U.S. patent number 3,779,705 [Application Number 05/171,771] was granted by the patent office on 1973-12-18 for process for dyeing fibers or fabrics of aromatic polyamides.
This patent grant is currently assigned to Teijin Limited. Invention is credited to Kazuo Kitamura, Fumiki Takabayashi, Setsuo Yamada.
United States Patent |
3,779,705 |
Kitamura , et al. |
December 18, 1973 |
PROCESS FOR DYEING FIBERS OR FABRICS OF AROMATIC POLYAMIDES
Abstract
A process for dip dyeing aromatic polyamide fibers or fabrics
with acid dyes with good dyeability and levelling properties,
without modifying measures which may cause deterioration of the
desirable properties of the aromatic polyamides, which comprises
dip dyeing fibers or fabrics of an unmodified aromatic polyamide in
a dye bath comprising an acid dye of the monosulfonic acid,
monosulfonic acid-carboxylic acid, disulfonic acid, disulfonic
acid-carboxylic acid, or carboxylic acid and at least 1 percent by
weight (based on the weight of the solution) of a neutral or acidic
inorganic salt, in the presence of a swelling agent having a
phenolic hydroxyl group, and alkali metal salts thereof; and
soaping the dyeing obtained.
Inventors: |
Kitamura; Kazuo (Ibaraki,
JA), Takabayashi; Fumiki (Ibaraki, JA),
Yamada; Setsuo (Ibaraki, JA) |
Assignee: |
Teijin Limited (Osaka,
JA)
|
Family
ID: |
27465349 |
Appl.
No.: |
05/171,771 |
Filed: |
August 13, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Aug 14, 1970 [JA] |
|
|
45/71249 |
Aug 31, 1970 [JA] |
|
|
45/76126 |
Dec 16, 1970 [JA] |
|
|
45/111713 |
Dec 18, 1970 [JA] |
|
|
45/113812 |
|
Current U.S.
Class: |
8/613; 8/924 |
Current CPC
Class: |
D06P
1/6422 (20130101); D06P 1/6735 (20130101); D06P
1/67366 (20130101); D06P 3/241 (20130101); D06P
3/26 (20130101); D06P 1/96 (20130101); D06P
1/67375 (20130101); Y10S 8/924 (20130101) |
Current International
Class: |
D06P
1/642 (20060101); D06P 1/673 (20060101); D06P
1/44 (20060101); D06P 1/96 (20060101); D06P
1/64 (20060101); D06P 3/24 (20060101); D06P
1/00 (20060101); D06P 3/26 (20060101); D06p
001/68 () |
Field of
Search: |
;8/172,173,178 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Guynn; Herbert B.
Assistant Examiner: Herbert, Jr.; T. J.
Claims
What we claim is:
1. A process for dyeing fibers or fabrics of an aromatic polyamide
having an aromatic ring in the recurring units with acid dyes,
which comprises dip dyeing said fibers or fabrics of an unmodified
aromatic polyamide in which the recurring unit of the molecular
chain is expressed by a recurring unit selected from the group
consisting of:
i. -- NH-Ar.sub.1 -CO -- , wherein Ar.sub.1 is an aromatic
ring,
ii. -- NH-Ar.sub.1 -NHCO-Ar.sub.2 -CO -- , wherein Ar.sub.1 and
Ar.sub.2 are the same or different, and represent an aromatic
ring,
iii. -- NH-R.sub.1 -Ar.sub.1 -CO -- , wherein Ar.sub.1 is an
aromatic ring, and R.sub.1 is a lower alkyl group,
iv. --NH-R.sub.1 -Ar.sub.1 -R.sub.2 -NHCO-Ar.sub.2 -Co -- , wherein
Ar.sub.1 and Ar.sub.2 may be the same or different, and represent
an aromatic ring, and R.sub.1 and R.sub.2 may be the same or
different and represent a lower alkyl group, and
v. combinations of two or more of units (i) to (iv),
in an aqueous dye bath comprising an acid dye of the monosulfonic
acid, monosulfonic acid-carboxylic acid, disulfonic acid,
disulfonic acid-carboxylic acid, or carboxylic acid type expressed
by the formula D----AM).sub.p
wherein D represents a dye molecule matrix, A represents --SO.sub.3
-- or --COO-- residue, M represents hydrogen or an alkali metal,
and p is an integer of 1 to 3, with the proviso that A is only
--SO.sub.3 -- and when A contains both --SO.sub.3 -- and --COO--,
the maximum number of --SO.sub.3 M is 2,
and at least 1 percent by weight, based on the weight of the dye
bath, of a neutral or acidic inorganic salt, in the presence of a
swelling agent selected from compounds having a phenolic hydroxyl
group expressed by the following formula HO--Ar.sub.3 --R.sub.3
wherein Ar.sub.3 is a phenyl or naphthyl group, R.sub.3 is a member
selected from the group consisting of hydrogen, lower alkyl groups,
halogen, a nitro group, lower alkoxy groups, and a phenyl group,
and when Ar.sub.3 is a naphthyl group, R.sub.3 is hydrogen or a
lower alkyl group,
and alkali metal salt thereof; and soaping the dyeing obtained.
2. The process of claim 1, wherein said phenolic
hydroxyl-containing compound or alkali metal salt thereof is
selected from the group consisting of phenol, alpha-naphthol,
beta-naphthol, cresol, o-phenyl phenol, p-phenyl phenol,
nitrophenol, chlorophenol, and 4-methoxyphenol.
3. The process of claim 1, wherein the amount of said swelling
agent is 0.5 to 50 percent based on the weight of said fibers or
fabrics (o.w.f.).
4. The process of claim 1, wherein the amount of said inorganic
salt is 1 to 40 percent based on the weight of the dye bath
(o.w.s.).
5. The process of claim 1 wherein said neutral or acidic inorganic
salt is an alkali metal salt or ammonium salt of an inorganic
acid.
6. A process for dyeing fibers or fabrics of an aromatic polyamide
having an aromatic ring in the recurring units with acid dyes,
which comprises dip dyeing said fibers or fabrics of an unmodified
aromatic polyamide in which the recurring unit of the molecular
chain is expressed by a recurring unit selected from the group
consisting of:
i. -- NH-Ar.sub.1 -CO -- , wherein Ar.sub.1 is phenyl,
ii. -- NH-Ar.sub.1 -NHCO-Ar.sub.2 -CO -- , wherein Ar.sub.1 and
Ar.sub.2 are the same or different, and represent phenyl or
naphthyl,
iii. -- NH-R.sub.1 -Ar.sub.1 -CO -- , wherein Ar.sub.1 is phenyl
and R.sub.1 is an alkyl group of 1 - 4 carbon atoms,
iv. -- NH-R.sub.1 -Ar.sub.1 -R.sub.2 -NHCO-Ar.sub.2 -CO--, wherein
Ar.sub.1 and Ar.sub.2 may be the same or different, and represent
phenyl or naphthyl, and R.sub.1 and R.sub.2 may be the same of
different and represent an alkyl group of 1 - 4 carbon atoms,
and
v. combinations of two or more of units (i) to (iv), in an aqueous
dye bath comprising an acid dye of the monosulfonic acid,
monosulfonic acid-carboxylic acid, disulfonic acid, disulfonic
acid-carboxylic acid, or carboxyiic acid type expressed by the
formula
D----am).sub.p
wherein D represents a dye molecule matrix, A represents --SO.sub.3
-- or --COO-- residue, M represents hydrogen or an alkali metal,
and p is an integer of 1 to 3, with the proviso that A is only
--SO.sub.3 -- and when A contains both --SO.sub.3 -- and --COO--,
the maximum number of --SO.sub.3 M is 2,
and at least 1 percent by weight, based on the weight of the dye
bath, of a neutral or acidic inorganic salt in the presence of a
swelling agent selected from compounds having a phenolic hydroxyl
group expressed by the following formula
Ho--ar.sub.3 --R.sub.3
wherein Ar.sub.3 is a phenyl or naphthyl group, R.sub.3 is a member
selected from the group consisting of hydrogen, lower alkyl groups,
halogen, a nitro group, lower alkoxy groups, and a phenyl group,
and when Ar.sub.3 is a naphthyl group, R.sub.3 is hydrogen or a
lower alkyl group,
and alkali metal salt thereof; and soaping the dyeing obtained.
7. The process of claim 6 wherein said neutral or acidic inorganic
salt is an alkali metal salt or ammonium salt of an inorganic acid.
Description
This invention relates to a process for dyeing fibers or fabrics of
unmodified aromatic polyamides which are very difficult to dye with
acid dyes. More specifically, the invention relates to a process
for dip dyeing aromatic polyamide fibers or fabrics with acid dyes
with good dyeability and levelling properties, without taking any
modifying measures which may cause deterioration of the desirable
properties of the aromatic polyamides.
According to the present invention, a process for dyeing fibers or
fabrics of aromatic polyamides having an aromatic ring in the
recurring units with acid dyes is provided, which comprises dip
dyeing fibers or fabrics of an unmodified aromatic polyamide in
which the recurring unit of the molecular chain is expressed by a
recurring unit selected from the group consisting of:
I. NH-Ar.sub.1 -CO, wherein Ar.sub.1 is an aromatic ring,
preferably phenyl,
Ii. NH-Ar.sub.1 -NHCO-Ar.sub.2 -CO, wherein Ar.sub.1 and Ar.sub.2
are the same or different, and represent an aromatic ring,
preferably phenyl or naphthyl,
Iii. NH-R.sub.1 -Ar.sub.1 -CO, wherein Ar.sub.1 is an aromatic
ring, preferably phenyl, and R.sub.1 is a lower alkyl group,
preferably having 1 to 4 carbon atoms,
Iv. NH-R.sub.1 -Ar.sub.1 -R.sub.2 -NHCO-Ar.sub.2 -CO, wherein
Ar.sub.1 and Ar.sub.2 may be the same or different, and represent
an aromatic ring, preferably phenyl or naphthyl, and R.sub.1 and
R.sub.2 may be the same or different and represent a lower alkyl
group, preferably having 1 or 4 carbon atoms, and
V. combinations of two or more of the units (i) to (iv), in a dye
bath comprising an acid dye of the monosulfonic acid, monosulfonic
acid-carboxylic acid, disulfonic acid, disulfonic acid-carboxylic
acid, or carboxylic acid type expressed by the formula
D----am).sub.p
Wherein D represents a dye molecule matrix, A represents --SO.sub.3
-- or --COO-- residue, M represents hydrogen or an alkali metal,
and p is an integer of 1 to 3, with the proviso that when A is only
--SO.sub.3 -- and when A contains both --SO.sub.3 -- and --COO--,
the maximum number of --SO.sub.3 M is 2,
And at least 1 percent by weight (based on the weight of the
solution) of a neutral or acidic inorganic salt, preferably alkali
metal salts or ammonium salts of inorganic acids, especially alkali
metal salts or ammonium salts of mineral acids in the presence of a
swelling agent selected from compounds having a phenolic hydroxyl
group expressed by the following formula
Ho - ar.sub.3 - R.sub.3
wherein Ar.sub.3 is a phenyl or naphthyl group, R.sub.3 is a member
selected from the group consisting of hydrogen, lower alkyl groups,
preferably those having 1 to 4 carbon atoms, especially a methyl
group, halogen a nitro group, lower alkoxy groups, preferably those
having 1 to 4 carbon atoms, especially a methoxy group, and a
phenyl group, and when Ar.sub.3 is a naphthyl group, R.sub.3 is
hydrogen or a lower alkyl group, preferably an alkyl group having 1
to 4 carbon atoms, especially a methyl group;
and alkali metal salts thereof; and soaping the dyeing
obtained.
It is known that linear polyamides such as nylon 6, nylon 66, nylon
610, or nylon 11 can be dyed with acid dyes with practical
dyeability. On the other hand, aromatic polyamides having an
aromatic ring in the recurring units have better flameproofing
properties, tenacity, elastic properties, and dimensional stability
than the above-mentioned polyamides ordinarily used, but have
higher hydrophobic properties and crystallinity. Therefore, dyeings
having practical value cannot be obtained from such aromatic
polyamides by dip dyeing with acid dyes in accordance with the
procedure used for ordinary polyamides. They are either not dyed at
all, or dyed only in very light colors.
This imposes serious restrictions in the application of fibers or
fabrics made from such aromatic polyamides, and constitutes a
setback in the utilization of the desirable properties of the
aromatic polyamide fibers or fabrics mentioned above.
With a view to removing such a defect, it was proposed to modify
aromatic polyamides to render them cationically dyeable, and dye
them with basic dyes in the presence of a swelling agent (Textile
Chemist and Colorist: Vol. 1, No. 18, pp. 388/27-319/30, 1969). It
is also known to dye aromatic polyamide fibers modified with a
tertiary amine-containing amide, sulfo-substituted amide, or a
quaternary ammonium-containing amide with basic or acid dyes (see
U. S. Pat. No. 3,506,990).
These prior proposals require an additional step of modifying the
polyamides, and suffer from other disadvantages including the
adverse effect on the properties of the aromatic polyamides as a
result of modification.
A method has also been proposed in which aromatic polyamides are
dyed with basic dyes in the presence of benzaldehyde and sodium
nitrate (Textile Chemist and Colorist: Vol 2, No. 15, pp.
25/262-28/265, 1970). According to this proposal, the modification
of the polyamides is not required. But it has been pointed out that
only basic dyes show practical dyeability, and acid dyes cannot
give dyeings having practical sunlight fastness and crockfastness.
As will be shown by a comparative example appearing later in this
specification, the dyeing effect of the present invention cannot be
produced even if the aromatic polyamides are dyed with acid dyes
using benzaldehyde instead of the compound having a phenolic
hydroxyl group as used in the process of the present invention.
Furthermore, in this dyeing method, the dispersibility of
benzaldehyde in the dye bath is poor, and it must be used in the
form of an emulsion which is troublesome and difficult to control;
frequently, the level dyeing properties are poor, and practical
dyeings cannot be obtained.
It has now been found that fibers or fabrics composed of unmodified
aromatic polyamides can be dyed with good results by a dye bath
comprising the acid dye and at least 1 percent by weight of the
neutral or acidic inorganic salt utilizing the compound having a
phenolic hydroxyl group expressed by the above given formula and
its alkali metal salts.
It is quite surprising that excellent dyeings of unmodified
aromatic polyamides can be obtained by easy dyeing means using the
acid dyes whose utilization proved unsatisfactory in the former
proposal in which modified aromatic polyamides are dyed with basic
or acid dyes, and was denied in the latter proposal in which
unmodified polyamides are dyed with basic dyes.
Accordingly, an object of the present invention is to provide a
process for dyeing fibers or fabrics composed of unmodified
aromatic polyamides with good dyeability using an acid dye without
adversely affecting the desirable properties of the polyamides.
Many other objects and advantages of the present invention will
become apparent from the following description.
In the present specification and claims, the term "fibers" is meant
to include all forms of fibers such as filaments, tows, yarns, or
staples, and the term "fabrics" includes woven fabrics, knitted
fabrics, felts, and nonwoven fabrics.
It is not clear what dyeing mechanism is responsible for the
excellent dyeability obtained by the process of the present
invention. It is assumed however that it is due to the ionic bond
between the aromatic polyamide and the --SO.sub.3 -- or --COO--
group of the acid dye expressed by the formula given above. Some
reasons given are that because the terminal amino group is a group
derived from an aromatic amine and the polyamide is not modified at
all, its basicity is not large enough to produce a sufficient
dyeability by the ionic bond with the acid dye, and that when the
polyamide is extracted with dimethyl formamide, a substantial
amount of the dye is dissolved out.
It is assumed that in accordance with the present invention the
excellent dyeability of the aromatic polyamide fibers or fabrics is
obtained by the synergistic action of (a) the swelling agent having
a phenolic hydroxyl group as expressed by the formula given above
which has been applied to the aromatic polyamide fibers or fabrics
in advance or is present in the dye bath, and (b) the neutral or
acidic inorganic salt. In fact, when the aromatic polyamide fibers
or fabrics are dyed with some acid dyes which are known to exhibit
good dyeability towards ordinary polyamides but do not correspond
to the general formula given above, the objects of the present
invention cannot be achieved as shown in Comparative Examples set
forth hereinafter. Furthermore, when benzaldehyde is used instead
of the specific swelling agent used in the invention, the objects
of the present invention cannot be achieved. Furthermore, if the
use of the neutral or acidic inorganic salt is omitted in the
process of the present invention, the objects of the present
invention cannot be achieved as will be shown by the Comparative
Examples given below.
Probably, a coated or permeated bayer of the swelling agent is
formed on the surface or surface layer of the difficultly-dyeable
aromatic polyamide fibers or fabrics, and the solubility of the
acid dye having a certain range of water solubility in water is
reduced by the copresence of the neutral or acidic inorganic salt,
and the solubility of the swelling agent in water is reduced for
the same reason. The dye molecules move into the coating or
permeated layer of the swelling agent to increase the concentration
of the dye at that portion, which in turn permits easy intrusion of
the dye molecules by the swelling of the aromatic polyamide fibers
or fabrics, and consequently, the aromatic polyamide fibers or
fabrics are dyed with markedly improved dyeability.
The material to be dyed by the process of the present invention is
fibers or fabrics of an aromatic polyamide in which the recurring
unit (i) to (v) constitutes the main chain of the polyamide.
Expecially, according to the process of the present invention,
fibers or fabrics of aromatic polyamides having recurring units
composed of (i), (ii) or a combination of these can be dyed with
excellent dyeability.
Examples of the polyamide having the recurring unit (i) above
include the aromatic polyamides disclosed in British Patent
901,159.
The polyamides having the recurring unit (ii) are disclosed, for
instance, in U. S. Pat. Nos. 3,063,966 and 3,006,899.
As the polyamide having the recurring unit (iii), homopolymers of
p-aminoalkylbenzoic acids produced by the same method as British
Patent 901,159 are typical examples.
The polyamides having the recurring unit (iv) can be produced, for
example, by the method disclosed in U. S. Pat. No. 3,232,910, and
include, for example, aromatic polyamides derived from p- or
m-xylylenediamine and iso- or tere-phthalic acid.
The polyamides having the recurring unit shown in (v) above can be
produced by optional combinations of the polyamide-forming
components above mentioned.
The swelling agent used in the present invention is selected from
compounds having a phenolic hydroxyl group expressed by the
following formula
Ho - ar.sub.3 - R.sub.3
wherein Ar.sub.3 is a phenyl or naphthyl group, R.sub.3 is a member
selected from the group consisting of hydrogen, lower alkyl groups,
preferably those having 1 to 4 carbon atoms, especially a methyl
group, halogen, a nitro group, alkoxy groups, preferably those
having 1 to 4 carbon atoms, especially a methoxy group, and a
phenyl group, and when Ar.sub.3 is a naphthyl group, R.sub.3 is
hydrogen or a lower alkyl group, preferably an alkyl group having 1
to 4 carbon atoms, especially a methyl group;
and alkali metal salts thereof.
Specific examples of such swelling agent include phenol,
alphanaphthol, beta-naphthol, o-, m-, and p-cresols,
o-phenylphenol, p-phenyl-phenol, nitro-phenol, chlorophenol,
4-methoxyphenol. The p-phenyl phenol gives most favorable
results.
The acid dye that is used in the present invention is selected from
acid dyes of the monosulfonic acid, monosulfonic acid-carboxylic
acid, disulfonic acid, disulfonic acid-carboxylic acid, or
carboxylic acid type expressed by the following formula
D--am).sub.p
wherein D represents a dye molecule matrix, A represents --SO.sub.3
-- or --COO-- residue, M represents hydrogen or an alkali metal,
and p is an integer of 1 to 3, with the proviso that when A is only
--SO.sub.3 -- and when A contains both --SO.sub.3 -- and --COO--,
the maximum number of --SO.sub.3 M is 2.
Acid dyes of the monosulfonic acid and monosulfonic acid-carboxylic
acid types are especially preferred. When p is 2 or 3, those dyes
in which the structure of the dye molecule matrix D is large, for
instance, those having at least 4 benzene rings, and which have low
solubility in water are preferred.
Of these acid dyes, especially preferred for giving dyeings of
aromatic polyamide fibers or fabrics having excellent light
fastness are:
a. acid dyes in which the dye molecule matrix contains a structure
expressed by the formula ##SPC1##
and which do not contain --NR'.sub.2, wherein R' is a hydrogen atom
or an alkyl group, as an auxochrome;
b. acid dyes in which the dye molecule matrix contains a structure
expressed by the formula ##SPC2##
c. acid dyes in which the dye molecule matrix contains a structure
expressed by the formula ##SPC3##
Of these, acid dyes of the types (a) and (c) are especially
preferred.
Specific examples of the acid dyes that are used in the present
invention are the following:
1. monosulfonic acid type (m=1, A=--SO.sub.3 --)
c.i. 14675, 14680, 14690, 14695 14710, 15510, 15575, 15635, 15705,
18835, 18940 26660, 26665, 50120, 62045 44025, 45100, 50320,
50085
2. disulfonic acid type (m=2, A=--SO.sub.3 --)
c.i. 16240, 18130, 22910, 23635 24820, 24780
3. sulfonic acid-carboxylic acid mixed type (n=2 - 3, A=--SO.sub.2
-- and --COO--)
c.i. 14095, 17590, 18821, 26520 26560, 26695, 43825, 62120
4. carboxylic acid type (n=1 - 3, A=--COO--)
c.i. 13060, 14000, 14135, 16315 18710, 18885, 25100, 45305 43865,
43830
other examples are:
Acid dyes of the formula ##SPC4##
wherein R" is phenyl, alpha- or beta-naphthyl, 2-, 3-, or
4-halogenophenyls, 2-, 3-, or 4- tolyl, 2-, 3- or 4-nitrophenyl,
4-alkoxy-2-tolyl, 4-nitro-2-tolyl, 3-nitro-2-tolyl,
2-nitro-4-tolyl, 2-nitro-4-methoxyphenyl, 2-chloro-4-nitro phenyl,
2-methoxy-4-chlorophenyl, 2-methoxy-4-nitrophenyl,
2-methoxy-5-nitrophenyl, 2,5-dimethoxy-4-nitrophenyl, ##SPC5##
acid dye of the formula ##SPC6##
acid dye of the formula ##SPC7##
As the neutral or acidic inorganic salt to be present in the dye
bath in the present invention, alkali metal salts of inorganic
acids, or ammonium salts thereof are preferred, and especially
preferred are the alkali metal salts or ammonium salts of mineral
acids.
Specific examples of the salts include potassium chloride, sodium
chloride, ammonium chloride, potassium bromide, sodium bromide,
ammonium bromide, potassium nitrate, sodium nitrate, ammonium
nitrate, potassium sulfate, sodium sulfate, ammonium sulfate,
potassium pyrosulfate, sodium pyrosulfate, ammonium pyrosulfate,
potassium phosphate, sodium phosphate, ammonium phosphate,
potassium pyrophosphate, sodium pyrophosphate, and ammonium
pyrophosphate. Of these, potassium sulfate, sodium sulfate,
ammonium sulfate, potassium phosphate, sodium phosphate, ammonium
phosphate, potassium pyrophosphate, sodium pyrophosphate, and
ammonium pyrophosphate are preferred, and next come potassium
nitrate, sodium nitrate, and ammonium nitrate. Ammonium sulfate
gives especially good results. These salts are used either alone or
in admixture.
The dye bath used in the present invention may contain various
dyeing assistants conventionally utilized in dip dyeing with acid
dyes, such as ultraviolet absorbants, pH adjusting agents, or
surface active agents. Examples of the ultraviolet absorbants are
4,4'-dimethoxy-2,2'-dihydroxybenzophenone,
2,4-dihydroxybenzophenone, and
2-(2'-hydroxy-5'-methylphenyl)benzotriazole. Examples of the pH
adjusting agents are sulfuric acid, formic acid, or succinic acid.
As the surface active agent, anionic surfactants can be cited and
nonionic surfactants.
The pretreatment of aromatic polyamide fibers or fabrics with the
swelling agent may conveniently be carried out by immersing the
fibers or fabrics in a solution, dispersion or emulsion containing
the swelling agent or padding them with such solution, dispersion
or emulsion, thereby bringing the fibers or fabrics into intimate
contact with the swelling agent, preferably under heating, and
thereby coating or permeating the swelling agent on or into at
least the surface or surface layer of the fibers or fabrics. Where
the boiling point of the swelling agent is very low, the fibers or
fabrics may be contacted with a vapor of such swelling agent. If
the swelling agent is a normally liquid compound, or a solid
compound having a low melting point, the fibers or fabrics may be
contacted with the liquid or a molten liquid of the swelling agent.
In the case of using the swelling agent in the form of solution,
dispersion or emulsion, not only water, but a solvent for the
swelling agent can be used. Solvents or semi-solvents which
dissolve or swell the aromatic polyamides can also be utilized.
When acid mordant dyes are used, mordanting metal ions such as
chromium, nickel, cobalt, and aluminum ions can be conjointly used
at the time of the pretreatment.
When alkali metal salts of compounds having a phenolic hydroxyl
group are used in the above-mentioned pre-treatment, organic or
inorganic acids in amounts sufficient to at least neutralize the
alkali salts are added to the dye bath in advance. Specific
examples of such acids are those mentioned with respect to the pH
adjusting agents.
The pretreatment can also be carried out in the copresence of the
compound having a phenolic hydroxyl group and an alkali metal
hydroxide or a salt of an alkali metal with a weak acid. In this
case also, an acid in an amount at least sufficient to neutralize
the alkali salt of the compound having a phenolic hydroxyl group
picked up by the fibers or fabrics as a result of the pre-treatment
should be added to the dye bath in advance.
In order to increase the solubility or dispersibility of the
swelling agent, a small amount of a water-miscible organic solvent,
such as alcohols or acetone, or an anionic surface active agent may
be added to a solution of the swelling agent to be used for the
pre-treatment.
The pre-treatment is conveniently performed by heating while the
aromatic polyamide fibers or fabrics are brought into intimate
contact with the swelling agent, and frequently, temperatures from
60.degree.C. to 160.degree.C., preferably from 80.degree.C. to
140.degree.C., are employed to this end.
When the pre-treatment is omitted in the process of the invention
and the swelling agent is incorporated into the dye bath in
advance, it is not necessary to pre-heat the fibers or fabrics to
be dyed, but they may simply be dyed at the dyeing temperature.
The amount of the swelling agent can be optionally changed
according to the type of swelling agent, the type of aromatic
polyamide to be dyed, the type of acid dye used, or the shape of
the fibers or fabrics. Generally, however, the preferred amount is
0.5 to 50 percent based on the weight of the fibers (o.w.f.),
especially 4 to 40 percent o.w.f., more especially 5 to 30 percent
o.w.f. At this time, the amount of the neutral or acidic inorganic
salt is 1 to 40 percent o.w.s. (based on the weight of the
solution), especially 3 to 30 percent o.w.s., and more especially 3
to 20 percent o.w.s.
The dyeing operation is not especially restrictive, and those
operations which are used for conventional dip dyeing can be
utilized. Since dyeings of deep color cannot be obtained when the
amount of the neutral or acidic inorganic salt in the bath is not
more than 1 percent by weight, the amount of this salt should be 1
percent by weight or more. The dyeing temperature is 80.degree.C.
to 200.degree.C., preferably about 100.degree.C. to
150.degree.C.
In the dyeing process of the present invention, the goods-to-liquor
ratio is important for dyeability. The preferred goods-to-liquor
ratio is 1:5 to 1:100, more preferably 1:5 to 1:50.
After dyeing, the resulting dyeing is soaped by a customary method.
The soaping is carried out with surface active agents, or alkalies.
The soaping with alkalies is especially recommended. It is of
course possible to soap the dyeing both with the surface active
agent and alkalies. The compound having a phenolic hydroxyl group
forms an alkali metal salt of phenol in an aqueous solution of an
alkali metal hydroxide or an alkali metal weak acid salt, and thus,
its affinity for the fibers is remarkably reduced, and on the other
hand, its solubility in water is very much increased. Consequently,
the compound having a phenolic hydroxyl group present in the dyeing
can be readily removed, and the absorbed dye is hardly liberated.
This is desirable for obtaining dyed aromatic polyamide fibers
having excellent flame-proofing properties and thermal
stability.
Examples of such alkaline compounds include hydroxides, carbonates,
bicarbonates, borates, silicates, or acetates of alkali metals, for
example, sodium hydroxide, potassium hydroxide, lithium hydroxide,
sodium carbonate, sodium bicarbonate, potassium carbonate,
potassium bicarbonate, sodium acetate, potassium acetate, lithium
acetate, sodium borate, potassium borate, sodium silicate, and
potassium silicate.
The amount of alkaline compound is, for example, 0.5 to 10 percent
by weight (o.w.s.), and it is used as an aqueous solution. The
soaping is carried out by immersing the dyeing in an aqueous
solution containing the alkaline compound at a temperature from
60.degree.C. to the boiling point, for 10 to 30 minutes.
The soaping of the dyeing can also be performed by utilizing a
solvent (including a water-containing solvent) for the dye or
compound having a phenolic hydroxyl group. Examples of such solvent
include aliphatic lower alcohols such as methanol, ethanol, or
propanol, aliphatic ketones such as acetone or methyl ethyl ketone,
halogenated hydrocarbons such as trichloroethylene or
perchloroethylene, and aliphatic amides sch as dimethyl acetamide,
or dimethyl formamide.
The following Examples will illustrate the present invention in
greater detail. In the Examples, the measurement of dyeability,
removability of swelling agent, light fastness, and flame proofing
properties was made as follows:
DYEABILITY
This is shown by the lightness (L value) of the dyeing which has
been measured using a color differential meter. This value differs
according to the dye used. When the same dye is used, larger L
values show lighter dyeings, and smaller values, deeper
dyeings.
REMOVABILITY OF SWELLING AGENT
The sample dyeing was soaped with N,N-dimethyl formamide at
100.degree.C. until the swelling agent on the sample was completely
removed, and its weight (X) g was measured. Using this as a
standard, the weight (Y gram) of a sample dyeing of the same size
which was soaped was measured. The removability is calculated as
follows:
(Y) -- (X)/(X) .times. 100 (%).
LIGHT FASTNESS
Measured using a fade-O-meter (JIS L-1044/59, carbn arc lamp
method, A method).
FLAME-PROOFING PROPERTIES
Measured in accordance with JIS-L1091/71 (horizontal-type A.sub.3
method).
WASHING FASTNESS
Measured in accordance with JIS-L0844/70
DRYCLEANING FASTNESS
Measured in accordance with JIS-L0860/65
FASTNESS TO DRY AND WET RUBBING
Measured in accordance with JIS-L0849/67
EXAMPLE 1 AND COMPARATIVE EXAMPLE 1
Aromatic polyamide having an inherent visocisty of 1.7 obtained by
the copolymerization of m-phenylene diamine and a 97:3 mixture of
isophthaloyl chloride and terephthaloyl chloride was dry spun from
its dimethyl acetamide solution containing calcium chloride, and
then drawn 400 percent in boiling water and a hot plate to obtain a
multifilament tow (1.8 denier per filament). The tow was crimped
under wet heat, and then cut to a staple length of 3.8 cm. A staple
fabric (250 g/m.sup.2) was prepared from the staples by spinning
and weaving operations.
The fabric obtained was scoured for 30 minutes at 80.degree.C. in
an aqueous solution containing 2 g/liter of sodium
dodecylbenzenesulfonate, and then pre-set at 220.degree.C. for 30
seconds, followed by dyeing under the following dyeing
conditions.
Dyeing conditions
Dye C.I. 15510 4% o.w.f. Swelling agent p-phenylphenol 7.5% o.w.f.
Inorganic salt ammonium sulfate 150 g/liter pH adjusting agent
acetic acid 20 g/liter Goods-to-liquor ratio 1:15 Temperature
130.degree.C. Time 90 minutes
After dyeing, the dyeing was thoroughly washed with water, and
treated in an aqueous solution containing 3 g/liter of sodium
carbonate (at a goods-to-liquor ratio of 1:30) at 85.degree.C. for
20 minutes to remove the swelling agent. The treated dyeing was
washed with water, and then dried in air. The results are shown in
Table 1 below.
For comparison, the foregoing procedure was repeated except that
the dye bath did not contain ammonium sulfate (Comparative Example
1); the dye bath did not contain p-phenyl phenol (Comparative
Example 2); Basic Orange 22, C.I. 48040 was used instead of the
acid dye (Comparative Example 3); and benzaldehyde was used instead
of p-phenyl phenol (Comparative Example 4).
TABLE 1
Properties of Dyeings Dyea- Remova- bility bility of (L- swelling
Light Flame- value) agent fastness proofing Hand* properties Ex. 1
48.5 4.0% Class 3 4.1 cm Com. Ex. 1 59.2 3.8% Below class 1 4.1 cm
Com. Ex. 2 67.4 3.6% Below class 1 4.3 cm Com. Ex. 3 49.3 0.5%
Class 3 8.2 cm harsh Com. Ex. 4 59.6 0.2% Below class 1 7 cm *
According to a functional test.
EXAMPLES 2 TO 5 AND COOPERATIVE EXAMPLES 5 TO 10
The staple woven fabric of Example 1 was dyed under the following
dyeing conditions. The dyes used were acid dyes which could dye
ordinary polyamides with only inferior light fastness but come
within the acid dyes specified in the present invention. The
results obtained are shown in Table 2.
Dye acid dye 6% o.w.f. Swelling agent p-phenyl phenol 20% o.w.f.
Inorganic salt ammonium sulfate 75 g/liters pH adjusting agent
acetic acid 20 g/liters Goods-to-liquor ratio 1:15 Temperature
130.degree.C. Time 90 minutes
For comparison, Table 2 also gives the results obtained when nylon
6 was dyed in a customary manner with the same dyes using a dye
bath of a pH 4 at 95.degree.C. for 60 minutes. ##SPC8##
The staple fabrics of Example 1 were dyed in the same way as in
Example 2 using acid dyes which dye ordinary polyamides with good
fastness characteristics but are outside the scope of the acid dyes
specified in the present invention. Using the same dyes, nylon 6
was dyed in the same way as set forth in Comparative Example 5. The
results are given in Table 2' as Comparative Examples 9 and 10 and
Controls 1 and 2. ##SPC9##
EXAMPLES 6 TO 17 AND COMPARATIVE EXAMPLES 11 TO 15
The same fabric as used in Example 1 was dyed under the following
conditions using the swelling agent and inorganic salt shown in
Tables 3 and 3' below. The results are given in Tables 3 and
3'.
Dyeing conditions
(a) (b) Dye C.I. 14680 C.I. 15510 4% o.w.f. 6% o.w.f.
p-phenylphenol Swelling agent 40% o.w.f. 11% o.w.f. Inorganic salt
Ammonium sulfate 100 g/l. 75 g/l. Acetic acid 20 g/l. 20 g/l.
Goods-to-liquor ratio 1:15 1:15 Temperature 130.degree.C.
130.degree.C. Time 90 minutes 90 minutes
After the dyeing operation, the resulting dyeing was washed
thoroughly with water, and washed for 20 minutes at 80.degree.C. in
an aqueous solution containing 2 g/liter each of sodium
hydrosulfite, sodium hydroxide and polyoxyethylene (20 mols)
stearylamine (the goods-to-liquor ratio being 1 : 100), followed by
washing with water and air drying.
TABLE 3
[Dyeing under the conditions
(a)] Run Nos. Swelling agent Dyeability (L value)* Example 6
beta-naphthol 26.2 Example 7 alpha-naphthol 27.1 Example 8
p-phenylphenol 30.3 Example 9 m-cresol 36.4 Example 10
o-phenylphenol 37.5 Comparative Ex. 11 resorcinol 48.7 Comparative
Ex. 12 chlorobenzene 50.8 Comparative Ex. 13 Methylnaphthalene 48.6
Comparative Ex. 14 Benzaldehyde 45.1 * With C.I. 14680 used in the
dyeing under the conditions (a), dyeings having an L value of less
than 45 are substantially dyed. If this value is below 35, the
dyeings are of deep color.
TABLE 3'
[Dyeing under the conditions
(b)] Run Nos. Inorganic salts Dyeability (L value)* Example 11
ammonium sulfate 48.4 Example 12 ammonium phosphate 49.7 Example 13
sodium sulfate 50.5 Example 14 sodium phosphate 50.1 Example 15
sodium pyrophosphate 49.4 Example 16 sodium nitrate 52.5 Example 17
sodium chloride 53.2 Comparative Ex. 15 sodium bicarbonate 60.2 *
With C.I. 15510 used in the dyeing under the conditions (b),
dyeings having an L value more than 65 are not substantially dyed,
but merely soiled. The dyeings having an L value of above 50 are of
deep color.
EXAMPLE 18 AND COMPARATIVE EXAMPLES 16 TO 21
A fabric woven from staple fibers of polymetaphenylene
isophthalamide terephthalamide was immersed in a homogeneous
aqueous solution obtained by adding 20 parts of p-phenyl phenol and
6 parts of sodium hydroxide to 75 parts of water, and heating the
mixture to 90.degree.C. Without cooling, the immersed fabric was
uniformly squeezed by a mangle so that the aqueous solution of a
sodium salt of p-phenyl phenol was uniformly impregnated in the
fabric (pick up 80 percent). The fabric so treated was then put
into a dye bath (goods-to-liquor ratio of 1 : 15) containing 6
percent o.w.f. of each of the dyes shown in Table 3, 75 g/liter of
ammonium sulfate, and 20 g/liter of acetic acid at 80.degree.C.,
and dyed at 140.degree.C. for 90 minutes. After dyeing, the dyed
fabric was washed with the same aqueous solution as used in Example
6, followed by washing with water and air drying. The L value and
fastness to light of the dyed fabric were measured, and the results
are shown in Tables 4-a to 4-c. ##SPC10## ##SPC11##
TABLE 4c
Color Dyeability Light fastness Run index of (L value) (class) No.
dyes 1 15620 23.5 3-4 2 15635 32.1 4 3 15510 45.0 3 4 15575 43.0
3-4 5 18835 71.9 3-4 6 18130 37.2 3 7 22910 67.3 3-4 8 24820 69.7 3
9 50315 24.3 4 10 50320 19.6 4 11 18940 35.1 3 12 26520 41.1 3 13
17055 19.5 3
EXAMPLE 19
In accordance with the method of producing a regular copolyamide
which is disclosed in Example 5 of U. S. Pat. No. 3,232,910,
N,N'-metaphenylene bis-(metaaminobenzamide) was polycondensed with
isophthaloyl chloride to form an aromatic polyamide having an
inherent viscosity of 1.2. A staple fabric was prepared from the
aromatic polyamide in the same way as set forth in Example 1. The
woven fabric was scoured and pre-set in the same way as set forth
in Example 1, and then dyed under the following conditions.
The woven fabric was immersed in a homogeneous aqueous solution
prepared by adding 25 parts of the sodium salt of para-phenyl
phenol to 75 parts of water, and heating the mixture to
85.degree.C. Without cooling, the immersed fabric was uniformly
squeezed by a mangle (pick up 80 percent), and then put into a dye
bath (goods-to-liquor ratio 1:10) containing 5 percent o.w.f. of
dye C.I. 18835, 75 g/liter of ammonium sulfate, and 15 g/liter of
formic acid. The dyeing was performed at 130.degree.C. for 2
hours.
The resulting dyeing was washed for 20 minutes at 70.degree.C. with
an aqueous solution (goods-to-liquor ratio 1:50) containing 2
g/liter of sodium hydroxide, and washed thoroughly with warm water.
The alkali remaining on the fabric was neutralized with water
containing a small amount of acetic acid, and then the fabric was
dried. The dyeing exhibited a brilliant deep yellow, and had an L
value of 70.3. It had a light fastness of class 3. In the
flame-proofing test, the maximum flame diameter was 4.5 cm, showing
satisfactory results. The fabric also had excellent fastness
characteristics such as fastness to washing (class 4), fastness to
drycleaning (class 5), and fastness to dry and wet rubbing (class
5).
EXAMPLE 20
Poly (m-benzamide) having an inherent viscosity of 1.3 prepared in
accordance with the method disclosed in British Patent 901,159 was
dry spun from its dimethyl acetamide solution containing lithium
chloride, and a fabric was woven from the resulting multifilament
tow in the same way as set forth in Example 1. The fabric was
immersed in a solution of 10 parts of beta-naphthol in 9 parts of
ethanol at 50.degree.C. Without cooling, the immersed fabric was
squeezed uniformly to a pick up of 80 percent, dried, and dyed in a
dye bath (goods-to-liquor ratio 1:6) containing 4 percent o.w.f. of
C.I. 15575 dye, 50 g/liter of sodium sulfate, and 10 g/liter of
acetic acid at 140.degree.C. for 90 minutes. After the dyeing
operation, the dyed fabric was washed twice with an aqueous
solution of 20 g/liter of sodium carbonate (goods-to-solution ratio
1:30) at 70.degree.C. for 20 minutes, then washed thoroughly with
water, and air dried to give a brilliant deep orange dyeing having
an L value of 43.0. The dyed fabric had fastness to light (class
3), washing (class 4), drycleaning (class 5), and dry and wet
rubbing (class 4).
EXAMPLE 21
Staple fibers were obtained in the same way as set forth in Example
1 from polymetaphenylene isophthalamide having an inherent
viscosity of 1.8 obtained by the polymerization of m-phenylene
diamine and isophthaloyl chloride, and made into a knitted fabric
(200 g/m.sup.2). The knitted fabric was scoured under the same
conditions as set forth in Example 1. The fabric was then
pre-treated with the swelling agent, washed with water, and then
dyed under the following dyeing conditions.
Conditions for treating with the swelling agent
Chromizing agent K.sub.2 Cr.sub.2 O.sub.7 15% o.w.f. Swelling agent
p-phenyl phenol 20% o.w.f. Acid acetic acid 8 g/l. Goods-to-liquor
ratio 1:15 Temperature 150.degree.C. Time 60 minutes
Dyeing conditions
Dye C.I. 43830 6% o.w.f. Swelling agent p-phenyl phenol 20% o.w.f.
Inorganic salt ammonium sulfate 75 g/l. pH adjusting agent acetic
acid 20 g/l. Goods-to-liquor ratio 1 : 15 Temperature 130.degree.C.
Time 60 minutes
After the dyeing operation, the dyed fabric was washed thoroughly
with water, and treated with an aqueous solution containing ethanol
(goods-to-solution ratio 1 : 30) at 80.degree.C. for 20 minutes to
thereby remove the swelling agent remaining in the fabric, followed
by washing with water and air drying. The resulting dyed fabric had
deep color with an L value 18.6. The dyeing had fastness to light
(class 3), washing (class 4), drycleaning (class 5), and dry and
wet rubbing (class 5).
EXAMPLE 22
Monofilaments (30 count) composed of polymetaphenylene
isophthalamide obtained in the same way as set forth in Example 1
were steamed at 100.degree.C. to set the twist, and scoured in the
form of skein in the same way as set forth in Example 1. The skein
was packed into a carrier of a cheese dyeing machine with a packing
density of 0.28 g/cm.sup.3, and at 90.degree.C. 5% o.w.f. of dye
(C.I. 15510), 25 percent o.w.f. of o-phenyl phenol, 50 g/l. of
ammonium sulfate, and 10 g/l. of acetic acid were put into the
machine in this order (goods-to-liquor ratio 1 : 15). The
temperature was raised at a rate of 10.degree.C. per 5 minutes, and
the dyeing was performed at 130.degree.C. for 90 minutes (in-out
only). After the dyeing operation, the liquor was discharged at
90.degree.C., and the yarn was thoroughly washed with warm water.
The swelling agent remaining in the yarn was removed by treatment
with an aqueous solution containing 2 g/l. of polyoxyethylene (20
mols) stearylamine and 5 g/l. of sodium carbonate
(goods-to-solution ratio 1 : 15) at 90.degree.C. for 30 minutes.
The dyed yarn was washed with warm water, and then dried. There was
no difference in the dyeing density between the inner and outer
layers of the yarn, and uniform dyeing could be effected.
* * * * *