 Br 12-58 o~=N~/ \~ - N ~ 1.25 631 ~< \:=/C2H5 _ , NHCOCH=CH 2 12- 59 ~ ~ \ C2H5 1.30 654 ~8~

NHCOCH=CH 2 12-60O=~=N~ N~ C2H5 1.30 637 ~=~< ~ C2H40C2H5 _ _ NHCOCH=CH 2 12-61O~=N~N~ C2H5 1.25 641 NHcocH=cH 2 .
NHCOCH=CH2 12- 62O=~=N~ N ~ C 2H 5 1.25 661 >=/ ~ C2H5 NHcocH=cH 2 _ _ . _ NHcoocH=cH 2 12 - 63 ~ ~ ~ C 2H5 1.25 641 : NHCOOCH=CH 2 _ NHCOOCH=CH 2 12 - 64 b N~ N~ C2H5 1.25 660 NHCOOCH=CH 2 _ _ NHCOCH=CH 2 12 - 65o=b=N~N~ C2H5 1.25 632 \ C2H40CCH=cH2 _ ~

~2~33~i~0 Br _ NHCOC=CH2 12-66 b ~ ~ C 2H 5 1.30 639 _, ..... _~ ~ ... __ _ ,. .
NHCOCH=C.H2 12-67 = b =N ~ -N~ 1O25 632 ~ C2H40CCH=CHCH3 _, ~______ NHCOCH=CH2 12-68 = b =N ~ -N~ 1.25 632 _ _ , ...... _ ._ _ ~ --.. . .

Claims (20)

1. A dye for heat-sensitive transfer recording which is of the general formula [I]

wherein -B represents , , , , , , , , , or , -Z1 and -Z2 each represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, halogen or -NHB, K represents , , , , , , , or , - R1, -R2, -R6 and -R7 each represent hydrogen; C1-C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, or phenoxy; vinyl optionally substituted by methyl or halogen; allyl; or phenyl, -R3, -R4 and -R5 each represent hydrogen or methyl, -X represents hydrogen; lower alkyl optionally substituted by fluorine; lower alkoxy; formylamino; lower alkyl-carbonylamino optionally substituted by fluorine; phenyl-carbonylamino; or halogen, and -Y represents hydrogen, lower alkyl optionally substituted by fluorine; lower alkoxy; or halogen

2. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[II]

wherein -X1 represents hydrogen, methyl, methoxy, formylamino, acetylamino, propionylamino, chlorine, bromine, iodine or fluorine, -Y represents hydrogen, methoxy, ethoxy, chlorine, bromine, iodine, fluorine or methyl, and -R8, -R9 and -R10 each represent hydrogen; C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy or phenoxy; allyl; or phenyl.

3. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[III]

wherein -X represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, formylamino, lower alkylcarbonylamino optionally substituted by fluorine, phenylcarbonylamino or halogen, -Z3, -Z4 and -Y each represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy or halogen, -R9 and -R10 each represent hydrogen; C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetra-hydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, or phenoxy; allyl; or phenyl, -B1 represents , , , , , , , , or , -R11 and -R12 each represent C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcar-bonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, phenoxy;
or phenyl.

4. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[IV]

wherein -X represents hydrogen, lower alkyl optionally substituted by fluorine; lower alkoxy; formylamino; lower alkylcarbonylamino optionally substituted by fluorine; phenylcarbonylamino; or halo-gen; -Y represents hydrogen; lower alkyl optionally substituted by fluorine; lower alkoxy or halogen, -Z5 and -Z6 each represent hydrogen, lower alkyl optionally substituted by fluorine; lower alkoxy or halogen, and -R8, -R9 and -R10 each represent hydrogen;
C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy or phenoxy; allyl or phenyl.

5. The dye for heat-sensitive transfer recording according to claim l which is of the general formula:

[V]

wherein -B2 represents , , , , , , , , , or , Z1 and -Z2 each represent hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, haloyen or -NHB2, -K1 represents , , , , , , , or , -R13, -R14 and -R15 each represent hydrogen; or C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxy-alkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcar-bonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy or phenoxy; -R3, -R4 and -R5 each represent hydrogen or methyl, -X represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, formylamino, lower alkyl-carbonylamino optionally substituted by fluorine, phenylcarbonyl-amino or halogen, and -Y represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy or halogen.

6. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[VI]

wherein -X represents hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, formylamino, lower alkylcarbonylamino optionally substituted by fluorine, phenylcarbonylamino or halogen, -Y represents hydrogenj lower alkyl optionally substituted by fluorine, lower alkoxy or halogen, -R16 and -R17 each represent hydrogen or C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydro-furyl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy or phenoxy, -B2 and -B3 each represent , , , , , , , , , or , -R13 and-R14 each represent C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcar-bonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy or phenoxy.

7. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[VII]

wherein -X1 represents hydrogen, methyl, methoxy, formylamino, acetylamlno, propionylamino, chlorine, bromine, iodine or fluorine, -Y1 represents hydrogen, methoxy, ethoxy, chlorine, bromine, iodine, fluorine, or methyl, -A-represents -CO- or -COO-, -R18 represents vinyl optionally substituted by methyl, -R9 and -R10 each represent hydrogen; C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, lower alkoxyalkoxy, cyano, halogen, phenyl, tetrahydrofuryl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, or phenoxy; allyl;
or phenyl, and -Z7 and -Z8 each represent hydrogen, lower alkyl optionally substituted by fluorine, lower alkoxy, halogen or -NH-A-R18.

8. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[VIII]

wherein -R19 represents hydrogen, C1 - C8 straight-chain or branched-chain alkyl, allyl, vinyl, methylvinyl, C3 - C8 alkoxy-alkyl, phenyl-lower alkyl, cyclohexyl, thienyl, trifluoromethyl or phenyl, -A- represents -CO- or -COO-, -Y1 represents hydrogen, methoxy, ethoxy, chlorine, bromine, iodine, fluorine or methyl, -Z9 and -Z10 each represents hydrogen, methyl, trifluoromethyl, methoxy, ethoxy, chlorine, bromine or -NH-A-R19, -X1 represents hydrogen, methyl, methoxy, formylamino, acetylamino, propionyl-amino, chlorine, bromine, iodine or fluorine, and -R20 and -R21 each represents hydrogen, C1 - C8 straight-chain or branched-chain alkyl, C3 - C8 alkoxyalkyl, C2 - C4 hydroxyalkyl, C1 - C8 halogenated alkyl, .beta.-cyanoethyl, vinyl, methylvinyl or tetrahydro-furfuryl.

9. The dye for heat-sensitive transfer recording according to claim 1 which is of the general formula:

[IX]
wherein -R22, -R23 and -R24 each represent C1 - C8 straight-chain or branched-chain alkyl or vinyl, -A-represents -CO- or -COO-, -X2, -Y2, -Z11 and -Z12 each represent hydrogen, methyl, methoxy or chlorine.

10. The dye according to claim 1, wherein in formula [I], -R1, -R2, -R6, and -R7 each represents C1 - C8 alkyl optionally substituted by lower alkoxy, hydroxy, (lower alkoxy) lower alkoxy, cyano, halogen, phenyl, tetrahydrofur-yl, lower alkylcarbonyloxy, lower alkenylcarbonyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, phenoxy.

11. The dye according to claim 2, wherein in formula [II], -X1 represents hydrogen, methyl, methoxy, formyl-amino, acetylamino, propionylamino, chlorine, bromine, iodine or fluorine;
-Y1 represents hydrogen, methoxy, chlorine, bromine, iodine, fluorine or methyl;

-R8 represents methyl, ethyl, n-propyl, n-butyl, 2-methoxyethyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-cyanoethyl, allyl, tetrahydrofurfuryl, phenyl, heptafluoro-n-propyl, pentafluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl, or i-propyl; and -R9 and -R10 each represents hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-(2-methoxy)ethoxyethyl, 2-cyanoethyl, 2-chloroethyl, allyl, tetrahydrofurfuryl, phenyl, benzyl, 2-phenylethyl, i-propyl, 2-acetoxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonyloxyethyl, 2-phenoxy-ethyl, 2-n-hexyloxyethyl or 2-hydroxybutyl, provided that when one of -R9 and -R10 is hydrogen, the other is not hydrogen.

12. The dye according to claim 3, wherein in formula [III], -X represents hydrogen, methyl, trifluoromethyl, chlorine, bromine, formylamino, acetylamino, trifluoroacet-ylamino, benzoylamino, or methoxy;
-Z3 and -Z4 each represents hydrogen, methyl, chlo-rine, bromine, methoxy, ethoxy, trifluoromethyl, or penta-fluoroethyl;
-Y represents hydrogen, methoxy, chlorine, methyl or trifluoromethyl; and -R9 and -R10 each represents hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-phenylethyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, allyl, or phenyl, provided that when one of -R9 and -R10 is hydrogen, the other is not hydrogen.

13. The dye according to claim 4, wherein in formula [IV], -X represents hydrogen, methyl, chlorine, bromine, iodine, fluorine, formylamino, acetylamino, propionylamino, methoxy, trifluoroacetylamino, trifluoromethyl, or benzoyl-amino;
-Y represents hydrogen, methyl, methoxy, chlorine, fluorine, iodine, bromine, or trifluoromethyl;
-Z5 and -Z6 each represents hydrogen, methyl, chlo-rine, trifluoromethyl, bromine, fluorine, iodine, methoxy, ethoxy or 2,2,2-trifluoroethyl, provided that when one of -Z5 and -Z6 is hydrogen, the other is not hydrogen;
-R8 represents methyl, ethyl, n-propyl, n-butyl, 2-methoxyethyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-cyanoethyl, allyl, tetrahydrofurfuryl, phenyl, heptafluoro-n-propyl, or trifluoromethyl; and -R9 and -R10 each represents hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-(2-methoxy)ethoxyethyl, 2-cyanoethyl, 2-chloroethyl, allyl, tetrahydrofurfuryl, ben-zyl, i-propyl, 2-phenylethyl, 2-acetoxyethyl, 2-methoxycar-bonylethyl, 2-ethoxycarbonyloxyethyl, 2-phenoxyethyl, 2-n-hexyloxyethyl, 2-hydroxybutyl, or phenyl, provided that when one of -R9 and -R10 is hydrogen, the other is not hydrogen.

14. The dye according to claim 5, wherein in formula [ V], -B2, -Z1 and -Z2 are as defined in claim 1;
-Z1 and -Z2 each represents hydrogen, methyl, acet-ylamino, chlorine, trifluoromethyl or methoxy;
-R13 represents methyl, ethyl, trifluoromethyl, heptafluoropropyl or 2-methoxyethyl;
-R14 represents methyl or ethyl;
-R15 represents hydrogen, methyl, ethyl or allyl;
-R3, -R4 and -R5 each represents hydrogen or methyl;
-X represents hydrogen, methyl, methoxy, trifluoro-methyl, chlorine, bromine, formylamino, acetylamino, or benzoylamino; and -Y represents hydrogen, methyl, methoxy or triflu-oromethyl.

15. The dye according to claim 6, wherein in formula [VI], -X represents hydrogen, methyl, trifluoromethyl, methoxy, chlorine, bromine, formylamino, acetylamino, trifluoroacetylamino, or benzoylamino;
-Y represents hydrogen, methyl, methoxy, ethoxy, chlorine, bromine or trifluoromethyl;

-R16 and -R17 each represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-phenylethyl, 2-hydro-xyethyl, allyl, 2-methoxyethyl, 2,2,2-trifluoroethyl or 2-chloroethyl;
-R2 and -R3 are as defined in claim 6; and -R13 and -R14 each represents methyl, ethyl, triflu-oromethyl or heptafluoropropyl.

16. The dye according to claim 7, wherein in formula [VII], -X1 represents hydrogen, methyl, methoxy, formyl-amino, acetylamino, propionylamino, chlorine, bromine, iodine, or fluorine;
-Y1 represents hydrogen, methoxy, methyl, chlorine, bromine, iodine or fluorine;
-A- represents -CO- or -COO-;
-R18 represents -CH=CH2, -C(CH3)=CH2 or -CH=CHCH3;
-R9 and -R10 each represents hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, allyl, 2-metho-xyethyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-(2-methoxy)ethoxy-ethyl, 2-cyanoethyl, 2-chloroethyl, tetrahydrofurfuryl, ben-zyl, i-propyl, 2-phenylethyl, 2-acetoxyethyl, 2-methoxycar-bonylethyl, 2-ethoxycarbonyloxyethyl, 2-phenoxyethyl, 2-n-hexyloxyethyl, 2-hydroxybutyl, phenyl, 2-acryloxyethyl or 2-methacryloxyethyl.

17. A method of sublimation heat-sensitive transfer recording, which method comprises heating a transfer sheet having an ink layer containing a sublimable dye coated on a base film to sublime the dye thereby transfer recording onto a recording body, wherein the said dye is of the formula as defined in claim 1.

18. A sublimation heat-sensitive transfer recording sheet, which comprises an ink layer containing a heat-sensi-tive sublimable dye coated on a base film, wherein the said dye is of the formula as defined in claim 1.

19. The recording sheet according to claim 18, wherein the ink layer further contains magenta and yellow color dyes.

20. A process for producing a sublimation heat-sensitive transfer recording sheet, which process comprises:
a) dissolving a heat-sensitive sublimable dye in a medium or dispersing the dye in a fine particle form in a medium together with a binder to prepare an ink, and b) coating the ink on a base film and drying the coating, wherein the said sublimable dye is of the formula as defined in claim 1.