U.S. patent number 3,619,234 [Application Number 04/799,531] was granted by the patent office on 1971-11-09 for process for the optical brightening of fibrous materials of synthetic polyamides or cellulose esters.
This patent grant is currently assigned to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning. Invention is credited to Gunter Rosch, Otto Smerz, Joachim Weihsbach.
United States Patent |
3,619,234 |
Weihsbach , et al. |
November 9, 1971 |
PROCESS FOR THE OPTICAL BRIGHTENING OF FIBROUS MATERIALS OF
SYNTHETIC POLYAMIDES OR CELLULOSE ESTERS
Abstract
Fibrous materials of synthetic polyamides or cellulose esters
are capable optical brightening according to the so-called
thermosol process (padding at ambient temperature with subsequent
fixation by a heat treatment) when fixing in the presence of an
auxiliary consisting of a polyalkylene glycol and a fatty alcohol
oxethylate. Optionally foam-depressing phosphoric acid alkyl esters
and branched carboxylic acid esters are used additionally.
Inventors: |
Weihsbach; Joachim
(Frankfurt/Main, DT), Smerz; Otto (Kelkheim/Taunus,
DT), Rosch; Gunter (Altenhain/Taunus, DT) |
Assignee: |
Farbwerke Hoechst
Aktiengesellschaft vormals Meister Lucius & Bruning
(Frankfurt am Main, DT)
|
Family
ID: |
5689694 |
Appl.
No.: |
04/799,531 |
Filed: |
February 14, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Mar 2, 1968 [DT] |
|
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P 17 19 355.4 |
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Current U.S.
Class: |
427/158; 427/384;
252/301.16; 516/133 |
Current CPC
Class: |
D06L
4/679 (20170101) |
Current International
Class: |
D06L
3/00 (20060101); D06L 3/12 (20060101); D06l
003/12 () |
Field of
Search: |
;252/31.2W,89,73,8.9
;117/33.5T |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levow; Tobias E.
Assistant Examiner: Demers; A. P.
Claims
We claim:
1. A process for the optical brightening of a fibrous material of a
synthetic polyamide or cellulose ester which comprises impregnating
the fibrous material with a liquor containing an optical
brightener, and subsequently fixing the optical brightener by a
heat treatment in the presence of an auxiliary consisting
essentially of
a. a polyalkylene glycol of the formula
HO--(C.sub.n H.sub.2n O).sub.x --H
wherein n represents 2 or 3 and x represents a number from 2 to 22,
and b. a fatty alcohol oxethylate of the formula
R--O--(C.sub.2 H.sub.4 O).sub.z --H
wherein R represents an alkyl or alkenyl group containing eight to
24 carbon atoms and z represents a number from 3 to 16,
the ratio of the components being about 0.01 to 1 part by weight of
oxethylate per one part by weight of glycol.
2. The process of claim 1, wherein there is added to the
auxiliary,
a. from 0.5 to 5 percent by weight, calculated on the weight of the
auxiliary, of a carboxylic acid ester of the formula
wherein R.sub.1 and R.sub.2 are alkyl or alkenyl of four to 18
carbon atoms, at least one of R.sub.1 and R.sub.2 being branched,
and
b. from 0.5 to 5 percent by weight, calculated on the weight of the
auxiliary, of a phosphoric acid alkyl ester, the alkyl radicals of
which contain four to eight carbon atoms.
3. The process according to claim 1, which comprises adding the
auxiliary together with the optical brightener to the fibrous
material.
4. An auxiliary composition consisting essentially of
a. a polyalkylene glycol of the formula
HO--(C.sub.n H.sub.2n O).sub.x --H
wherein n represents 2 or 3 and x represents a number from 2 to 22,
and
b. a fatty alcohol oxethylate of the formula
R--O--(C.sub.2 H.sub.4 O).sub.z --H
wherein R represents an alkyl or alkenyl group containing eight to
24 carbon atoms and z represents a number from 3 to 16,
the ratio of the components being about 0.01 to 1 part by weight of
oxethylate per one part by weight of glycol.
5. The composition defined in claim 4 wherein the ratio of
components is 0.05 to 0.5 parts by weight oxethylate to one part by
weight glycol.
6. The composition defined in claim 4 which additionally contains
from 0.5 to 5 percent by weight of an aliphatic carboxylic acid
ester of the formula
wherein R.sub.1 and R.sub.2 are alkyl or alkenyl of four to 18
carbon atoms, at least one of R.sub.1 and R.sub.2 being
branched.
7. The composition defined in claim 4 which additionally contains
from 0.5 to 5 percent by weight of a phosphoric acid alkyl ester,
the alkyl radicals of which contain four to eight carbon atoms.
8. The composition defined in claim 4 which additionally
contains
a. from 0.5 to 5 percent by weight of an aliphatic carboxylic acid
ester of the formula
wherein R.sub.1 and R.sub.2 are alkyl or alkenyl of four to 18
carbon atoms, at least one of R.sub.1 and R.sub.2 being branched,
and
b. from 0.5 to 5 percent by weight of a phosphoric acid alkyl
ester, the alkyl radicals of which contain four to eight carbon
atoms.
Description
The present invention relates to a process for the optical
brightening of fibrous materials consisting of synthetic polyamides
or cellulose esters by impregnating the material with a liquor
containing an optical brightener with subsequent fixation by a heat
treatment which comprises fixing the brightener in the presence of
an auxiliary consisting of a polyalkylene glycol of the formula
HO--(C.sub.n H.sub.2n O) .sub.x --H
in which n is 2 or 3 and x is a number of 2 to 22, and a fatty
alcohol oxethylate of the formula
RO(C.sub.2 H.sub.4 0).sub.z --H
in which R is alkyl or alkenyl of eight to 24 carbon atoms and z is
a number of 3 to 16.
A further object of this invention is a composition of matter,
useful as an auxiliary in said process, consisting of a
polyalkylene glycol of the formula
HO--(C.sub.n H.sub.2n 0).sub.x --H
in which n is 2 or 3 and x is a number of 2 to 22 and a fatty
alcohol oxethylate of the formula
RO(C.sub.2 H.sub.4 O).sub.z --H
in which R is alkyl or alkenyl of eight to 24 carbon atoms and z is
a number of 3 to 16.
It is known to optically brighten synthetic fibrous materials of
linear polyesters according to the so-called thermosol process with
a satisfactory effect. Said method comprises padding the material
at ambient temperatures with solutions or suspensions of an
appropriate water-insoluble brightener and submitting it to a
subsequent heat treatment. The heat treatment aimed at the fixation
of the brightener is preferably effected at temperatures allowing
simultaneous thermostabilization of the fibrous material. With
polyester fibers these temperatures generally range from about
170.degree. to 220.degree. C.
It has been attempted to apply the thermosol method also to the
treatment of fibrous materials of synthetic polyamides, however, in
that case the effects produced with the optical brighteners are
essentially worse than achieved with usual exhaustive methods.
Owing to this fact the thermosoling of optical brighteners on
polyamide fibers has not attained yet any importance.
In optically brightening fibrous materials of cellulose esters,
especially cellulose triacetate according to the thermosil process,
substantially the same drawbacks are met with.
Now, it has been found that said difficulties can be overcome and
fibrous materials on the basis of synthetic polyamides or cellulose
esters can be brightened by the thermosoling method with a good
effect using as auxiliary a mixture of a polyalkylene glycol and an
oxethylated fatty alcohol.
The object of the invention hence is a process for the optical
brightening of fibrous materials of synthetic polyamides or
cellulose esters by impregnating the material with a liquor
containing an optical brightener and fixing the brightener,
subsequently, by a heat treatment in the presence of an auxiliary
consisting of a polyethylene glycol of about 2 to 22 --(C.sub.n
H.sub.2n O)-- units in which n is 2 or 3 and an oxethylated fatty
alcohol, the aliphatic radical of which contains at least eight to
24 carbon atoms comprising 3 to 16 ethylene glycol ether units.
To the composition of matter to be used according to the invention
a foam-depressing compound is advantageously added, for example an
aliphatic carboxylic acid ester corresponding to the general
formula
wherein R.sub.1 and R.sub.2 represent saturated or unsaturated
aliphatic groups which may be identical or different, having from
four to 18 carbon atoms, one or both of said groups containing at
least one side chain of one to four carbon atoms which chains
preferably are in the .alpha.-position in the acid radical while in
the .alpha. or .beta.-position in the alcohol radical. As
appropriate esters of the indicated type the following may be cited
by way of example: 2-ethyl-capric acid-2-ethylhexyl ester,
2-ethyl-capric acid-2-ethyl-butyl-ester, 2,2,3-trimethyl-butyric
acid-2-ethylhexyl ester, 2-ethyl-capric acid isooctyl ester,
2-ethyl capric acid isobutyl ester, the ester of 2-ethyl capric
acid and 2,6,8-trimethylnonanol-(4) as well as the 2-ethyl capric
acid ester of 2,6-dimethyl-heptanol-(4).
The carboxylic acid esters are preferably applied in admixture with
a phosphoric acid ester of an aliphatic alcohol having four to
eight carbon atoms, such as tri-n-butyl-phosphate,
tri-n-octylphosphate, especially triisobutyl phosphate.
The foam-depressing agents are generally added to the composition
of matter of the invention each in an amount in the range of from
0.5 to 5 percent, referred to the weight of the composition.
The instant process may be carried out by applying to the material
to be brightened a solution, dispersion or emulsion containing the
optical brightener, the polyalkene glycol, the oxethylated fatty
alcohol and, optionally, further adjuvants, predying said material,
subjecting it to a heat treatment in a thermosoling device and
finishing it thereafter, in usual manner. The optical brightening
agents can be applied from an organic or, preferably, aqueous bath.
It is likewise possible to apply the brightener and the auxiliary
of the invention with, optionally, the foam-depressing agents to
the fibrous material separately in any sequence, prior to the heat
treatment. The heat treatment for the fixation of the optical
brightener is generally conducted at temperatures between about
170.degree. and 220.degree. C., preferably 180.degree. and
210.degree. C. It lasts, approximately, 5 to 60, preferably 5 to 40
seconds and proceeds either in the form of dry heating or, if
desired, in using a small amount of steam.
As polyalkylene glycols to be used according to the invention
compounds of the general formula
HO--(C.sub.n H.sub.2n 0).sub.x H,
are suitable wherein n is 2 and 3 and x represents a number from
about 2 to 22. Preferred are polyethylene glycols of a medium
molecular weight in the range of from 200 to 600. However,
polypropylene glycols or polyethylene-propylene glycols or mixtures
of both are likewise appropriate.
As oxethylated fatty alcohols may serve compounds of the
formula
RO--(CH.sub.2 --CH.sub.2 --0).sub.z H
wherein z represents a number from about 3 to 16, preferably 5 to
10, and R is a saturated or unsaturated aliphatic radical of eight
to 24, preferably 12 to 18 carbon atoms.
The mixing ratio of the polyalkylene glycols and oxethylated fatty
alcohols may vary within wide limits. Generally, about 0.01 to 1
part by weight, preferably 0.05 to 0.5 part, of oxethylated fatty
alcohol is used per each part by weight of the polyalkylene glycol.
The composition of matter of the invention should advantageously be
applied in an amount from about 0.05 to 2.5 percent, preferably,
0.2 to 1.5 percent, calculated on the weight of the fibrous
material.
The process of the invention may be carried out with the aid of
optical brightening agents suitable for fibrous materials of
polyamide or cellulose acetate. Preferred are optical brighteners
of the pyrazoline series corresponding to the general formula
##SPC1## in which R' stands for an aryl radical, which may be
substituted and X for the vinyl group or the radical --CH.sub.2
--CH.sub.2 --Y in which Y is a hydroxy group, a primary or
secondary amino group, an acylamino group or an alcoxy radical
which may be substituted, a --OSO.sub.3 Me--or --SO.sub.3 Me--group
wherein Me represents hydrogen or a metal cation. Such optical
brighteners have, for example, been disclosed in Belgian Pats. Nos.
631,367, 661 139, 670 161 and 701 986. For use on fibrous materials
of synthetic polyamides predominantly water-soluble brighteners of
the indicated type are employed.
The brightening agents are applied in usual concentrations,
generally, in an amount in the range of from about 0.01 to 2
percent, preferred to the weight of the fibrous material.
The instant process is applicable to fibrous materials on the basis
of polyamides, for example those prepared from adipic acid and
hexa-methylene diamine (polyamide 66) or adipic acid,
hexamethylene-diamine and caprolactam (polyamide 66/6), caprolactam
(polyamide 6) or .omega.-aminoundecylic acid (polyamide 11) and
also to fibrous materials of cellulose esters, especially cellulose
triacetate. Said process provides goods of a uniform, high degree
of whiteness.
The following examples are to illustrate the invention but they are
not intended to limit it thereto. The parts and percentages being
by weight unless otherwise stated.
EXAMPLE 1
A knit fabric made of polycaprolactam (polyamide 6) was impregnated
with a liquor containing per liter 15 g. of an auxiliary consisting
of 85 parts of polyethylene glycol of a molecular weight of 400, 10
parts of an addition product of 5 mols of ethylene oxide to 1 mol
of a fatty alcohol having on an average 13 carbon atoms, 2.5 parts
of triisobutyl phosphate and 2.5 parts of 2 ethylcapric
acid-2-ethyl-butyl ester, 15 g./l. of an optical brightening agent
corresponding to the formula ##SPC2##
and 0.3 g./l. of citric acid.
The fibrous material was squeezed off between cylinders until its
moisture content represented 70 percent of its dry weight and,
subjected, subsequently, for 20 seconds to a treatment by hot air
of 190.degree. C.
The knit fabric thus treated displayed an outstanding degree of
whiteness substantially higher than that produced, under equal
conditions, without the use of the auxiliaries.
EXAMPLE 2
A laundered and dried fabric of polyamide 6.6 was treated with a
liquor containing per liter 25 g. of an auxiliary consisting of 75
parts of polypropyleneglycol of a molecular weight of 250, 15 parts
of an addition product of 8 mols of ethylene oxide to 1 mol of a
branched fatty alcohol having on an average 13 carbon atoms, 5
parts of triisobutylphosphate and 5 parts of 2 ethyl-capric
acid-2-ethyl-butyl ester, 25 g./l. of an optical brightening agent
having the composition specified in example 1 and 0.5 g./l. of
citric acid. To the liquor moreover, 30 mg./l. of dyestuff C.I. No.
51 319 (cf. Color Index, 2nd edition (1956))were added in order to
improve the shade of the brightener.
The fibrous material was squeezed off in usual manner between
cylinders to a moisture content representing 55 percent of its dry
weight, dried subsequently, during 30 seconds at 130.degree. C. and
subjected, thereafter, for 20 seconds to a treatment in hot air at
200.degree. C.
The fabric thus treated showed an excellent degree of whiteness
essentially superior to that produced, under equal conditions,
without the auxiliaries.
EXAMPLE 3
A knit fabric made from polyamide 6 was treated with a liquor
containing per liter 25 g. of an auxiliary consisting of 85 parts
of polyethylene glycol of a molecular weight of 200, 10 parts of an
addition product of 5 mols of ethylene oxide to 1 mol of stearyl
alcohol, 2.5 parts of triisobutyl phosphate and 2.5 parts of
2-ethyl capric acid-2-ethylbutyl ester, 5.7 g./l. of an optical
brightening agent corresponding to the formula ##SPC3## (disclosed
in French Pat. No. 1,300,489) The fibrous material was squeezed off
between cylinders to a moisture content of 30 percent of its dry
weight and subjected, subsequently, during 20 seconds to treatment
in hot air of 190.degree. C.
The knit fabric thus handled displayed a high degree of
whiteness.
EXAMPLE 4
A fabric of triacetate fibers was impregnated with a liquor
containing per liter 20 g. of the auxiliary specified in example 1,
2.25 g./l. of an optical brightening agent of the formula ##SPC4##
and 5 g./l. of an addition product of 8 mols of ethylene oxides to
1 mol of nonylphenol. The fibrous material was squeezed off between
cylinders to a moisture content of 60 percent of its dry weight and
exposed during 20 seconds to a temperature of 190.degree. C. The
fabric exhibited an excellent degree of whiteness.
EXAMPLE 5
A knit fabric of polyamide 6 was treated with a liquor containing
per liter 25 g. of an auxiliary consisting of 85 parts of
polyethylene glycol of a molecular weight of 200, 10 parts of an
addition product of 5 mols of ethylene oxide to 1 mol of
olealcohol, 2.5 parts of triisobutyl phosphate and 2.5 parts of
2-ethyl capric acid 2-ethyl-butyl ester, 5.7 g./l. of an optical
brightening agent of the formula specified in example 1 and 0.5
g./l. of citric acid. The fibrous material thus wetted was squeezed
off between cylinders until having a moisture content of 50 percent
of its dry weight and subjected, thereafter, for 20 seconds to a
hot air treatment at 190.degree. C.
The knit fabric thus treated displays an excellent degree of
whiteness.
* * * * *