Note: Descriptions are shown in the official language in which they were submitted.
~13~i3~6~
This invention relates to imprGved brightener compositions
comprising a mixture of three different components.
Our Canadian Patent No. 1,110,013 relates to mixtures of
optical brighteners consisting of from 0.05 to 0.95 part by weight
of a compound of the formula I
R2 ~ ~ ~ CH=C~ A
and of from 0.95 to 0.05 part by weight of a compound of the
formula II / C
,~ \\
\ _ ~
\ II
D
in which the symbols X, Rl, R2, A, s, C and D are defined as
follows:
X is oxygen or sulfur, Rl and R~, which may be identical or differ-
ent, are radicals selected from the group consisting of hydrogen,
fluorin~ or chlorine atoms; phenyl, Cl galkyl, Cl 4alkoxy, Cl 4-
dialkylamino, acylamino groups or optionally functionally modified
carboxy or sulfo groups, or two ~icinal radicals Rl and R2, when
taken together, stand for a benzo r-.ng, for lower alkylene or 1,3-
dioxapropylene; A is cyano, a group of the formula -COOR or CONR2
with R3 being hydrogen, Cl l~alkyl, cycloalkyl, aryl, alkylaryl,
halogenaryl, aralkyl, alkoxyalkyl, halogenalkyl, hydroxyalkyl,
alkylaminoalkyl, carboxyalkyl or carboalkoxy-
.1 -2-
,. . .
. .
... . .. . .
~3~i3~
_ 3 _ _OE 78/F 182
alkyl, or two allcyl or alkylene radical.s standing for R3,
when taken together with the nitrogen atom, being morpho-
lino, piperidino or piperazino ring; or A is a group of
the formula
or
in which
Rl is straight chain or branched alkyl having from 1 to 10
carbon atoms, preferably l to 6 carbon atoms, which may be
substituted by hydroxy, halogen, lower alkoxy, dialkylami-
no, lower alkylmercapto, chloroaryloxy, aryloxy, arylmer-
capto or aryl radicals both alkyl groups contained in the
dialkylaminoalkyl groups, when taken together, standing
optionally for a morpholino, piperidino or piperazino ring;
or R4 is a group of the formula -(CH2CH20)n-R with n being
1, 2 or 3 and R being hydrogen; lower alkyl, dialkylamino-
alkoxyalkyl or alkylthioalkoxyalkyl, the alkyl groups in
dialkylaminoalkoxyalkyl, when taken together, forming op-
tionally a piperidino, pyrrolidino, hexamethylenimino,
morpholino or piperazino ring; or R4 is a group of the
formula -(CH2)m-CH=CH-R with m being an integer of from 0
to 5, or R4 is a radical of the formula
R5
~ R6
wherein R5 and R6, which may be the same or different, are
radicals selected from the group consisting of hydrogen,
fluorine or chlorine atoms, phenyl, lower alkyl, lower alk-
,
.
,: :
: ::
~: :
~3~3516
_ L~ _ HOE_78/~ 182oxy, C1 4acylamino groups or optionally modified carboxy
or sulfo groups, two vicinal radicals R5 and ~6, when taken
together, standing optionally for lower alkylene, a fused
benzo ring or 1,3 dioxapropylene;
B is a polycyclic aromatic radical having at least three
condensed r.ings optionally carrying non chromophoric sub-
stituents;
C is amino, substituted by one or two alkyl, hydroxyalkyl,
acyl or phenyl groups, the phenyl group containing optio-
nally one or several non chromophoric radicals and twoalkyl groups, when talcen together with the nitrogen atom
of the amino group forming optionally a pyrrolidino or
piperidino ring or a piperazino or morpholino ring; or C
is alkoxy, hydroxyalkyl, acyloxy, alkylthio or carbalkyl-
mercapto;D independant from C is defined as C and may further stand
for a chlorine atom.
By further modifying this invention it has now been
found that the brightening effect of these mixtures can be
improved when addine to the above-described mixture a
third component of the series of the bis-benzoxazolyl- or
bis-benzothiazolyl-stilbenes.
Subject of the present invention, consequently, are
mixtures of optical brighteners consisting of from
a) 0.98 to 0.50, preferably 0.98 to 70, in particular 0.98
to 0.90, part by weight of a mixture consisting of from
0.05 to 0.95 part by weight of a compound of formula I
as defined above and of from 0.95 to 0.05 part by weight
29 of a compound of formula II as defined above and of from
' ;
~ :,: :. -
~, . . .
113ti3~6
- 5 - HOE 78/F 18?
b) 0.02 to 0.50, preferably 0.02 to 0.30, particularly pre-
ferably 0.02 to 0.10, part by weight of a compound of
formula III
2 ~ ~ ~ ~ CH = C~l - ~ - ~ ~ III
R R2
wherein X, R1 and R2 are defined as in formula II.
Compounds of the formula I, wherein X, A, R1 and R2
are defined as above and R4 stands for a member of the f`ol-
lowing group: C1_6alkyl, C1_6chloroalkyl, dimethyl- or di-
ethylamino-C1_4alkyl, morpholinoethyl, N-~-piperidinoethyl,
N-~-(N'-methylpiperazino)-ethyl, benzyl, phenoxy-C1 4alkyl,
chlorphenoxy-C1_4alkyl, C1 4alkylmercapto-C1 4-alkyl,
phenylmercapto-C1_l~alkyl, phenyl, C1 6alkylphenyl, di-C1 6-
alkylphenyl, chlorphenyl, dichlorophenyl, C1 6alkoxyphenyl,
~- or R-naphthyl or a group of the formula -(CH2CH20)n-R with
n being 1, 2 or 3 and R being hydrogen, C1 7alkyl, C1 4al-
kylmercapto-C1 4alkyl, dimethyl- or diethylamino-C1 4alkyl
or morpholino-C1 4alkyl, are particularly interesting.
Especially preferred are those compounds of the formula
-I wherein X is O or S, R1 and R2 in 6 or 7 position each
are hydrogen or chlorine atoms, C1 lialkyl, phenyl or, when
taken together, a fused benzo ring and R4 in the group A
is C1 6alkyl, C1 6chloroalkyl, C1 4alkoxy-C1 4-alkyl,
hydroxy-C1 4alkyl or a group of the formula -(CH2CH20)n-R'
with n being 2 or 3 and R' being hydrogen or C1 4alkyl.
Particularly interesting as a subgroup are further
those compounds of the formula I wherein X is oxygen, R
~3~35~
- 6 - HOE 78/F 182
in 5 position is hydrogen or chlorine, methyl or phenyl,
R2 is hydrogen or R1 and R2 each are a methyl group in 5,6
or 5,7 position and R4 in the group A is methyl, ethyl, n-
or iso-propyl, n- or isobutyl, pentyl, chloromethyl, B-
chloroethyl, ~-hydroxyethyl, ~-methoxyethyl, B-ethoxyethyl,
benzyl, phenyl, o-tolyl, 2,3-dimethylphenyl, o-chlorphenyl,
p-chlorophenyl, 2,4-dichlorophenyl or p-methoxyphenyl.
Preferred compounds of formula III are those wherein
R1 and R2 in the 5-, 6- and 7-position denote hydrogen or
chlorine atoms, C1 llalkyl or phenyl, particularly prefer-
red are those compounds wherein R in the 5-position de-
notes hydrogen or chlorine atom, methyl or phenyl, R2 de-
notes hydrogen or R1 and R2 both denote methyl in the 5,6-
or 5,7-position.
Especially preferred are those compounds of the for-
n3ula II in which B is pyrene and C and D independant from
each other are C1 ~alkoxy.
By the term "functionally modified carboxy group" there
are to be understood carboxylic acid derivatives in the
largest sense, i.e. compounds having one carbon atom, three
bonds of which are occupied by hetero atoms, in particular
oxygen, nitrogen and sulfur. In a narrow sense these com-
pounds include salts with colorless kations, among which
alkali metal~or ammonium ions are preferred, and further
the cyano group, a carboxylic acid ester group or a carbon-
amide group. Carboxylic acid ester groups include in par-
ticular those of the formula COOQ1 wherein Q1 is a phenyl
radical or optionally branched C1 4alkyl. Carbonamide groups
29 include in particular those of the formula CoNQ2Q3 wherein
,
3~5~
- 7 - HOE 78/F 182
Q2 and Q3 each are hydro~en atoms or C1 4, optionally sub-
stituted alkyl groups, which may form a hydroaromatic ring,
when taken together with the nitrogen atom.
By the term "functionally modified sulfo groups" there
are to be understood, in analogy to the above statements,
radicals with a sulfo group linked to a hetero atom, i.e.
salts with colorless kations, preferably alkali metal or
ammonium ions, the sulfonic acid ester groups and the
sulfonamide group. Sulfonic acid ester groups include in
particular a group of the formula S020Q1 wherein Q1 is
defined as above and sulfonamide groups include those of
the formula So2NQ2Q3 wherein Q2 and Q3 are defined as
above.
Suitable acyl groups include in particular those of
the formula COQ~ wherein Q4 is optioanlly substituted, pre-
; ferably lower, alkyl or phenyl, in particular unsubstituted
C1 4alkanoyl or benzoyl. Preferred substituents for R3 are
C1 6alkyl, halogenalkyl or alkoxy.
In addition to the above subgroups any other subgroups
may be formed from the definitions for X, R1, R2, A, B, Cand D. It is quite natural that it is not intended to
introduce new matter according to 35 U.S.C. 132 by the
formation of such new sub-groups.
Unless stated otherwise, alkyl groups and other groups
derived therefrom, each have of from 1 to 4 carbon atoms.
The following radicals may stand for R1 and R2:
methyl, ethyl, n- or isopropyl, n- or iso-butyl, pentyl,
hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy,
29 dimethylamino, diethylamino, trimethylammonium, triethyl-
,
. , ~ .
~36356
_ 8 _ HOE 78/~ 182ammonium, acetylamino, cyano, -S03H, carboxy], carbometh-
oxy, -ethoxy-, -propoxy, -butoxy and the corresponding
groups of the class of sulfonic acid alkyl esters, methyl-,
ethyl-, propyl-, butyl-carbonamide, and the corresponding
groups of the class of alkylsulfonamides and the corre-
sponding dialkylcarbonamide groups or -sulfonamide groups.
Two vicinal groups R1 and R2 may form thogether a fused
benzo or cyclohexyl ring. Those compounds are preferred
that contain the benzoxazolyl group (X - O).
R4 may stand for the following groups:
methyl, ethyl, n- or isopropyl, n- or iso-butyl, pentyl,
hexyl or the chloroalkyl, hydroxyalkyl, dimethylaminoalkyl,
diethylaminoalkyl, methoxyalkyl, ethoxyalkyl, propoxyalkyl,
butoxyalkyl, methylenmercaptoalkyl, ethylmercaptoalkyl,
chlorophenoxyalkyl, phenoxyalkyl, phenylmercaptoalkyl,
phenylalkyl and naphthylalkyl groups which derive there
from; R4 may further stand for groups of the formula
(CH2CH20)nR with n being 1, 2 or 3 and R being hydrogen,
methyl, ethyl, propyl or butyl, dimethyl- or diethylamino-
alkoxyalkyl having from 1 to 4 carbon atoms in the alkyl
- or alkoxy moiety or those alkylthioalkoxyalkyl groups which
have likewise of from 1 to 4 carbon atoms in the alkyl or
alkoxy moieties. Examples of these radicals are those of
the formulae
~ 25 CH CH OCH , -CH2CH20C2H5, -CH2CH20C3 7, 2 2
-CH2CH20c6Hl3J -CH2cH20cH < C H ~ -CH2cH20c6H11~
2 2 2 3~ (CH2CH20)2c2Hs~ -(CH2cH20)2cl~H9
2 2 3 2 5J CH2cH2ocH2cH2sc2Hs~ -CH2CH20CH2CH2-N(CH2)
29 -cH2cH2ocH2cH2-N(c2H5)2 or -cH2cH20 2 ~ ~
.~ : : i , :
1~L3~3~;6
Alternatively R4 may be unsubstituted phenyl or phenyl
substituted once or twice, in which case the alkyl, alkoxy, acyl,
carboalkoxy, alkylcarbonamido, alkyls~lfonam;do and sulfonic acid
alkyl ester groups may have of from 1 to 4 carhon atoms. Two
substituents R5 and R~ may also form together a fus~d benzo ring.
Suitable polycyclic aromal:ic radic~ls of the formula II
are pyrene, anthracene, acenaphthene and chrysene radicals,
preferably pyrene. Examples of ~lkyl, alkoxy or acyl groups are
those which have of from 1 to 4 carbon atoms. As ncn chromophoric
radicals th~re may be mentioned halogen, alkyll alkoxy, mono- and
di-alkylamino, acylamino, cyano, sulfo, sulfoacid alkyl esters,
carboxy~ carboalkoxy, sulfonamido. carbonamido and the mono- and
di-alkyJamides derived therefrom, each alkyl, acyl or alkoxy group
having 1 - 4 C-atoms.
The compounds of the formula I as far as they possess
no oxadiazole ring, are known from the following Japanese patent
applications: Sho 43-7045 published March 15, 1968; Sho 44-6980,
Sho 44-6981, and Sho 44-6982 each published March 27, 1969 and
Sho 42-21013 published October 18, 1967.
The compounds of the formula I wherein A is an oxadiazole
ring, may be prepared accordinq to ~elgian patent 852 278 by
reacting a compound of the formula IV
~ ~ X ~ ~ ~ IV
with a compound of the formula V
--3--
,:: . -
.: ~ :~: ::,
~ : i
~L~3~35~
- 10 - HOE 78/F 182
R - Z V
wherein R1, R2, X and R4 are defined as above and Y is a
group of the formula VI
N - OH
-C ~ VI
--NH2
and Z is simultaneously a group of ~he formula VII
- COCl
or Y is a group of the formula VII and Z is simultaneously
a group of the formula VI.
In the first case there are obtained compounds of the
formula I which contain a 1,2,4-oxadiazolyl-3 group and in
the second case the compounds obtained contain the 1,2,4-
oxadiazolyl-5 group. The reaction occurs preferably in
the presence of an acid binding agent in an inert solvent,
at a temperature of from 20 to 200C.
The starting compounds of the formula V wherein Z is
a group of the formula VII, may be prepared according to
the process disclosed in Chem. Rev. 62 (1962), pages 155
et seq.. The starting compounds of the formula IV wherein Y
is a group of the formula VI may likewise be prepared in
analogous manner according to this process.
The compo`unds of the formula II are known from DT-AS
1,273,479 and may be prepared according to the process
disclosed in this publication.
The compounds of the formula III are known from the
following patent specification~ DE-AS 1,255,077; BE-PS
648,674; DE-AS 1,288,608; DE-AS l,445,694 and DE OS
1,469,207.
The reaction products obtained in the aforesaid pro-
29 cesses may be subjected to further known conversions,
~, .
, . .
:, , ~ .: ,
.: , : , : ,, ,
~L:3L3~3~6
11 HOE 78/F 1~?for example those in which sul~o- or carboxy groups are
funtionally modified or those in which sulfo- or carboxy
groups are converted to provide other groups of this type
or the free acids. Furthermore chloromethyl groups may be
incorporated in known manner or methyl groups may be oxi-
dized. In addition, the incorporated halogen atoms may
be halogenated or subjected to further reactions, for
example chlorine or bromine may be exchanged for the amine
function.
The mixing ratio of the components I and :~I ranges
between 0.05 and 0.95 part by weight of the compound I and
the corresponding quantity (0.95 to 0.05 part by weight)
of the compound II. The optimum mixing ratio depends in
each oase of the nature of the individual compounds of the
formulae I and II and may be readily determined by preli-
minary tests. Component III is added to components I and
II in the above-specified mixing ratios.
As is customary for optical brighteners, the indi-
vidual components are brought into a commercial form by
dispersion in a solvent, for example by dispersing them
separately and by combining the dispersions. Alternative-
ly the individual components can be mixed in substance and
be dispersed together. Dispersing is effected in usual
- manner in ball mills, colloid mills, bead mills, or disper-
sion kneaders. The mixtures according to the invention
are especially useful for brightening linear polyesters,
polyamides and acetyl cellulose. However, they can like-
wise be used with the same good result in blended fabrics
29 consisting of linear polyesters and other synthetic or na-
~ .,'
::: ::~,: ~ . .~:
; . , . :: , : ,
" ;:
3L~ 635~i
- 12 - HOE 78/~ 18?
tural fibers, especially hydroxyl groups-containing fibers,
in particular cott,on, These mixtures are applied onto the
fibers under conditions that are customary for the applica-
tion of optical brighteners, for example according to the
exhaust process, at a temperature of from 90 to 130C with
or without the addition of accelerators (carriers) or ac-
cording to the thermosol process. Brighteners that are
unsoluble in water and the mixtures according to the inven-
tion can alternatively be dissolved in organic solvents
such as perchloroethylene prior to being used, In this
operation the textile materiai may be treated with the
solvent liquor that contains the optical brightener in a
dissolved state according to the exhaust process. Another
way consists in impregnating, padding or spraying the
textile material with the solvent liquor that contains the
; brighteners and then drying the textile material at a tem-
perature of from 120 to 220C to fix all optical brightener
in the fiber.
An advantage of the use of the mixtures as described above
resides in the fact that an unexpected synergistic effect as
regards the degree of whiteness is achieved, i.e. a mixture
of compounds of the formulae I, II and III gives a higher degree
of whiteness than an identical quantity of only one of the
compounds of the formulae I, II or III.
- 25 This signifies that the quant~ty of the mixture accord-
ing to the invention which is required for achieving a de-
fined degree of whiteness is smaller than that of the indi-
vidual components.
29 The following examples illustrate the invention.
: . . . - . .
. , ", ~. ::,. ' : : ;
~. : . , , :. .
~3~3.~6
_ 13 _ HOE 78/F 182
Parts and percentages are by weight unless otherwise
stated. The ternperature is indicated in degrees Celsius.
The degrees of whiteness have been measured according to
the formulae of Stensby (Soap and Chemicals Specialities,
April 1967, pages 411 et seq.) and Berger (Die Farbe, 8
(2g59), pages 187 et seq.).
E X A M P L E 1:
Tissu sections consisting of polyester staple fibers
were washed and dried in usual manner before being impreg-
nated on a padding mangle with an aqueous dispersion con-
taining 0.5 g/1 of a mixture consisting of 70 weight % of
the compound of the formula
Cl
CH_CH- ~ -COOCH3
and of 30 weight % of the compound of the formula
\/==-=N
OCH3
The material was squeezed with a padding mangle be-
tween rollers to an 80 % liquor take-up which corresponds
- to a total take-up of optical brightener on the material
of 0.04 ~. The padded material was then dried on a tenter
frame for 30 seconds at 120C and thermosoled for a further
30 seconds at 190C to provide a degree of whiteness of
143 (Berger) and of 146 (Stensby).
,
~,, . .:: - :
``` ~3 3~356
_ 14 _ HOE 78/F 182
When proceeding in the manner indicated above, but with
the use of 0.45 g/l of the above-described brightener mix-
ture and additionally 0.05 g/l of the brightener of the
formula
CH
~ CH=C11- ~ -~ ~
a significant irnprovement of the degree of whiteness can
be observed. The degree of whiteness was found to be l46
(Berger) or 148.5 (Stenby).
E X A M P L E 2-
Polyester curtains having a raschelle tulle binding werewashed in usual manner in a continuous washing machine ?
then dried on a tender frame at 120C and impregnated on a
padding mangle with an aqueous dispersion containing 0.5
g/l of a mixture consisting of 75 weight % of a compound
of the formula
~ CH-CH- ~ -/ ~-CH3
and of 25 weight % of a compound of the formula
N \\~
=~,,
: OC~3
The material was then squeezed between rollers to
_,
~L~3~i3S~
- 15 - HOE 78/E 182
yield a liquor absorption of 80 %, which corresponds to a
take~up of optical brightener on the material of 0.04 ~.
The padded material was dried on a tenter f`rame for 30
seconds at 120C and thermofixed for a further 40 seconds
at 180C. The brightened goo~ were found to have the fol-
lowing degrees of whiteness: 145 (Berger) or 146 (Stenby).
When proceeding in the above manner but with the use
of 0.47 g/1 of the above-descr:ibed brightener mixture and
additionally 0.03 g/l of the brightener of the formula
C~
~ C3:C3- ~ - \ ~
the degrees of whiteness were found to be 147 (Berger) and
149 (Stensby). This signifies that a significant improve-
ment of the degree of whiteness can be reached with the
addition of the third component.
-: ' : ~ : ~ ..- ~ ;. , : :
. . -
