DETAILED DESCRIPTION OF THE INVENTION
[0001] The present invention concerns a wool treatment agent, and more specifically concerns
a wool treatment agent that shows superior stability against ionic substances.
[0002] It is known that wool fabrics suffer from the drawback of extensive shrinkage and
conversion to felt when laundered in the household. Conventional methods for preventing
such shrinkage (anti-shrinkage treatment methods) have included methods in which wool
fibers are chemically treated or treated with organic resins. Furthermore, methods
involving treatment with organosilanes or amino-group containing organopolysiloxanes
are known as methods for endowing such fabrics with a good hand (JP-A 4-119173). Among
these methods, the most widely utilized is the Chlorine Hercosett Process, generally
represented by US Patent 5928380. See also Senshoku Kogyo, Vol. 36, pp. 260-269).
In this treatment method, wool is subjected to a chlorination treatment, and is then
treated with a finishing agent. Ordinarily, the chlorine is neutralized using sodium
sulfite, etc., following the chlorination treatment. Next, the treatment with a finishing
agent is performed after the unnecessary ionic substances generated and the excess
sodium sulfite have been removed in a rinsing tank. However, trace amounts of ionic
substances still remain even after being passed through a rinsing tank. As result,
if an emulsion of an organopolysiloxane which has ionizable functional groups, such
as amino groups is used, the result is often separation and destruction of the emulsion.
[0003] As a result of diligent research conducted to solve the abovementioned, we have found
that an aqueous emulsion composition that is stable against ionic substances is obtained
by using a nonionic emulsifying agent that has an Hydrophobic Lipophilic Balance of
less than 15 and a nonionic emulsifying agent that has an HLB of 15 or greater. This
discovery led to the perfection of the present invention.
[0004] Specifically, the object of the present invention is to provide a wool treatment
agent which shows a superior stability against ionic substances, and which is useful
as an anti-shrinkage finishing agent.
[0005] The present invention is a wool treatment agent which is characterized by the fact
that said agent is an aqueous emulsion composition consisting of(A) an amino-group
containing organopolysiloxane, (B) a nonionic emulsifying agent with an HLB of less
than 15, (C) a nonionic emulsifying agent with an HLB of 15 or greater, and (D) water.
[0006] The amino-group containing organopolysiloxane of component (A) may be any organopolysiloxane
that has at least one amino group per molecule. There are no particular restrictions
on the type, of organopolysiloxane used; however, organopolysiloxanes in which amino
groups are bonded to silicon atoms via carbon atoms are highly desirable. Such amino-group
containing organopolysiloxanes may be linear, branched or cyclic. Examples of such
organopolysiloxanes include organopolysiloxanes having the following average molecular
formulae:
In said formulae, R indicates a substituted or unsubstituted monovalent hydrocarbon
group which has 1 to 20 carbon atoms. Concrete examples include aliphatic saturated
hydrocarbon groups, such as methyl groups, ethyl groups, propyl groups, butyl groups,
pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups and dodecyl
groups, aliphatic unsaturated hydrocarbon groups such as vinyl groups, allyl groups
and hexenyl groups, alicyclic unsaturated hydrocarbon groups such as cyclopentyl groups
or cyclohexyl groups, aromatic hydrocarbon groups such as phenyl groups, tolyl groups
and naphthyl groups, and substituted hydrocarbon groups in which the hydrogen atoms
bonded to carbon atoms of the abovementioned groups are partially replaced by halogen
atoms.
[0007] These groups need not be the same in each molecule; combinations of two or more different
types of groups may be used. Among these groups, methyl groups, or combinations of
methyl groups with other organic groups, are especially desirable. R
1 indicates a hydrogen atom or a monovalent hydrocarbon group examples of such hydrocarbon
groups include methyl groups, ethyl groups, propyl groups, phenyl groups and cyclohexyl
groups. X indicates a group selected from a set consisting of the aforementioned groups
expressed by R, hydroxy groups and alkoxy groups with 1 to 5 carbon atoms. Examples
of such alkoxy groups include methoxy groups, ethoxy groups and propoxy groups. Among
these groups, hydroxy groups or alkoxy groups are especially desirable. Y indicates
a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Q indicates a divalent
hydrocarbon group. Concrete examples of such hydrocarbon groups include alkylene groups,
such as methylene groups, ethylene groups, propylene groups and butylene groups; arylene
groups expressed by the formula -C
6H
4-; and alkylene-arylene groups expressed by the formula -(CH
2)
2C
6H
4-. Among these groups, propylene groups are especially desirable. m and n are integers
of 1 or greater. It is desirable that the dynamic viscosity of the organopolysiloxane
used be 10 mm
2/s or greater at 25°C. A viscosity in the range of 50 to 10,000 mm
2/s is even more desirable, a indicates an integer from 0 to 5, and is preferably 0
or 1. The amino-group containing organopolysiloxane of this invention can be manufactured
by subjecting a hydrolytic condensation product obtained by hydrolyzing, an organoalkoxysilane
expressed by the formula H
2N(CH
2)
3Si(CH
3)(OCH
3)
2, and [b] a dimethylpolysiloxane, to an equilibrium reaction while heating to a temperature
of 80 to 110°C using a basic catalyst, such as sodium hydroxide. Then, the basic catalyst
is neutralized by means of an acid when the reaction product has reached the desired
viscosity (see JP-A 53-98499). Diorganopolysiloxanes expressed by the following average
molecular formulae are examples of amino-group containing organopolysiloxanes that
are used as Component A.
[0008] Components (B) and (C) of the present invention are nonionic emulsifying agents.
These emulsifying agents are characterized by the fact that the nonionic emulsifying
agent of component (B) has an HLB of less than 15, and the nonionic emulsifying agent
of component (C) has an HLB of 15 or greater. In particular, it is desirable that
component (B) have an HLB in the range of 9 to 13, and an HLB in the range of 10 to
12 is even more desirable. Examples of useful nonionic emulsifying agents that can
be used include polyoxyethylene alkyl ethers, polyoxyalkylene alkylphenyl ethers,
polyoxyalkylene alkyl esters, sorbitan alkyl esters and polyoxyalkylene sorbitan alkyl
esters. One or more compounds with an HLB of less than 15 are selected from these
compounds for use as component (B), and one or more compounds with an HLB of 15 or
greater are also selected from these compounds for use as component (C). In regard
to the amount used, it is desirable that the total amount of components (B) and (C)
be in the range of 2 to 100 parts by weight per 100 parts by weight of component (A);
and an amount in the range of 2 to 60 parts by weight per 100 parts by weight of component
(A) is even more desirable. In regard to the ratio of component (B) to component (C),
these components are ordinarily used in the range of(1 : 99) to (99: 1) (weight ratio),
and a weight ratio in the range of (50: 50) to (99: 1) is even more desirable. Furthermore,
the abovementioned "HLB" is an indicator of the balance of hydrophilic groups and
lipophilic groups in the emulsifying agent molecule. The following calculation formulae
have been proposed for nonionic emulsifying agents: for example, in cases where the
emulsifying agent used is a fatty acid ester of a polyhydric alcohol, HLB is conveniently
calculated using the formula
(in this formula, S is the degree of saponification of the ester, and A is the acid
value of the fatty acid). Furthermore, in cases where only polyoxyethylene groups
are included as hydrophilic groups, HLB is calculated using the formula HLB = E/5
(in this formula, E is the weight percentage of oxyethylene groups). The nonionic
emulsifying agents of components (B) and (C) can be used simultaneously in the emulsification
of the amino-group containing organopolysiloxane of component (A). Alternatively,
this emulsification can be performed using one of the emulsifying agents; and the
other emulsifying agent can then be added to the aqueous emulsion thus obtained.
[0009] The emulsifying agents used for the aqueous emulsion composition of the present invention
may consist only of the above mentioned components (B) and (C). If necessary, however,
cationic emulsifying agents or amphoteric emulsifying agents such as aliphatic amine
salts, quaternary ammonium salts or alkylpyridinium salts, may also be used in combination
with these claimed components.
[0010] The water of component (D) is used to form the above mentioned components (A) through
(C) into an emulsion. There are no particular restrictions on the amount of water
used; ordinarily, however, the amount used is in the range of 100 to 1,000,000 parts
by weight per 100 parts by weight of component (A).
[0011] The aqueous emulsion composition of the present invention consists of the abovementioned
components (A) through (D). If necessary, however, organopolysiloxanes other than
component (A); alkoxysilanes such as methyldimethoxysilane, dimethyldiethoxysilane,
methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
γ -aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane
or γ-glycidoxypropyltrimethoxysilane, and the hydrolyzates of the preceding, colloidal
silica; metal salts of organic acids, such as dibutyltin dilaurate, dibutyltin dioctate,
dioctyltin dilaurate, dioctyltin diacetate, tin octylate, zinc stearate, zinc octylate
or iron octylate, condensation reaction catalysts, e. g., amine compounds such as
n-hexylamine or guanidine, and other additives such as anti-wrinkling agents, thickeners,
coloring agents, preservatives, anti-mold agents and anti-rust agents, may also be
used in addition to the abovementioned components. Furthermore, the mean particle
size of the aqueous emulsion of the present invention is ordinarily 0.1 µm or greater.
[0012] This wool treatment agent of the present invention is stable against ionic substances;
in particular, it is characterized by the fact that there is no separation or destruction
of the emulsion caused by sodium sulfite or ionic substances generated by the neutralization
process that is performed following the chlorination treatment. This wool treatment
agent of the present invention imparts superior anti-shrinkage properties and a good
hand to all types of wool, such as tops, bulk wool, knitwear and cloth.
EXAMPLES
[0013] Next, the present invention will be described in detail in terms of working examples.
In these examples, all parts and percentages are parts by weight or weight percentages.
Furthermore, all viscosity values are values measured at 25°C.
Example 1
[0014] 30 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
2 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8)
and 1 part of a polyoxyethylene (ethylene oxide -20 moles) lauryl ether (HLB = 16.6)
were uniformly mixed. Afterward, 3 parts of water were added and the resulting mixture
was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill and an additional 64 parts of water were added. A uniform aqueous emulsion composition
was thus produced. The mean particle size of this aqueous emulsion composition was
0.31 µm.
[0015] Three pieces (45 × 45 cm) of an undyed 100% wool clothing-material serge were immersed
for 30 seconds in a treatment bath using the above aqueous emulsion composition as
a treatment liquid. Afterward, these samples were wrung out by means of mangle rollers
with the wringing rate adjusted to 100%. The samples were then spread on a metal mesh
and dried for one day and night at room temperature. Next, the samples were heat-treated
for 5 minutes at 130°C in a hot air drier. After the samples were allowed to stand
until they cooled to room temperature, 30 cm marks were applied at three places each
in the warp and woof directions; and the samples were laundered under the laundering
conditions described below. Following this laundering, the wool material samples were
spread horizontally and dried. The laundering shrinkage rate (%) was measured for
the warp and woof directions.
Laundering Conditions
[0016] After being laundered once under the following conditions, the material samples (from
which the detergent had been removed) were rinsed twice with water under the same
conditions.
- Bath ratio
- 1: 50
- Temperature
- 40°C
- Detergent
- ZABU™ (a weakly alkaline detergent manufactured by Kao K.K.)
- Time
- 15 minutes
[0017] To investigate the stability of the above mentioned aqueous emulsion composition
against ionic substances, 3 parts of the above mentioned emulsion was uniformly dispersed
in 97 parts of water, after which 10 parts of a 10% aqueous solution of sodium sulfite
were added and uniformly mixed. Afterward, the resulting mixture was allowed to stand
at room temperature until the following day, and the external appearance of the emulsion
was investigated by visual inspection. The results obtained are shown in Table 1.
Example 2
[0018] 30 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
and 3 parts of a polyoxyethylene (ethylene oxide -6 moles) lauryl ether (HLB = 11.8)
were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill, and 63 parts of water were added and uniformly mixed. Then, 1 part of a polyoxyethylene
(ethylene oxide -20 moles) lauryl ether (HLB = 16.6) was added, thus producing an
aqueous emulsion composition. The mean particle size of this aqueous emulsion composition
was 0.30 µm.
[0019] Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate
and stability against ionic substances were measured in the same manner as Example
1. The results obtained are shown in Table 1.
Comparative Example 1
[0020] 30 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
and 3 parts of a polyoxyethylene (ethylene oxide -6 moles) lauryl ether (HLB = 11.8)
were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill, and 64 parts of water were added and uniformly mixed, thus producing an aqueous
emulsion composition. The mean particle size of this aqueous emulsion composition
was 0.30 µm.
[0021] Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate
and stability against ionic substances were measured in the same manner as Example
1. The results obtained are shown in Table 1.
Comparative Example 2
[0022] 30 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
and 3 parts of a polyoxyethylene (ethylene oxide -20 moles) lauryl ether (HLB = 16.6)
were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill and 64 parts of water were added and uniformly mixed, thus producing an aqueous
emulsion composition. However, this aqueous emulsion composition separated after only
a few hours.
Comparative Example 3
[0023] 30 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
2 parts of a polyoxyethylene (ethylene oxide -6 moles) lauryl ether (HLB = 11.8)
and 1 part of a polyoxyethylene (ethylene oxide - 10 moles) lauryl ether (HLB = 14.1)
were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill, and 64 parts of water were added and uniformly mixed, thus producing an aqueous
emulsion composition. The mean particle size of this aqueous emulsion composition
was 0.32 µm.
[0024] Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate
and stability against ionic substances were measured in the same manner as Example
1. The results obtained are shown in Table 1.
Comparative Example 4
[0025] The laundering shrinkage rate of a 45 × 45 cm sample of an undyed 100% wool clothing-material
serge that had not been treated by means of the above-mentioned aqueous emulsion composition
was measured in the same manner as Example 1. The results obtained are shown in Table
1.
Table 1
|
HLB of Emulsifying Agent |
Laundering Shrinkage Rate (%) |
Stability Against Ionic Substances |
Comprehensive Evaluation |
|
|
Warp Direction |
Woof Direction |
Total |
|
|
Example 1 |
11.8 |
16.6 |
4.8 |
2.7 |
7.5 |
Stable |
Extremely Good |
Example 2 |
11.8 |
16.6 |
4.6 |
2.5 |
7.1 |
Stable |
Extremely Good |
Comparative Example 1 |
11.8 |
-- |
4.9 |
2.4 |
7.3 |
Emulsion Separated |
Stability Insufficient |
Comparative Example 2 |
16.6 |
-- |
-- |
-- |
-- |
-- |
Storage Stability Unsatisfactory |
Comparative Example 3 |
11.8 |
14.1 |
4.7 |
2.6 |
7.3 |
Emulsion Separated |
Stability Insufficient |
Comparative Example 4 |
-- |
-- |
10.3 |
7.4 |
17.7 |
-- |
-- |
Example 3
[0026] 30 parts of an amino-group-containing diorganopolysiloxane expressed by the average
molecular formula
3 parts of a polyoxyethylene (ethylene oxide -6 moles) lauryl ether (HLB = 11.8)
and 1 part of a cationic emulsifying agent expressed by the formula (CH
3)
3(C
12H
25)N
+Cl
- were uniformly mixed. Afterward, 4 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill. Then, 51 parts of water and 1 part of a polyoxyethylene (ethylene oxide -20
moles) lauryl ether (HLB = 16.6) were added and uniformly dissolved and dispersed.
Afterward, 0.5 part of methyltrimethoxysilane and 9.5 parts of water were added, thus
producing a uniform aqueous emulsion composition. The mean particle size of this aqueous
emulsion composition was 0.29 µm.
[0027] Using the aqueous emulsion composition obtained as described above, the stability
against ionic substances was measured in the same manner as Example 1. The results
obtained are shown in Table 2.
Comparative Example 5
[0028] 30 parts of an amino-group-containing diorganopolysiloxane expressed by the average
molecular formula
3 parts of a polyoxyethylene (ethylene oxide -6 moles) lauryl ether (HLB = 11.8)
and 1 part of a cationic emulsifying agent expressed by the formula (CH
3)
3(C
12H
25)N
+Cl
- were uniformly mixed. Afterward, 4 parts of water were added, and this mixture was
agitated to a uniform consistency. Next, this mixture was emulsified using a colloid
mill. Then, 52 parts of water were added and uniformly dissolved and dispersed. Then,
0.5 part of methyltrimethoxysilane and 9.5 parts of water were added, thus producing
a uniform aqueous emulsion composition. The mean particle size of this aqueous emulsion
composition was 0.30 µm.
[0029] Using the aqueous emulsion composition obtained above, the stability against ionic
substances was measured in the same manner as Example 1. The results obtained are
shown in Table 2.
Table 2
|
HLB of Emulsifying Agents |
Stability Against Ionic Substances |
Example 3 |
11.8 |
16.6 |
Stable |
Comparative Example 5 |
11.8 |
- |
Emulsion separated |
Example 4
[0030] 29.5 parts of an amino-group containing diorganopolysiloxane expressed by the average
molecular formula
0.5 part of a partial hydrolysis product of methyltriethoxysilane (dynamic viscosity:
75 mm
2/s) and 3.5 parts of a polyoxyethylene (6 mole) lauryl ether (HLB = 11.8) were uniformly
mixed. Afterward, 3 parts of water were added and the resulting mixture was agitated.
Next, this mixture was emulsified using a colloid mill, after which 65.5 parts of
water and 1.0 parts of a polyoxyethylene (45 moles) nonyl ether (HLB = 18.1) were
added. Thus a uniform aqueous emulsion composition was produced with a mean particle
size of 0.33 µm.
[0031] Using the aqueous emulsion composition obtained as described above, the stability
against ionic substances was measured in the same manner as Example 1. As a result,
it was found that the stability was good, with no destruction of the emulsion being
seen. Furthermore, when the laundering shrinkage rate was measured in the same manner
as Example 1, the total of the laundering shrinkage rates in the warp and woof directions
was only 7.5%. In contrast, the laundering shrinkage rate of an untreated sample of
the same material was 18.9%. Thus, it was confirmed that laundering shrinkage rate
can expeditiously be lowered by more than half by treating the material with the aqueous
emulsion composition of the present invention. It is apparent from this that the aqueous
emulsion composition of the present invention has an extremely favorable effect as
an anti-shrinkage finishing agent.
[0032] The wool treatment agent of the present invention is an aqueous emulsion composition
comprising the above-mentioned components (A) through (D). Therein, the above-mentioned
nonionic emulsifying agent of component (B) has an HLB of less than 15, and the above-mentioned
nonionic emulsifying agent of component (C) has an HLB of 15 or greater. As a result,
the wool treatment agent of the present invention shows superior stability against
ionic substances, and is useful as an anti-shrinkage finishing agent.
1. A wool treatment agent comprising an aqueous emulsion composition characterised in
that the emulsion comprises (A) an amino-group containing organopolysiloxane, (B)
a nonionic emulsifying agent with an HLB of less than 15, (C) a nonionic emulsifying
agent with an HLB of 15 or greater, and (D) water.
2. The wool treatment agent according to Claim 1, in which component (A) is an amino-group
containing diorganopolysiloxane in which both ends of the molecular chain are selected
from hydroxy groups, alkoxy groups, monovalent hydrocarbon groups of 1 to 20 carbon
atoms, and combinations thereof.
3. The wool treatment agent according to Claim 1 or 2, wherein component (B) has an HLB
of 9 to 13.
4. The wool treatment agent according to Claim 3, wherein component (B) has an HLB of
10 to 12.
5. The wool treatment agent according to any of Claims 1 to 4, wherein the total amount
of components (B) and (C) is in the range of 2 to 100 parts by weight per 100 parts
by weight of component (A).
6. The wool treatment agent according to Claim 5, wherein the total amount of components
(B) and (C) is in the range of 2 to 60 parts by weight of component (A).
7. The wool treatment agent according to any of claims 1 to 6, wherein component (D)
is present in an amount of 100 to 1,000,000 parts by weight per 100 parts by weight
of component (A).
8. A method of treating wool which comprises contacting the wool with a treatment agent
according to any of Claims 1 to 7.