CA1073154A - Dyestuff compositions, their preparation and use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
New dyestuff compositions of triphenylmethane dyestuffs containing no sulfo group, have been found which contain 5 to 60% of said triphenyl-methane dyestuff and 40 to 95% of an oxidatively drying varnish on the basis of unsaturated compounds, of a physically drying varnish on the basis of dissolved hard resins, of a varnish which is drying by the cross-linking of low-moleuclar-weight unsaturated compounds to yield high-molecular-weight films under the action of high-energy radiation, or of a varnish prepared using conventional further additives, or of their mixtures, and optionally additional conventional dyestuff pigments, which compositions are well suited for the brightening and shading of black printing inks and pastes containing soot and do not show disturbing viscosity and thixotropy effects as often usual similar pigment compositions do.

Description

` ~ F~
~73~1LS~
The present inven~ion relates to novql dyestu.~ composi-tions~
their preparation and their use for the brightening and shading o~ black print~ng inlcs and pastes.
Black printing pastes and inks cont,in soot as a basis of their color-yielding ~ortion. ~ependin,g on the nuality o~ the soot used, the prints produced therew.it~h have a more or less marked grey or brown tinge. To ob-tain a neutral or bluish black shade, from about 1 to 10.% n~ blue pigment dyes are gcnerally added to the black printing i~ks and pastes. Such dyes are9 for example, phthalocyanines, Milori Blue (complex iron cyanides), sulfated Alkali Blue brands or basic dycs laked with heteropoly acids. Those brightening and shading components have the drawback of being only difficult to dis-perse in the printing ~nks and pastesO Moreover9 the tinc-torial strength and hiding power of these pigments are verymuch ~unctions o~ granulation and particle size distribution~
As experience ha~ shown, it is not possible to achieve entirely optimum conditions as to granulation and thus the brightening ef~ect. Although no dispersing operation is necessary whe~
being mixed with the printing varnish; flushed pigment dye pastes also require optimum granulation of -the pigment.to ensure a high tinctorial strength.
It is ~urther ~nown to ~olubilize dyestuf~ bases in organic acids, such as oleic acids, ~at-ty acids~ wax or resin acids, ?5 and to u.se these solubilized compounds for shading b1ack letter print.ing inks. Those compound~, however~ have the disadvantage of containing too much acid as a result of the stoichiometrîcal ratio o~ dyestu~ base to acid. Such a high acid content is) 29 in many cases, not desirable for applicæ~ion purpose~9 i.ea in . - 2 ~

~ .. ,: . .. . .. .

H0~ 7~ F~

t~e printing techniques.
We have now ~ound new dyestu~f compositions which do not include the disadvantages of the pigments and solubilized . acids and which are excellentlg.suitabl.e ~or -the brightening or shading of black printi~g inks and pastes. In addition to a varnish and optionally a usual dyestuff pigment9 the com positions of the invention contain one or more tr~phenyl-methane dyestu~ bases of.the general f`ormu7a I

1:2 \01 (I) ¢~3 '' , ~ , .

.. .. .. . R4 . . . . : . . . .
in which R1 and R2, ~hich are identical or different from each other~ each stands for a hydrogen or halogen atom9 for example a fluorine9 chlorine or bromine atom9 a lower alkyl, hycdroxy, lower alkoxy, phenyloxy, amino, lower alkylamino, lower dialkyl-amino or phenylamino group, or two vicinal radicals R1 and R2 toge-ther ~orm a fusecl benzene nucleus, R3 stands for a hydrogen or halogen atom~ ~or example a chlorine or bromine atom, a methyl or ethyl group 9 R4 stands for a hydrogen or halogen atomS
~or example a chlorine or bromine a-tom, a hydroxy or lower alk-oxy group, a phenyloxy, d-naph~hylo~J or B-naphthyloxy group~
the phenyloxy and naphthylox~ groups may be substitu-ted by R1 9 for an amino 9 lower alkyl or lower d.ialkylamino group, the alkyl ~9 moie-ty of which may be substitu-ted by a phenyl group 9 for . :

.,: , ', : "' ~3~4~

example a methylamino, ethylamino, benz~l~mino, phenylethyl-amino, dimethylamino or diethylamino grc~up, ~or a phenylamino or naphthylamino group which may be substituted in the nucleus by R1 and/or R2; and R5 stands for a hydrogen atom, a methyl or e~hyl ~ro-up.
Especially preferred are triphenylmelthane dyestuff base~ of formula IJ in which R1 and R2~ which arle identiGal or different from each other9 each stands ~or a hydrDgen or chlorine atom9 a lower alkyl group, especially the methyl, e~hyl or propyl group,. or a lower alkoxy group, especially the methoxy or ethoxy group, R3 stands ~or a hydrogen atom, and R4 ~or a lower alkoxy group, especially the methoxy or ethoxy grou.p, the amino group~ a 3.ower alkylamino group, especially the methylamino or ethyl-amino group, a lower dialkylamîno group, especially the dimethyl~
amino or diethylamino group, or a phenylamino group which may be - substituted in the nucleus by R1 and/or R2; and R5 stands for a hydrogen atom.
The dyestuff bases of the above general ~ormula may also be available in the anhydro ~orm,lacking one watsr molecule. The varnishes;which are contained in the compositions o~ the in-ven~ion and are liquid at room temperature or at a slightly elevated temperature, are of such a nature that the dyestuf~
bases of ~ormula I used according -to the invention are soluble in them~ Such a varnish may contain both natural and synthetic ~5 substanoes and mixtures thereof9 for example oxidatively drying varnishes on th~ basis o~ ~nsaturated compounds, such as tall oil 9 linseed oil~ castor oil, oli~e oil~ cotton~seed oil~
peanut oil; rapeseed oil, soybean oil~ Lish oil or modified 29 colophony resins; physically drying ~arnishes on the basis of , 73~5~

hard resins, for example metal resinates, hydrocarbon resins, modified colo-phony resins or polymer resins dissolved in suitable solvents, for example toluene, gasoline or mineral oil; as well as varnishes or mixtures thereof~
which dry by cross-linking low-molecular-weight unsaturated compounds to yield high-molecular-weight films under the action of high-energy radiation, as well as varnishes prepared using further addi~ives usual in practice, such as wax pastes (up to 5 %), siccatives (up to 3 %) and/or matting agents ~up to 15 %).
The dyestuff bases of formula I have a good to very good solubility in the said varnishes and when dissolved they are in a molecule-dispersed form. The compositions of the invention contain :Erom 5 to 60 % by weight, preferably 10 to ~0 %, of one or more dyestuff bases, the content of the varnish may be ~0 to 95 %by weight. The content o:E pigments may be up to 35 %, preferably up to 20 % by weight.
In particular, the present invention provides a dyestuff composi-tion having a content of from 5 to 60 % of one or more tr~phenylmethane dye-stuff bases of the general formula I

1 ~ ~ ~ N

~H

.~

_ 5 _ ~, . , , 1~73~

or of the corresponding anhydro bases in which Rl and R2, which are identical or different from each other, each stands for a hydrogen or halogen atom, a lower alkyl, hydroxy, lower alkoxy, phenyloxy, amino, lower dialkylamino or phenylamino group, or two vicinal radicals Rl and R2 together stand for a fused:b~n~ene nucleus, R3 stands for a hydrogen or halogen atom, a methyl or ethyl group, R4 stands for a hydrogen or halogen atom, a hydroxy or lower alkoxy group, a phenyloxy, ~-naphthyloxy or ~-naphthyloxy group, which are un-substituted or substituted by Rl, or R4 stands for an amino group, a lower alkyl or dialkylamino group, the lower alkyl moiety of which being unsub-stituted or substituted by a phenyl group, or R~ stands for a phenylamino or naphthylamino group unsùbstituted or substituted in the nuclei by Rl or R2 or both and R5 stands for a hydrogen atom, a methyl or ethyl group, of from 40 to 95 % o an oxidatively drying varnish on the basis of unsaturated com-pounds, ofaphysically drying varnish on the basis of dissolvecl hard resins, of a varnish which is drying by the cross-linking of low-molecular-weight unsaturated compounds to yield high-molecular-weight films under the action of high-energy radiation, or of a varnish prepared using conventional further additives, or of their mixtures, and 0 to 35% of conventional dyestuff pig-ments.
The compositions of the invention may be prepared by various methods:
One or more dyestuff bases of formula I may be dissolved while stirring and optionally heating in a varnish of the above-cited type; a solution of one or more dyestuff bases of formula I in an adequate volatile solvent may be blended with a non-volatile varnish and the mixture may be freed from the solvent used by distillation; the aforementioned solutions of one or more dye-stuff bases may be blended with one or more dyestuff pigments or with a flushing paste of a pigment; a solution of one or more dyestuff bases of ~ - 5a -: , : :. .
:: ,; : ~ , : : , , :,, ::: , , ~ :
, . ;, i: : ., ~7~S~L

Formula I in a varnish instead of pure varnish is used for flushing an aqueous pigment press cake.
Since the solution of the dyestuf bases in the varnish has - 5b -~, . . .

: ' , . ' : , ' :: ~, , :: ~ ;

. . HOE ~
~3~5~
the llature of a real solution~ the phenomenon o~ structural ~iscosity or thixotropy, as very frequently observed with pastes made from dyestuff pigments, does not occur in the com-positions of the in~ention or it occurs to only a minor exten~
S ~ ~ there i s ~ ~certAin c.onten~ of dyestu:Ef ~igment invol~ed, thus making processing substantially easier. Depending on the concentration of dyestuff bases and pigments and on the viscosity of the pure varnish9 the compositions o~ the in-vention result in high- or low-vi~cosity pastes that remain pourable even a~ter prolonged storage.
Compositions of the invention which simultaneously contain dyestuf~ bases and dyes~uff pigments have a ver~ advantageous viscosi-ty. This is of a particular interest when a solution o~ one or more dyestuff bases in a ~arnish is intended for the flushing o~ an aqueous pigment press cake, since in this manner compositions having a high ~otal content of dyeing agents and nevertheless a low viscosity and thixotropy can be preparPd .
The compositions o~ the invention may be added while shor~ly stirring to an unbrightened printing ink or paste o~
a printing varnish and soo-t and distributed therein to give a homogenous mixture, All the compositions of the invention lead~
with an equally good effect~ to brightened or shaded black printing inks or pastesS whose ~iscosity is hardly altered by

2~ the brightening or shading with the oompositions of the in-ventionO
The brightened or shaded printing inks or pas~'es con-tain from 2 to 50 %, preferably 5 to 30 %, of soot and from 0,1 to 29 15 %s preferably ~rom 2 to 1b %9 of dyestuff base, as well as~

-- , , : ................ . .-. .

. ; ' : . -: :

~L Z

~73 optionally~further.dyeing agents.
~hen brought into contact with the acid groups on the sur face of the soot pigments (cf. Ullmann, Vol. 14, pages 794-7g5 and with -the acid groups of the varnish" i~ any, the dyestuff 5-- bases of formula I9 used according to the invention, bring about immediate ~ormation of the corresponding dyestuff salts which show violet, blue or green, preferably blue9 shades.
When ~uch a salt is formed with the acid groups of the soot pigments9 the bro~nish or greyish black intrinsic color of soot is shaded directly on the surface o~ the soot pigments9 i.e. it is transformed into a brightened neutral or bluish black color. The ~act accoun-ts for the outstandingly high ef~iciency and hiding power of the compositions used according to the inve~tion.
Another effect is that -the marked bronze tone caused by brightening and shading soot with monosul~ated Alkali Blue pigments 9 i . e a reddish metal-like color of the resulting black print, may be reduced to any extent desire~ by partly re-plaoing the monosulfated Alkali Blue pigments by the compo-sitions of the dyestuf~ bases of the cited general ~ormula I
according to the in~ention. The use o~ compositio~s exclusively containing -the dyestuff bases for the brightening of soot does not resul-t in a perceptible bronze, so that a brilliant in-tense black color impression is obtained.
2~ The brightened or shaded printing inks or pas~es prepared with the co~positions o~ the invention may be used for the sheet or reel prin-ting in the letter or offset-printing technique9 optionally while expos.ing the printecl m~terial to 29 heat ~heat ~et), in the intaglio printing or in the non 7 ~

,, , . : ~ : .. . -, . ., , . ~ . . .

HOE ~ 7 ' aqueous ~lexo-printing technique.
The ~ollowing Example~ illustrate the ~nvention, the parts and percentages being by weight unless stated otherwise~
E ~ A M P L E 1:
__ 30 ~rt~ of ^ dyo ~U~ P baæ~ of '-he c-~mu.

\C/~ \¢~
~H3 ~ ~H3 C~3 . were dissol~ed at room temperature, by means of a ~neader~ in 70 parts ~f a varnish o.f 95 % of linseed oil and 5 % of zinc resina~e -to yield a homogenous dark blue solution. 10 Part~
of this composition were homogenously incorporated in 90 parts of a commercial-type book-o~set printing ~arnish containing 20 parts of a Channel-type soot by passing i.t through a three-roller~mill.
Printing o~ this brightened black ink on art paper with a color pick-up o~ 1.5 g/m2 resulted in an intense black im~
pression without any bronze e~ect.
According to Æxample 1, the dyestuf~ bases given in the ~ollowi~g Table 1 may also be used~

. . : .
. , , : ::: "
~ : :
... . . ~ .. .. , . " : . . ;
. : : .:
.

~7 , T A B L E
Example Dyestuf:E base Shading of printi.ng soot 2 ~ i~ "~ ~) '` ''~~ ' ' ~ . ,' ` ' .
NH ' , `'. , , ' {~1 , ,

3 . ~ ~ ~jN~

~ redd:L~h blue '` '- , ~y , . .

N~I

- CH CH

4 . I ~i ~ 3 ~' C ~
Cl ~iolet Il `I
fI
~C13 -- g c~

: ; : ~: i ~C~73~5 CH30 ~ \~C~'~ ~
O(:~H3 , .
.
.g~e~n:Lsh .bluQ
' ' ~,J . ' :' ' - ~
' . OC~I . -.
3 . .
:' . . , ` ' 6 ~ . ~ ~¢~ ~N ~¢~
~~g~een~~~ ~=
.-, ....... ' ~ , .
., ., .. OC2~I5 '.

7 $~
- 1 reddish. }~lue "' . ¢~ ' .
.. '' ' ~ .
"~
;, ' .
.

- 10 ~

:: :

, . ; . - :... . . .. . .

;, . . ::: . . ,, ~ , . ; .: .

~7 ~3 8~ Iue~~
' ' -. ~ -' ~
, '' ~ ',.

. ~ .
.. .. . .
9 Cl CH3 C~3 Cl NH ~ ~ N ~ violet NH
. . ¢~,~Cl E X A M P I. E 10:
50 Parts of a 30 % solution o~ a dyes~ufI base of the 20f ormula ¢~C ~

3 ¢~ . CH3 NH

~ CII
in -t~l1. oil were mixed while shortly stirring with 50 par ts of 2~ a :`lushing pas-te prepar~ed according to the known met;hod from . ~
:, ` ". ' ' ' ~

.. .. ~ . , . , .
.

7 ~F 037 ~7~5~

42.5 parts of the Alkali Blue pigment of the ~ollowing con-stitution r~ ~ ~ /[;3 )~ o4- ~ 0,l ~ C~3 and.~rom 57.5 parts of tall oil at room temperakure to yield an only weakly thixotropic composition.
In letter printing, the composition produced a brightened black shade o~ good color depth having a neutral or bluish shade, depending on the amount used, and compared with a print produced with a pure flushing paste o~ the speci~ied type, it gave an-only slight reddish bronze; bronze being understood to mean a reddish metal-like color impression on the sur~ace.
2~ E X A M P L E 11-When 25 par-ts o~ the aforementioned dyestuf~ base solution and 75 par-ts of the said flushing paste were used according to the method described in Example 109 the composition ob-tained produced a brightened black print having an increased bronze e~ect as compared with -that obtained with the composition o~
Example 10.
E X A M P L ~ 12:
When 75 parts of ~he said dyestuf~ base solution and 25 29 parts oP the said flushi~g paste were used accord.in~ to the _ 12 --, . .... .

. . ' ,, ' ', ' ' .. . ' ' . '`
,.
. , .. - ;

HOE ~7_LF~
~73 method described in Example 10; the composition obtained pro-duced a brightened black print ha~ing a reduced bronze ePfect as compared with that obtained with the composition of Example 10.
E X A M P L E 13~
When, according to the method of Example 10p a dyestuPP
base of the formula H C

5 2 . . . ~2 . ~ C ~
~ .
., ~J - .
. ~I

~ ~ -C2H5 was used ~or the dyestuff base solution and this solution was m.ixed with the flushing paste mentioned in Example 109 the re-sulting composition showed a weakly bronzed brightened black color having a reddish blue shade.
E X A M P L E 14:
60 Parts of a 30 % aqueous press cake oP a dyes-tuPf pig-ment of the constitution r~ ~ ~ ~NH
~ ~, ~ S3 o 8 (S0~)0~1 ¢~1 29 ~ ( 2)o 3 ~ ~ ) 0~7 -_.

were mixed with an 18 % solution of a dyestuff base of the formula ~ ~ ,~ ,~N ~
W -~c~J W

N~

lo ¢~ oc~3 in a varnish of 95 parts o~ soybean oil and 5 parts o~ zinc resinate in a double trough kneader of the known type in such proportions tha~ a 1ushing process, i.e~ separation o~ water~
took place. The ~ater was eliminated 9 and the added amo~n-t of the above dyestuff base solution was increased to a total o~
82 parts. The residual water content was eliminated in vacuo~
The resulting low-viscosity composition produced brilliant bluish shaded black prints of high gloss and low bronze.
E X A M P L E 15:
.__. . .. .
When the soybean oil used in Example 14 was replaced by saf-flower oil, sperm oil or deodorized ~ish oil, the same good compositions as in Example 14 were obtained.
_ _ 16:
80 Parts of a 40 % solution of a dyestuff base of the formula .. .: , , . . .
. .
. ., ,. : , .: . . : . .

; . .
. .

: ,. .. :, ~ .

..
. ~ ' .

73~5~L

¢~ --~ C "~
3 ~ CH~

J ~ NH

in m-toluidi~e were hea~ed in vacuo while vigorously stirring, so that only a ~mall amount of m-toluidine was distilled of~
at a temperature o~ at most 140C, After addition of 68 parts o~ a varnish of 92 par-ts of soybean oil and 8 parts of zinc resinate, distillation of -the solution which then had a lower viscosity was continued until the remaining m-toluidin~ was ~liminated~
The resulting low~viscos~ty homogenous composition pro~
duced non-bronzed outstandingly deep brightened black prints.
~L .
When according to the method of Example 16 a solution of a dyestuff base of the formula ~0 ¢~ ~C~ ~
¢~ ' . / N \
CE~ 3 in aniline was used~ the homogenous compositi.on ob-tained pro-~
- duc2d a non-brorlæed reddish blue shade on printing soot, ,. .
; ~ ,,. , , :
.. . . . ,. :~;
. , . . -;
. : ,. . . -,, ,. , . ~ , , . ~ ,. . .

- , . ~ . . ..
,, HOE ~ Z
~73 ~1 A M r I, E 18:
When according to the method o~ Example 16 a solution of a dyes~uff base o~ the formula ~H3 ~H3 ~C

. ~H2 in o-toluidine was used~ the homogenous composition obtained produced a non-bronzed violet shade on printing soo-t.
~ Y A M r L E ~
A solution o~ 40 parts of a dyes-tuff base of the formula [~ ~ C ~/ [~
'. ~ , , .

in 80 parts of a ~arnish of 45 parts of linseed oil, 45 parts of soybean oil and 10 parts of zinc resinate was blended in a kneader with 20 parts of a dry pigment dyestuff o~ the ~ormula a5 ~ ~H ~_ ~ ~ ~I
¢~ ' _ 16 -.. .
.

:

9~S~
and homogenized b~ kneading it therein .~or 1 hour. The re-sulting composition produced a brigh~ening effect of out-standi~g hiding power on printing soot with a weak bronze on the black print.

When instead o~ the pigment dyestuff used in Example 19~
the same amoun~ of Milori Blue (complex iron cyanide) was used9 the resulting composition produced a marked blue brilghtening or shading ef~ect on printing soot.

When instead of the pigment dyestu~ used i.n Example ~9, the same amount of a copper-phthalocyanine plgment was used, the resulting composition produced an out~s-tancling greenish blue brightening or shading ef~ect on printing soot and imparted a very good fast~ess to light.
E X A M P L E ~2-60 Parts of a dyestuff base of the fo~mula ~ ~TH ~ ~ N

" ¢

NEI
,~
~5 ~ -were introduced portionwise into 150 parts of linseed oi:l (acid number iess than 69 viscosity 65 P at 20~C) 9 and the mix-ture was s~tirred for 2 hour at 35& by means of a h-gh-capaci-ty~
29 hi~h~peed stirrer o~ the known type. The resulting bl~e ~ 17 ~

.
.
.
. . . :
;:. .. .:
' '': ~ : .' ."
- ~ ~

. HOE ~ ~

~C~73~5~
solution was pourable and had a viscosity of 80 P at ~1C;
when used a~ in Example 1~ it provided a deep bluish black print.
E X A M P L E 23:
.
: 5 61 Part~ of ~ re_tll~4 b_~e o vh^ ~o~mula NH~

Br . l Br ,rq ~
.. N~

Br were introduced portionwise into a laboratory kneader provided "15 with sigma-shaped blades and containing 150 parts of a varnish.
This varnish was obtained by heating 1300 parts of varnish linseed oil (iodine number 185 and acid number 2) a~d 20 parts o.~ calcium resinate to 180C for half an hour. After the mixture had been kneaded ~or 1 hour at 30 - 40C, a blue -pourable paste was obtained which had a viscosity of 120 P
at 20C and which was very well suitable for brightening prin-ting soot.
E X A M P L ~ 24:
Heating of 80 parts of ~arnish linseed oil and 80 parts of an ester o~ dimeric resin acid to 260~ under a carbon dioxide . inert gas a~mosphere while stirrillg :~or one hour and subseque.rlt : diluting wi~h 40 p~rts of mineral oil boiling betwee~ 280 and 310C resu:Lted` in a varnish having all acid number of 3 and a 29 viscosity o~ 50 Poise. 130 Parts o~ a dyes-tuf~ ba~e of the r HOE

~or~ula ~ ¢r~J
0~ . ~ C~ Ir ~, c, ' ' ~
. . NH
¢~
c2~5 were divided in 200 parts of the said varnish by means of a high-speed stirrer of ~he known type to yield a pourable paste having a viscosity o~ 200 P at 20C and providing deep brightened black prin-ts.
E X A M P L E 25:
In a manner analogous -to Example 24, a honey-colored varnish having a viscosity of 190 P at 20C was prepared by introducing 80 parts of a colophony-modified phenol resin into 80 parts of a linseed oil heated to 150C7 then heating the mixture to 260C for 45 minutes under an iner-t gas atmosphere and dilu-ting i~ with 40 par-ts of a mineral oil boiling between 280 and 310C~ 100 Parts of the dyestuff base described in Example 1 were dissolved in 200 par-ts o~ -the above varnish in a laboratory kneader provi~ed with sigma-~haped blades and heated -to 60C~
ThQ resulting pourable dark blue paste havi~g a viscosity of 250 P a~ 20C pro~ided deep brightened black prints.
~X~ 26:
~._ 70 Parts o~ a phenol~modi:Eied colophony resin were mixed 29 w~lile s-~irring at 200~C with 40 parts Gf a lln~ed oil-- 19 .

-, . .
.. : .

HGE ~ ~7 ~73~S~
modlfied alkyd resi.n to yield a limpid mixture which was stirred with 90 parts of a mineral oil fraction, boiling from 260 to 290C, ~or another 60 minutes at 180C. The resulting honey-colored varnish had a viscosity o~ 220 P at 20C. 20 Parts of t.h~ ~y~qt.l~f~ h~R ~s~ribed in F.xampl.e 1 were disso]ved in 150 parts of this varni~h at 50C in a laboratory kneader.
The resulting paste which was pourable at room tempera~ure had a viscosity of 350 P at 20G and was very well suitable ~or brightening printing soots.
E X A _ P L E 27:
25 Parts of an alkyd resin having a low oil content (vis-cosity of a 50 % solution in white spirit: 600 cP, acid number 5) were dissolved .in 110 parts o~ a mineral oil boiling from 260 to 290C. To this solution~ 44 parts of a hydrocarbon resin polymerized in the known manner from Cg~fractions of the mineral oil a~d having an indene content o.~ less than 20 % o~
the polymerized portions, a melting point of 86C (capillaries), a viscosity of 13 cP (as a 50 % solution in toluene) and a medium molecular weight of 900, and 44 parts of a hydrocarbon resin prepared by polymerization of a Cg~raction having an indene content o~ 25 % o~ the polymerizable portions and showing a melting point of 125UC, a viscosity o~ 36 cP (as a 50 % solution in toluene) and a medium molecular weight of 1600t ~ere added. After a clear solution had been obtained~
this was cooled. Charac~eristics: solids 50 56, viscosi*y 500 cPg acid number 1.
By means of a high-capacity stirrer of the known type~
20 parts of the dyestu.ff ba.se described in Example 1 were rlis~
29 sol~ed in 10Q parts o~ thi.s ~arnish at 30 - 40~C to yield a - 2~ ~

.. . ...
. : . , . ::, :: , , ~
. , .
.

. .

~1~73~L5~
`, pourable paste ha~ing a viscosity of 150 P at 20C and being very well suitable for brightening printing soots.

A homogenous paste was prepared by mixing 20 parts of the dyestuff base described in example 19 40 parts of a polyester that had been prepared from a diol having 3 carbon atoms and ; a long-chain hydroxy dicarboxylic acid and esterifled with acrylic acid and having a mediu~ molecular weight of 2,000y and 40 parts of trimethylolpropane triacrylate in a three-roller mill. 12 Parts of this paste were stirred with 12 parts of a printing soot, 8 parts of a photo initia-tor (benzophenone/
Michler's ketone at a ratio of 1 : 3~ 9 41 parts of the above polyester and 27 parts of trimethylolpropane triacrylate.
A pri.nt prodllced with ~he brightened black ink thus prepared (viscosity 280 P at 23C)dried ~ery ~uickly w.ith a brilliant deep black shade when exposed to ultraviolet light.
According to the method mentioned in Example 28, the dye~
stuf~ bases of the following Table 2 may also be used:

____ Example Dyestuff base . Shadin~r of ~r~

C2ll5 l~ ~ C ~ ~ C~l~s blue NH

OcM~

21 -~

, .
....
. .. .. . .
: .

HOE
';73~5~ --Example DyestufI base Shadi~lg of ~o) : ' '' ~l'o~ ~ ~.o~
- ~ - ` ¦ ` violet NH
. ~ .
. - : ..

C ~ ~

blllR
,.
~ .

~ 2 '.

32) ~ll~C~ ~

1~1 blue --' ~
NH
~3 .
i`l~CH3)2 .~ . . .. . .
:. , . ;

., , . . . ~

HOE 7,~
" ~CD73~5fl~ ~
Example DyestuI:E base Shading o:E printingSoot e~NH ~0 \ C ~

b~:u-e'~
N~

~3 !

, ,~, N
~J ~ blu.'Lsh gx eër~
~_Br 3~) ~~ ~ C ~ N ~ bl-iish green C~3-N~ CH3 Cl E~ N ~ ~ N ~3 b~:ue ~3 . .
0~1 - 23.--- . .. . . . .. . .

.: . . . . .

HOE__~L 037 73~4 .- Example D;~re5tuf E b~se Shading of ~r~

~ ~ C ~
~J~ ljluish-` gr~n . . .
O

38) ~ N ~ ~ ~3 3 ~ ~ h--11 ~- green ,~ ...........

.

..~.
39) riol~*
~3 N ( C2Hs ) 2 _ ~4 --. . ~. . . .

. i , . .

;" , : -, . : .

HOF, 75 ~73~S~L
I~xample . DyestuPI base Shading of ~o) ,.

~31'' N
.... ' ~ .
vi~let NII-- c~3 ~, N ~ ~ N ~

violet 2 ) , ,c.

~3 T~ c blu~

N~ CII3 ~ .
Z5 ~

.. - .

: : :

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A dyestuff composition having a content of from 5 to 60% of one or more triphenylmethane dyestuff bases of the general formula I

(I) or of the corresponding anhydro bases in which R1 and R2' which are identical or different from each other, each stands for a hydrogen or halogen atom, a lower alkyl, hydroxy, lower alkoxy, phenyloxy, amino, lower dialkylamino or phenylamino group, or two vicinal radicals R1 and R2 together stand for a fused benzene nucleus, R3 stands for a hydrogen or halogen atom, a methyl or ethyl group, R4 stands for a hydrogen or halogen atom, a hydroxy or lower alkoxy group, a phenyloxy, .alpha.-naphthyloxy or .beta.-naphthyloxy group, which are un-substituted or substituted by R1, or R4 stands for an amino group, a lower alkyl or dialkylamino group, the lower alkyl moiety of which being unsubstituted or substituted by a phenyl group, or R4 stands for a phenylamino or naphthyl-amino group unsubstituted or substituted in the nuclei by R1 or R2 or both and R5 stands for a hydrogen atom, a methyl or ethyl group, of from 40 to 95% of an oxidatively drying varnish on the basis of unsaturated compounds, of a physically drying varnish on the basis of dissolved hard resins, of a var-nish which is drying by the cross-linking of low-molecular-weight unsaturated compounds to yield high-molecular-weight films under the action of high-energy radiation, or of a varnish prepared using conventional further additives, or of their mixtures, and 0 to 35% of conventional dyestuff pigments.

2. A dyestuff composition according to claim 1, containing tri-phenyl-methane dyestuff bases of formula I, or their corresponding anhydrobases in which R1 and R2 which are identical or different from each other, each stands for a hydrogen or chlorine atom, a lower alkyl or lower alkoxy group, R3 stands for a hydrogen atom, and R4 stands for a lower alkoxy, amino, lower alkylamino, lower dialkylamino, benzylamino or phenylamino group, this latter being optionally substituted in the nucleus by R1 and R2, and R5 stands for a hydrogen atom.

3. A dyestuff composition according to claim 1, containing from 10 to 40% of one or more triphenylmethane dyestuff bases of the general formula I defined in claim I or their corresponding anhydro bases.

4. A dyestuff composition according to claim 1 which is a homogenous solution.

5. A process for the preparation of a dyestuff composition according to claim 1, which comprises dissolving a dyestuff base of formula I or an anhydro base thereof in the varnish at a temperature of up to 180°C while using a stirring or kneading apparatus.

6. A process for the preparation of a dyestuff composition according to claim 1, which comprises blending the varnish with a melt of the dyestuff base of formula I defined in claim 1 or an anhydro base thereof.

7. A process for the preparation of a dyestuff composition according to claim 1, which comprises flushing an aqueous pigment press cake with a solution of a dyestuff base of formula I defined in claim 1 or an anhydro base thereof in a varnish.

8. A process for the preparation of a dyestuff composition according to claim 1, which comprises distilling off the solvent from a solution of a dyestuff base of formula I or an anhydro base thereof and a varnish in a solvent.

9. A process for preparing a printing paste or ink comprising incor-porating a dyestuff composition according to claim 1 into a soot containing acid groups.

10. A printing paste or ink containing from 2 to 50% by weight of soot, from 0.1 to 15% by weight of one or more dyestuff bases of the formula I defined in claim 1 or anhydro bases thereof, and a varnish.

11. A printing paste or ink containing from 5 to 30% by weight of soot, from 2 to 10% by weight of one or more dyestuff bases of the formula I
specified in claim 1 or the anhydro bases thereof, and from 30 to 90% by weight of a varnish.

12. A printing paste or ink according to either of claims 10 or 11 which includes a further coloring agent.

13. A dyestuff composition according to claim 1 wherein said dyestuff base is a dyestuff of the formula

14. A dyestuff composition according to claim 1 wherein said dyestuff base is a dyestuff of the formula

15. A dyestuff composition according to claim 1 wherein said dyestuff base is a dyestuff of the formula