U.S. patent number 3,632,419 [Application Number 04/728,843] was granted by the patent office on 1972-01-04 for method for imparting durable soil-resistant finish to polyamide and polyester fabrics and the treated fabrics.
This patent grant is currently assigned to Fukui Seiren Kako Co., Ltd.. Invention is credited to Tadao Hirano, Hajime Horie, Atumi Ishimoto, Hideo Okuyama.
United States Patent |
3,632,419 |
Horie , et al. |
January 4, 1972 |
METHOD FOR IMPARTING DURABLE SOIL-RESISTANT FINISH TO POLYAMIDE AND
POLYESTER FABRICS AND THE TREATED FABRICS
Abstract
A method of imparting a durable soil-resistant finish to
synthetic fabrics selected from the group consisting of polyamide
and polyester fabrics comprising padding the fabrics in a treating
bath containing 2-10 percent by weight of a polymer hydrosol
selected from the group consisting of polymethacrylic acid,
polyvinyl alcohol and carboxymethyl cellulose in the form of
colloidal dispersion, 0.1-4.0 percent by weight of precondensate
resin of a member selected from the group consisting of cyclic
ethylene-urea and melamine-formaldehyde resins, and acidic catalyst
for these resins, squeezing the treated fabrics with a mangle at a
pickup of 40-100 percent, drying the squeezed fabrics at
80.degree.-110.degree. C. and subjecting the fabrics to a
high-temperature treatment at 140.degree.-170.degree. C. for 30-40
seconds; washing the resultant fabrics with an aqueous solution
containing a detergent maintained at above 40.degree. C., drying
and finishing.
Inventors: |
Horie; Hajime (Fukui-shi,
JA), Hirano; Tadao (Fukui-shi, JA),
Okuyama; Hideo (Fukui-shi, JA), Ishimoto; Atumi
(Fukui-shi, JA) |
Assignee: |
Fukui Seiren Kako Co., Ltd.
(Fukui-shi, Fukui-ken, JA)
|
Family
ID: |
13521441 |
Appl.
No.: |
04/728,843 |
Filed: |
May 13, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Nov 15, 1967 [JA] |
|
|
42/73550 |
|
Current U.S.
Class: |
442/93; 252/8.62;
427/369; 427/354; 427/381 |
Current CPC
Class: |
D06M
15/09 (20130101); D06M 15/423 (20130101); D06M
15/263 (20130101); D06M 15/333 (20130101); Y10T
442/2279 (20150401) |
Current International
Class: |
D06M
15/37 (20060101); D06M 15/263 (20060101); D06M
15/423 (20060101); D06M 15/333 (20060101); D06M
15/09 (20060101); D06M 15/21 (20060101); D06M
15/01 (20060101); D06n 015/16 (); B32b
027/06 () |
Field of
Search: |
;117/161UB,161UN,161LN,161UE,139.5A,139.5C,138.8F,138.8N,166 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Husack; Ralph
Claims
1. A method of imparting a durable soil-resistant finish to
synthetic fabrics selected from the group consisting of polyamide
and polyester fabrics comprising padding the fabrics in a treating
bath consisting essentially of 2-10 percent by weight of a polymer
hydrosol selected from the group consisting of polyvinyl alcohol
and carboxymethyl cellulose in the form of a colloidal dispersion,
the particles of said hydrosol having a particle size in the range
of 0.05-5.mu.; 0.1-4.0 percent by weight of precondensate resin of
at least a member selected from the group consisting of cyclic
ethyleneurea and melamine-formaldehyde resins, and an acidic
catalyst for these resins, squeezing the treated fabrics with a
mangle at a pickup of 40-100 percent, drying the squeezed fabrics
at 80.degree.-110.degree. C. and subjecting the fabrics to a
temperature of from 140.degree. to 170.degree. C. for 30 to 40
seconds; washing the resultant fabrics with an aqueous solution
containing a detergent
2. A method of claim 1, wherein the particles of said hydrosol have
a
4. A method of claim 1, wherein the hydrosol is a carboxymethyl
cellulose.
6. A method of claim 1, wherein the hydrosol is a
melamine-formaldehyde
7. A synthetic fabric selected from the group consisting of
polyamide and polyester fabrics which has been treated by the
method of claim 1.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a method of imparting soil-resistant
finish to knitted or woven fabrics of polyamides or polyesters.
2. Description of the Prior Art
Though synthetic fibers have been remarkably developed in recent
years due to their superior properties, there still remain some
drawbacks with them in that, for example, they tend to be easily
soiled, among others.
In an early stage of studies on soiling of knitted or woven
fabrics, efforts were concentrated on analyses of soil components
and clarification of adhesion mechanism of soils on cotton and
wool, and some soil-resistant finishes were proposed based on the
observations obtained. However, a reliable method of soil-resistant
finish had not been developed when synthetic fibers appeared, and
owing to their property to be easily soiled, the problem of soil
resistance was again closed up and it was studied from different
standpoints. Nevertheless, there has been found no reliable method
of imparting soil-resistant finish to synthetic fibers,
particularly against soils by contact. Though there are some
effective methods of soil release finish for preventing and
inhibiting soil redeposition (which may be referred to as resoiling
hereinafter) of polyester/cotton fabrics during laundering, the
fundamental concept of these methods is that generally a film of a
hydrophilic material is formed on the surface of hydrophobic
synthetic fibers to inhibit redeposition of oily soils during
laundering. For example, there has been proposed a method wherein
polyester fibers are treated with a block copolymer of polyethylene
glycol and polyethylene terephthalate. However, the methods
proposed heretofore have drawbacks in that they are not effective
for preventing resoiling by relatively hydrophilic soils with a
tendency to affect adversely, and that the soil resistance of
thus-treated fabrics to the soils floating in the air is not
improved but affected adversely due to the tacky film formed on the
surface thereof. Of course, it will be hardly expected to find a
perfect soil-resistant finish effective for all sorts of soils,
since the properties of soils adhering on clothes on wearing are so
complicated and there will be so many soils having various
contradictory properties to each other. Nevertheless, we have
concentrated our efforts from the consumer's standpoint to find an
effective soil-resistant finish to prevent soils from adhering on
the fabrics by contact without having serious adverse influence,
and accomplished the present invention.
The conventional methods of soil-resistant finish known heretofore
for natural textiles and regenerated cellulose fibers may be
classified as follows: (1) chemical modification such as
mercerization, acetylation, amino-alkylation, formalation,
carboxymethylation, and treatment by urea-formaline resins, (2)
application of film-forming agents such as carboxymethyl cellulose,
starch, polyvinyl alcohol, gelatine, polyvinyl acetate, acrylic
esters, cationic and anionic softening agents, silicon water
repellents, and organic fluorides, and (3 ) application of
fine-particle fillers such as colloidal silica, alumina, and iron
oxide. Although none of these methods affords a decisive and
satisfactory soil-resistant effect, some of them, for example,
treatment with carboxymethyl cellulose, show a temporary activity
to prevent resoiling and the treatment with colloidal silica shows
an activity to prevent soil adhesion by contact. However, such
effects obtained do not last for a prolonged period of time.
As described above, the concentrated studies on soil resistance of
synthetic fibers have just been started and practically no reliable
result has been obtained so far. Therefore, there is found no
permanent soil-resistant finish which is expected to show any
satisfactory effect in practice.
There is no established conclusion as to the soil-resisting effect
of antistatic agents and some of them show a soil-resistant effect,
though others act adversely depending on the type of the agents.
They have been studied only from the aspect of the antistatic
activity but not from the aspect of the soil resistance. The same
is said with regard to softening agents and there has been known
that, for example, polyethylene-, acrylic ester- or silicon-derived
softening agents adversely affect soil resistance considerably. The
method of imparting a soil-resistant finish to synthetic fibers is
now being earnestly studied under such circumstances as mentioned
above.
SUMMARY OF THE INVENTION:
The present invention relates to a method of imparting a
soil-resistant finish for knitted or woven fabrics of polyamides or
polyesters which is particularly effective for preventing soiling
by contact. In brief, the present invention is directed to render
knitted or woven fabrics more soil resistant and washfast than
those which have been achieved, by padding the knitted or woven
fabrics with a polymer hydrosol together with cyclic ethyleneurea
and/or melamine-formaldehyde resin, squeezing and drying the
fabrics, treating them at an elevated temperature and soaping the
fabrics thus treated.
In accordance with this invention, there is provided a method of
finishing knitted or woven fabrics of polyamides or polyesters
which affords excellent soil resistance, particularly to the
soiling by contact with dirt under dry conditions, as well as to
the resoiling in laundering, and excellent fastness against
laundering and drycleaning, free from any adverse effect on the
soiling by other types of dirt.
The method of this invention essentially comprises a process
comprising padding knitted or woven fabrics of polyester or
polyamide fibers in a treating bath containing 2-10 percent by
weight of a polymer hydrosol such as polymethacrylic acid,
polyvinyl alcohol or carboxyl methyl cellulose in the form of an
aqueous colloidal dispersion, 0.1-4.0 percent by weight of
precondensate resin of cyclic ethyleneurea and/or
melamine-formaldehyde resins, and an acidic catalyst for these
resins, squeezing the treated fabrics with a mangle at a pickup of
40-100 percent, drying the squeezed fabrics at
80.degree.-110.degree. C. and subjecting the fabrics to a
high-temperature treatment at 140.degree.-170.degree. C. for 30-40
seconds; and washing the resultant fabrics with an aqueous solution
containing anionic and/or nonionic detergent maintained at above
40.degree. C., drying and finishing.
In the padding described above, some cationic softening agents such
as an acrylamide softening agent may be added to said treating bath
in a small amount, e.g., less than 2 percent by weight calculated
as a solid component, for the purpose of obtaining a soft touch of
the treated fabrics as well as further enhancing the soil
resistance.
The knitted or woven fabrics treated as mentioned above exhibit an
excellent activity to prevent soils from adhering by contact under
dry conditions as well as a good soil-resistant activity to
resoiling in washing at home or in drycleaning, and also show
excellent fastness against washing and drycleaning.
The principle of the soil-preventing mechanism of the present
invention has not been completely clarified theoretically, but it
may be believed that the cleavages on the surface of the said
fibers into which soils may adhere are previously sealed with fine
particles of a colorless polymer to form a barricade against soils
thereby preventing adhesion of soils by contact, and the fine
particles of the said polymer are simultaneously fixed in the
cleavages on the surface of the said fibers chemically and
physically so that the barricade is kept resistant to soils in
washing. Then, by soaping the fabrics further, not only the quality
of the processed article is improved by removal of the excess fine
particles of the polymer settled on the surface of the treated
fabrics, but also the remarkably durable resistance to soils by
contact can be obtained by removing the unreacted
precondensate.
In the padding of the method of the present invention, the particle
size of the polymer hydrosol is a very important factor and the
particles having a size of about 0.5 .mu. give the most effective
soil resistance. In practice, it is necessary to use the polymer
hydrosol having the particle size ranging from 0.05-5.0 .mu..
The polymer hydrosols referred to herein designate those having
particle sizes as set forth above, thus, they are somewhat
different from those polymer hydrosols generally and commonly
referred to. Namely, a colloid or sol generally meant involves the
particle sizes ranging from an upper limit of about 0.2 .mu. to a
lower limit of about 5 m.mu., thus, the polymer hydrosol referred
to herein designates such colloid or sol involving particle sizes
near the upper limited mentioned above, or very fine suspension or
dispersion.
Such polymer hydrosols as used herein may be prepared relatively
easily, for example, by copolymerizing methacrylic acid with a
hydrophilic comonomer or by finely dispersing such hydrophilic
material in polymethacrylic acid. Alternatively, when using
water-soluble polymers such as polyvinyl alcohol or carboxy methyl
cellulose, the hydrosols may be prepared according to such
procedures as partial formalization, incomplete saponification,
partial conversion into metal salts, or the like.
The deviation of the particle size distribution in the polymer
hydrosol used in the method of this invention from the range set
forth above inevitably leads to fatal results such as very
unsatisfactory soil resistance, adversely affected touch and very
poor resistance to washing of finished fabrics.
If the soil resistance were brought about by filling with fine
particles, there might be used fine particles of an inorganic
material such as SiO.sub.2, however, in reality, there can be
obtained merely a temporary effect with these particles. Even if
the resin of the present invention is used together with such
inorganic materials, there cannot be achieved such a durable soil
resistance as that obtained by using the polymer hydrosol of the
present invention.
The resins used together with the polymer hydrosol not only affect
substantially the durability of the soil resistance of the treated
fabrics but also influence directly the soil resistance itself.
Moreover, the combination of the polymer hydrosol and the resin is
very essential and an indispensable factor in the present
invention. The compatibility of the hydrosol with various resins
was examined completely, e.g., with respect to water-soluble
polyurethane resins, methylated methylol-melamine primary
condensation resins, melamine-formaldehyde resins, cyclic
ethyleneurea resins, polyacrylic ester resins, polyvinyl acetate
resins, polyacrylamide resins, polyethylene resins, silicon resins,
phenol resins, oil-soluble polyurethane resins, oil-soluble
polyacrylic resins, and isocyanate resins. However, only cyclic
ethyleneurea resins and melamine-formaldehyde resins were found to
be suitable for the purpose of this invention. When employing these
resins together with the polymer hydrosol, the soil resistance of
the treated fabrics is increased and is given durability, that is,
the soil resistance is not reduced after laundering and
drycleaning.
The other resins used together with the polymer hydrosol cannot
give such good results. For example, such treatment results in an
insufficient adhesive effect on polyesters or polyamides, inferior
fastness to washing and drycleaning, and formation of a very tacky
film of the resins on which dirts adhere. The adhesive effect and
the amount of the resin employed together with the polymer hydrosol
greatly affect the soil resistance. An insufficient adhesive effect
and tackiness of the film give defects as described above, while,
the use of a resin having a higher adhesive effect in an excess
amount results in depositions of both the polymer hydrosol and the
resin in places other than cleavages on surface of the fibers, and
the deposit gives a negative influence on the soil resistance and
also gives a rough touch. That is, there are close relations among
the types of fibers, cleavage filler and resin used together with
the filler. It is necessary that such resin is hard and does not
yield tackiness, but possesses an adequate adhesive property. Fine
particles other than those of polymer hydrosol, such as silicate,
are not suitable as previously described because a suitable resin
used together therewith has not been found as yet.
When treating the fabrics with cyclic ethyleneurea resin or
melamine-formaldehyde resin along, a remarkable soil resistance
cannot be obtained, but a resistance slightly better than that
obtained usually may be recognized. When treating the fabrics with
cyclic ethyleneurea resin and/or melamine-formaldehyde resins and
then treating with the polymer hydrosol, there are gained the soil
resistance and its durability similar to those obtained by treating
with both above-mentioned agents together.
When treating the fabrics with each of the polymer hydrosol,
ethyleneurea resin or melamine-formaldehyde resin of the present
invention, respectively alone, the resulting soil resistance and
durability thereof is obviously lower than those obtained by
treating the fabrics with these agents all together. Considering
these facts, it is presumed that there occur some physical and
chemical changes to improve the soil resistance and its durability
when using these agents together. As previously explained, even
when using cyclic ethyleneurea resin or melamine-formaldehyde resin
together with fine particles such as SiO.sub.2 which have been
considered to have the soil-resisting activity, the soil resistance
and durability thereof may not be improved. That is, the increase
in the soil resistance and its durability cannot be obtained by
using cyclic ethyleneurea resin or melamine-formaldehyde resin
together with an already known agent for soil resistance other than
the polymer hydrosol of the present invention. Therefore, a durable
soil resistance can be gained only by using cyclic ethyleneurea
resin and/or melamine-formaldehyde resin together with the polymer
hydrosol of the present invention.
The amount of the polymer hydrosol used is in the range of 2-10
percent by weight calculated as concentration of the solid
component; and an amount less than specified above only affords
insufficient soil resistance. The use of the polymer hydrosol with
a higher concentration should be avoided because of sedimentation
of the excess fine particles on the surface of the treated fabrics
which degrades appearance of the knitted or woven fabrics, and also
causes falling off of the fine particles upon handling.
The resin in an amount of less than 0.1 percent by weight
calculated as the concentration of the solid component hardly
affords a sufficient durability of the soil resistance of the
treated fabrics.
A softening agent can be added to the treating bath, as described
above, for the purpose of adjusting the touch of the finished
fabrics, but, since the soil resistance tends to be greatly
deteriorated by the addition of an anionic or ampholytic
surfactant, only a specific type of cationic surfactants such as
the acrylic amide softening agent can be employed in practice.
The high-temperature treatment after drying is substantially
similar to the curing process in the conventional resin processing
of fabrics known heretofore, and it is indispensable for obtaining
a sufficient durability. The treatment should be performed at
temperatures in the range of 140.degree.-170.degree. C., and lower
temperatures than specified above only afford an insufficient
durability, while higher temperatures leads to deterioration in the
properties of the finished fabrics, such as dyeing fastness, thus,
the temperature should be maintained in the range set forth
above.
A brief explanation has been given above with regard to the soaping
in the posttreatment, and so far as the detergent used therefore is
concerned, either anionic or nonionic surfactants may be employed,
and the most important point in this treatment is to use the
detergents adequately and sufficiently to remove the excess fine
particles of the high polymer and the unreacted precondensate from
the surface of the finished fabrics.
EXAMPLE 1
A dyed cloth of woolly Tetron (polyester) fabrics was padded in a
bath obtained according to the following formulation with 70
percent pickup, dried at 105.degree. C., and cured at 150.degree.
C. for 40 seconds. Then, soaping in a bath of 3 g./liter of a
sodium sulfate of higher alcohol manufactured by Daiichi Kogyo Co.
was carried out at 60.degree. C. for 20 minutes with a winch,
followed by water rinsing, drying and finishing. The soil
resistance of the treated cloth is shown in table 1.
Components Aqueous colloidal dispersion of polymethacrylic acid in
a concentration of 20 % by weight 10 parts Precondensate of cyclic
ethyleneurea in a2 parts ration of 50 % by weight Organic amine
catalyst in a concentration of 20 % by weight 0.2 part Acrylic
amide softening agent in a concentration of 60 % by weight 3 parts
Water 84.8 parts
---------------------------------------------------------------------------
Table 1
soil adsorption Resoiling Resoiling by contact (A) (B)
__________________________________________________________________________
Untreated cloth 65 % 40 % 95 % Treated cloth 10 % 35 % 50 % Treated
cloth after dry-cleaning five times 15 % 37 % 58 %
__________________________________________________________________________
Soil adsorption by contact in table 1 was measured as follows:
The soils in a home vacuum cleaner were collected and filtered
through cloth to obtain soil powder, which was used as a soiling
agent. The agent and cloth specimens were weighed so that the
weight ratio may be 1:2, and were put together into a polyethylene
bag blown 200 times with air, and sealed; then, the bag was shaken
up in a tumbler drier for 30 minutes. The specimens were removed
and the surfaces were lightly padded three times by hand. Then, the
soil degree of the surface of the specimen was measured.
Resoiling (A) was measured as follows:
A soiling agent was prepared by mixing the soils collected from a
home vacuum cleaner employed above with an oil mixture consisting
of 15 percent stearic acid, 15 percent oleic acid, 15 percent
hardened oil, 15 percent olive oil, 10 percent cetyl alcohol, 25
percent solid paraffin, and 5 percent cholesterol, in a ratio of
1:1; 20 grams of the soiling agent were weighed, and after adding 3
grams of an anionic detergent, a domestic detergent manufactured by
Kao Soap Co., the mixture was mixed with 1,000 cc. of water. Into
the thus-prepared bath, cloth specimens were immersed and stirred
at 40.degree. C. for 10 minutes, water rinsed, and dried. The soil
degree of the soiled cloth specimen was measured.
Resoiling (B) was measured as follows:
Cloth specimens were immersed and stirred in an aqueous bath
consisting of 1 gram of carbon black, 9 grams of olive oil, and 20
g./liter of a sodium sulfate of higher alcohol manufactured by
Daiichi Kogyo Co., at 50.degree. C. for 5 minutes, water rinsed and
dried. The soiled specimens thus treated were then observed.
The soil degree was measured by using a spectro-reflectometer. The
reflectivity of the magnesium oxide plate at the dominant
wavelength of 530 m.mu. was assumed as 100 and the reflectivity of
cloth specimen was measured three times for piled six specimens,
and the average soil degree was obtained according to the following
equation:
R.sub.o - R.sub.s / R.sub.o .times. 100= Soil degree
wherein
R.sub.o : the reflectivity of the specimen before soiled;
R.sub.s : the reflectivity of the specimen after soiled.
EXAMPLE 2
A dyed cloth of Tetron Astralen Jersey was padded in a bath of the
following formulation, dried, cured at 160.degree. C. for 30
seconds, and then soaped with 3 g./liter of a nonionic detergent
manufactured by Daiichi Kogyo Co., at 60.degree. C. for 20 minutes
with a winch, dried and finished. The soil resistance of
thus-treated specimens is shown in table 2.
Components Colloidal dispersion of polyvinyl alcohol in a
concentration of 10 % by weight 40 parts Precondensate of a
melamine-formaldehyde resin in a concentration of 50 % by weight 3
parts Ammonium chloride (catalyst) 0.1 part Water 56.9 parts
---------------------------------------------------------------------------
Table 2
Soil Degree Soil adsorption Resoiling Resoiling by contact (A) (B)
__________________________________________________________________________
Untreated cloth 62 % 45 % 93 % Treated cloth 14 % 30 % 52 % Treated
cloth after washing with an electric washing machine 20 % 30 % 60 %
__________________________________________________________________________
EXAMPLE 3
A dyed Nylon elastic fabric (cashmere) was padded in a 3 percent
solution of precondensate of cyclic ethyleneurea (50 percent) and
dried. The said fabric was padded in a bath of the following
formulation, dried, soaped with 3 g./liter of the sodium sulfate of
a higher alcohol referred to hereinbefore and 1 g./liter of the
nonionic detergents referred to hereinbefore at 60.degree. C. for
20 minutes with a winch, and then water rinsed and dried to be
finished.
Components Aqueous colloidal dispersion of Poly-methacrylic acid in
a concentration of 20 % by weight 10 parts Aqueous colloidal
dispersion of carboxymethyl cellulose in a concentration of 10 % by
weight 10 parts Precondensate of ethyleneurea in a concentration of
50 % by weight 2 parts Precondensate of melamine-formaldehyde resin
1.5 parts Organic amine catalyst in a concentration of 20 % by
weight 0.5 parts Water 76 parts
The soil resistance of the treated cloth specimen is shown in table
3.
---------------------------------------------------------------------------
TABLE 3
Soil adsorption Resoiling Resoiling by contact (A) (B)
__________________________________________________________________________
Untreated cloth 72 % 28 % 89 % Treated cloth 16 % 18 % 72% Treated
cloth after washing 15 times 21 % 21 % 75 %
__________________________________________________________________________
EXAMPLE 4
A scoured woolly Tetron fabric (cashmere) was padded in a bath of
the following formulation and after drying, cured at 160.degree. C.
for 40 seconds; then, it was dyed at an elevated temperature under
a high pressure, as usual, and dried to be finished.
Components Aqueous colloidal dispersion of polymethacrylic acid in
a concentration of 20 % by weight 15 parts Aqueous colloidal
dispersion of polyvinyl alcohol in a concentration of 5 % by weight
5 parts Precondensate of cyclic ethyleneurea in a concentration of
50 % by weight 3 parts Organic amine catalyst in a concentration of
20 % by weight 1 part Water 76 parts
The soil resistance of the said fabric was excellent as seen in
table 4.
---------------------------------------------------------------------------
TABLE 4
Soil adsorption Resoiling Resoiling by contact (A) (B)
__________________________________________________________________________
Untreated cloth 67 % 37 % 96 % Treated cloth 45 % 30 % 70 % Treated
cloth after washing 10 times 47 % -- -- Treated cloth after
dry-cleaning 10 times 46 % -- --
__________________________________________________________________________
The washfastness of the said fabric was measured as follows:
The fabric was treated 10 times in a cycle consisting of stirring
in an electric washing machine in a bath containing 2 g./liter of
an anionic detergent, at 40.degree. C. for 10 minutes and water
rinsing for 5 minutes. The fastness to drycleaning was measured
after treating the fabric similarly to the treatment in a usual
laundry.
The fabrics treated according to the present invention have other
advantageous properties such as an excellent resistance to pilling,
which is one of the defects of synthetic fibers.
* * * * *