Note: Descriptions are shown in the official language in which they were submitted.
~8~;5
Cation optical brighteners of the naphthalimide series containing
quaternary nitrogen atoms are known. French Patent 1,557,945 describes cationic
naphthalimide derivatives containing trialkylammonium radicals bound to the imide
nitrogen via a chain of two or three methylene groups.
The present invention provides novel cationic compounds of the
formula (1) CIH3 (+) / 3
lH2 C - CH2 - IN ~ CH3 X~
~j
in which OR
R denotes alkyl, hydroxyalkyl, alkoxyalkyl,phenylalkyl,or phenoxyalkyl,
Rl denotes alkyl, hydroxyalkyl, benzyl, or allyl and
X( ) denotes a colorless anion.
The radicals R and R' preferably contain ] to 4 carbon atoms in the
alkyl or alkoxy gIOUpS and are, for example, ethyl, propyl, butyl, hydroxyethyl,
methoxyethyl, ethoxyethyl, propoxyethyl, phenoxyethyl, or benzyl and, in par-
ticular, methyl because of the favorable manufacturing conditions. X( ) stands,
for example, for a halide, alkyl sulfonate, alkyl sulfate, alkylphenyl sulfonate,
or phenyl sulfonate ion.
Compounds of the formula (1) are manufactured in known manner by
alkylation of a compound of the formula ~2)
CIH3 ~ ~ CH3
CH2 Cl CH2 N ~ (2)
o~N~ CH3 3
OR
: .
' . ,
; :
,
.
3SS
- 3 - ~OE 79/F 295
with a compound of the formula
X - R'.
The alkylation is preferably carried out in a suitable
inert organic solvent such as toluene, xylene, chlorobenzene,
dimethylformamide, or tetralin, at a temperature in the
range of from room temperature to 100C, preferably room
temperature to 60C.
The naphthalimides of the formula (2) used as starting
materials are obtained by reaction of the 4-chloro- or 4-
bromo-naphthalic anhydrides with N,N,2,2-tetramethylpropane-
1,3-diamine (dimethylamino-neopentylamine) to give the
corresponding N-(2,2-dimethyl-3-dimethylaminopropyl)-4-
halogenonaphthalimides with subsequent exchange of the
halogen atoms by reaction with alcohols of the formula HOR
or their alkali metal salts.
The novel compounds can be used for brightening
organic materials such as cotton and, above all, for
synthetic fibers, for example of polyamides such as polymers
on the basis of hexamethylene-diamino-adipate or caprolactam,
cellulose esters such as cellulose-2 1/2 acetate and
cellulose triacetate, and preferably polyacrylonitrile.
For brightening the organic materials a small amount
of optical brightener according to the invention,
preferably 0.001 to 1 ~, calculated on the material to be
brightened, is incorporated therein, optionally together
with other substances such as plasticizers, stabilizers or
pigments. The brighteners can be incorporated, into the
plastic material,for example, in the form of a solution in
a plasticizer, for example dioctyl phthalate, or together
with a stabilizer, for example dibutyl tin dilaurate or
sodium pentaoctyl tripolyphosphate, or together with pig-
ments, for example titanium dioxide. Depending on the
material to be brightened, it is also possible to dissolve
the brightener in the monomers prior to polymerization, in
the polymer mass, or in a solvent together with the polymer.
The material pretreated in the above manner is then
transformed into the desired final shape by processes known
per se, such as spinning and drawing. Alternatively, the
, . . .
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brightener carl be incorporated into finishing agents, for
example those ~or textile fibers, such as polyvinyl alcohol,
or into resins or resin precondensates such as methylol
compounds of ethylene urea, used for textile treatment.
The compounds of the invention are also suitable to
br:Lghten the surface coat of paper. It is preferable, however,
to brighten therewith colorless, high molecular weight
organic materials in the form of fibers. For brightening ,
said fiber materials it proved advantageous to use an
aqueous solution of the compounds of formula (1) according
to the invention. The solutions preferably contain from
0.005 to 0.5 ~ of naphthalimides of the invention, calcu-
lated on the fiber material. The solutions may further
contain auxiliaries such as dispersing agents, for example
condensation products of C10-C18 fatty alcohols or alkyl-
phenols with 15 to 25 moles of ethylene oxide or condensation
products,of, C16-C18alkyl,mono- or polyamines with at least
10 mols of ethylene oxide, organic acids such as formic acid,
oxalic acid or acetic acid, detergents, swelling agents such
as di- or trichlorobènzenes, wetting agents such as sulfo-
succinic acid alkyl esters, bleaching agents such as sodium
chlorite, peroxides or hydrosulfites, retarders and
optionally other brighteners of the same or another series,
for example derivatives of stilbene having an affinity for
cellulose.
The fiber material is brightened with the aqueous
brightener bath either by an exhaust process at temperatures
preferably in the range of from 30 to 150C or by a padding
process. In the latter case the material is impregnated,
for example with a 0.2 to 0.5 % brightener solution and
finished by a dry or moist heat treatment, for example by
steaming under 2 atmospheres or, after drying, by a short
dry heating to 180 to 220C, optionally with simultaneous
thermofixation of the fabric. The fiber material treated in
this manner is then rinsed and dried.
Colorless, high molecular weight, organic material
which has be~n optically brightened according to the
invention, in particular natural or synthetic fiber material
~ ,
~ . , .
3~5
- 5 - HOE 7g/F 295
that has been briyntened by the exhausiion process, has a
pleasant, pure white, blue-violet to blui~h, fluorescent
aspect. When dyed light shades and whitened according to the
invention the material is distinguished by a clear shade.
When textile fibers, for example of synthetic polyamide
and cellulose ester fibers, in particular polyacrylonitrile
fibers, are washed with washing liq~lors containing a
naphthalimide of the formula (1), the material acquires a
brilliant aspect in daylight.
It should ~e stressed that the compounds of the
invention have a good stability to light, a high stability
to chlorite, a high tinctorial strength and especially a
high degree of whiteness and, on the whole, an outstanding
tinctorial behavior.
The compounds of the formula (1) containing a quaterna-
ry carbon atom in B-position with respect to the quaternary
ammonium group-and--i-n B-position with respect to the imide
nitrogen are extremely stable. They are distinctly superior
as regards the brightening effect, especially in the
one-bath chlorite bleaching of polyacrylonitrile fibers, to
the above mentioned cationic naphthalimides containing tri-
alkylammonium radicals bound to the imide nitrogen via a
chain of two or three methylene groups.
The following examples illustrate the invention.
E X A M P L E
For preparing the compound
CIH3 l+)
CH2 - C~ - Cll2 N(CH3)3 CH30S03
o~; r N ~
3 "'
17 g of ~--methoxy-N-dimethylamino-neopentyl-naphthalimide
are dissolved in 100 ml of acetone and 5.2 ml of dimethyl
sulfate are added dropwise at room temperature. Stirring of
,
~. ' . ' . ', , .
- 6 - HOE 79/F 295
the mixture is continued for 18 hours at room temperature,
the mixture is filtered with suction and the residue is
washed with acetone. After drying in vacuo at 60C, 21.2 g
of a yellowish crystalline powder are obtained, corres-
ponding to 91 % of the theoretical. Melting point 231 to233C, sintering point 228C.
The 4-methoxy-N-dimethylamino-neopentyl-naphthalimide
required as starting material is prepared as follows: An
autoclave with stirrer is charged with 121 g of 4-chloro-
naphthalic anhydride and 81.4 ml of dimethylamino-neopentyl-
amine in 750 ml of methanol, the autoclave is heated to
70C and kept at said temperature for 5 hours. Next, the
autoclave is cooled to 50C, 60 g of 40 ~ sodium hydroxide
solution are added and the whole is heated to 100C. The
reaction mixture is stirred for 2 hours at the indicated
temperature, cooled to room temperature and the precipitated
reaction product is filtered off with suction, washed in
portions with 500 ml of methanol and then with water. The
precipitate is dried in vacuo at 60C. 142.0 g of a yellow
powder are obtained melting at 107 to 110C, corresponding
to 83.5 ~ of the theoretical.
E X A M P L E _
0.24 g of sodium chlorite, 0.1 g of a commercial
bleaching auxiliary and 0.3 ml of 2N acetic acid are
dissolved at 60C in 200 ml of water. A solution is prepared
from the optical brightener obtained according to Example 1
by dissolving 0.02 g thereof in 1 ml of dimethyl formamide.
The solution is added to the aqueous bath and the pH of the
bath is adjusted to 3,5 by adding dropwise acetic acid
(10 ~ strength). 5 g of a polyacrylonitrile fabric are
introduced into the aqueous bath containing the brightener
and having a temperature of 60C. The fabric is first
bleached for 30 minutes at 80C and then for 30 minutes at
100C, whereupon it is rinsed with hot and cold water and
dried. The fiber material treated in this manner has a
pleasant white aspect with a violet hue. A similar effect
is obta~ned by bleaching in the absence of sodium chlorite
and bleaching auxiliary and adjusting the pH of the bath to
-
8~
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4 with 10 ~ acetic acid.
E X A M P L E 3
0.12 ml of 85 ~ formic acid is added to 100 ml of water.
A solution of the optical brightener accordiny to Example 1
is prepared by dissolving 1 g thereof in 100 ml of water.
1.5 ml of the solution obtained are added to the above
solution, the mixture obtained in heated to 60C and 3 g of
a polyacrylonitrile fabric are introduced. The temperature
is raised to 95 to 98C within 10 to 15 minutes and the
fabric is treated at said temperature for 1 hour. It is
then rinsed for 2 minutes in running cold water and dried
at 60C. The treated fabric has a white brilliant aspect.
In the manner described in Example 1 the compounds
listed in the following table are prepared
.- -CH2 ' 3 CH - N ~ 3 CH3 X( )
O ~ N ~ C~3
~ _
OR
:
,
8~3S5
R R' X(-)n reaction medium melting point
reaction tempe- (purification
rature _ agent)
_
C2H5- COCH2CH2 Cl( ) 1 2-chloroethanol 204.5C with
128C decomp. (from
_ pyridine)
CH3CH2CH2 CH3 CH30S03( ) toluene 60C 184 - 192C
_ _. .
3 H2C 2 HOCH2CH2 Cl( ) 2-chloroethanol 113 - 116.5C
_ _ 128C (from ethanol)
, ~ _ _
CH3- CH3- CH3C6H5S3 1 toluene 60C 222 - 225C
i ~ _
CH3- C2H5- C2H5S03~ J 1 diethyl sulfate 198 - 200C
50C (from methanol~
_
CH3- HOCH2CH2 Cl( ) 1 2_chloroethanol 218 - 220C with
128C decomp. (from
ethanol~
_
CH3- CH3(CH2)3- Br( ) 1 n-butyl bromide 192 - 193C with
102C decomp. (from
_ sopro~ol)
C2H5- CH3- CH30S03( ) 1 toluene 60C 233 - 237C with
decomp. (from n-
butanol~
_ I
CH30CH2CH2- CH3 CH30S03( ) 1 ¦toluene 60C 220 - 225C
~ 8
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