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Description  |
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BACKGROUND OF THE INVENTION
The present invention relates to a deterging solvent composition to be used
as a substitute for chlorofluorocarbon (hereinafter referred to as "flon")
solvents and chlorine solvents, and a method for washing an article with
the same.
The flon and chlorine solvents have been widely used heretofore. Various
techniques of stabilizing and using flon and chlorine solvents were
developed. For example, Japanese Patent Unexamined Published Application
(hereinafter referred to as "J.P. KOKAI") No. Hei 3-173835 discloses a
stabilizing method wherein a stabilizer selected from the group consisting
of nitro compounds, phenols, amines, ethers, amylenes, esters, organic
phosphites, epoxides, furans, alcohols, ketones and triazoles is added to
an azeotropic mixture comprising trichlorodifluoroethane and a
hydrocarbon, alcohol, ketone, ether, ester or the like.
However, the use of the flon and chlorine solvents is limited in recent
years because they cause environmental problems. Under these
circumstances, the development of an excellent deterging solvents usable
in place of the above-described solvents and a technique of stabilizing
them has been eagerly demanded.
On the other hand, brominated hydrocarbons have not been used as solvents
for degreasing and deterging metal parts and plastics, since they are
inferior in the chemical stability and incombustibility to the flons and
chlorinated hydrocarbons.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a new deterging
solvent composition having an excellent deterging effect and usable as a
substitute for the flon and chlorine solvents.
Another object of the present invention is to provide a deterging solvent
composition having a high stability.
Another object of the present invention is to provide a method for washing
an article with the above-described solvent composition.
These and other objects of the present invention will be apparent from the
following description and examples.
After intensive investigations on brominated hydrocarbons, the inventors
found that specific brominated hydrocarbons are flame-retardant and have a
high power of dissolving oils and excellent degreasing and deterging
properties. However, the inventors also found defects with brominated
hydrocarbons the reactivity of these solvents with metals, particularly
aluminum and its alloys is extremely high. The problem is that this
reaction occurs even at ambient temperature, and particularly when the
temperature is elevated for the deterging with a vapor, the reaction
becomes vigorous. Namely, the solvent reacts with aluminum in a short time
of 10 to 20 min to form a dark brown tar or carbide and also to seriously
corrode aluminum and finally to completely dissolve aluminum. After
further investigations made for the purpose of finding a stabilizer which
can be stably usable for the vapor deterging for a long period of time,
the inventors have found that the reactivity of the detergent with the
metal can be remarkably reduced by adding a specified stabilizer. The
present invention has been completed on the basis of this finding.
In the first aspect of the present invention, there is provided a deterging
solvent which essentially consists of (A) a brominated hydrocarbon of the
formula: C.sub.n H.sub.2n+1 Br wherein n represents a number of 3 or above
and/or a brominated hydrocarbon of the formula: C.sub.m H.sub.2m-1 Br
wherein m represents a number of 2 or above.
In the second aspect of the present invention, there is provided a stable
deterging solvent composition which comprises the above-described solvent
(A) and a stabilizer selected from the group consisting of nitroalkanes,
ethers, epoxides and amines.
In the third aspect of the present invention, there is provided a stable
deterging solvent composition which comprises the above-described solvent
(A), a solvent selected from the group consisting of (B) nitroalkanes,
ethers, epoxides and (C) amines.
In the fourth aspect of the present invention, there is provided a method
for washing an article with the solvent or solvent compositions mentioned
above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Examples of the brominated hydrocarbons represented by the formula: C.sub.n
H.sub.2n+1 Br or C.sub.m H.sub.2m-1 Br usable in the present invention
include n-propyl bromide, iso-propyl bromide, n-butyl bromide, isobutyl
bromide, sec-butyl bromide, n-amyl bromide, isoamyl bromide, n-hexyl
bromide, n-heptyl bromide, n-octyl bromide, 2-ethylhexyl bromide, n-nonyl
bromide, n-decyl bromide, allyl bromide, butylene bromide and hexylene
bromide. They are usable either singly or in the form of a mixture of two
or more of them.
In the formulae, n in the above formula represents a number of 3 or above,
preferably 3 to 8, still preferably 3 to 6, whereas m in the above formula
represents a number of 2 or above, preferably 2 to 9, still preferably 3
to 7. Among these, n-propyl bromide and iso-propyl bromide are the most
preferable.
The nitroalkanes usable in the present invention include nitromethane,
nitroethane, 1-nitropropane, 2-nitropropane and nitrobenzene. They are
usable either singly or in the form of a mixture of two or more of them.
The ethers include 1,2-dimethoxyethane, 1,4-dioxane, diethyl ether,
diisopropyl ether, dibutyl ether, trioxane, alkyl "Cellosolves" in which
the alkyl group has 1 to 10 carbon atoms such as methyl "Cellosolve",
ethyl "Cellosolve" and isopropyl "Cellosolve", acetal, acetone
dimethylacetal, .gamma.-butyrolactone, methyl t-butyl ether,
tetrahydrofuran and N-methylpyrrole. They are usable either singly or in
the form of a mixture of two or more of them.
The epoxides include epichlorohydrin, propylene oxide, butylene oxide,
cyclohexene oxide, glycidyl methyl ether, glycidyl methacrylate, pentene
oxide, cyclopentene oxide and cyclohexene oxide. They are usable either
singly or in the form of a mixture of two or more of them.
The amines include hexylamine, octylamine, 2-ethylhexylamine, dodecylamine,
ethylbutylamine, hexylmethylamine, butyloctylamine, dibutylamine,
octadecylmethylamine, triethylamine, tributylamine, diethyloctylamine,
tetradecyldimethylamine, diisobutylamine, diisopropylamine, pentylamine,
N-methylmorpholine, isopropylamine, cyclohexylamine, butylamine,
isobutylamine, dipropylamine, 2,2,2,6-tetramethylpiperidine,
N,N-diallyl-p-phenylenediamine, diallylamine, aniline, ethylenediamine,
propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine,
dibenzylamine, diphenylamine and diethylhydroxyamine. They are usable
either singly or in the form of a mixture of two or more of them.
The quantity or relative amount of the stabilizer necessitated for the
stabilization of the above-described brominated hydrocarbons varies in a
wide range depending on the kind of the oil adhering to the material to be
deterged and also on the deterging conditions such as deterging method. It
is preferably in the range of 0.1 to 15% by weight, more preferably in the
range of 0.5 to 10% by weight, based on the total weight of the brominated
hydrocarbons. When it is below 0.1%, the stabilizing effect is
insufficient and, on the contrary, an amount exceeding 15% is economically
disadvantageous.
Although the stabilizer exhibits its effect even when it is used solely, a
combination of two or more stabilizers is also usable. In the latter case,
the total amount of the stabilizers is preferably in the range of 0.1 to
15%.
The composition preferably contains at least one compound (B) selected from
the group consisting of nitromethane, nitroethane and nitropropane and
also at least one compound (C) selected from the group consisting of alkyl
"Cellosolves" and dioxane. In this connection, n-propyl bromide and
iso-propyl bromide are preferable as solvent (A).
The alkyl "Cellosolves" (C) are those in which the alkyl group has 1 to 10
carbon atoms, preferably 1 to 3 carbon atoms, such as methyl "Cellosolve",
ethyl "Cellosolve" and isopropyl "Cellosolve". They are usable either
singly or in the form of a mixture of two or more of them. The term
"Cellosolve" is a registered trademark for ethylene glycol monoalkyl
ethers.
Although amounts of the component (B) and (C) relative to the amount of
component (A) are not particularly limited, it is preferred that the
component (A) contains 0.5 to 15%, particularly 1 to 5%, of the component
(B) and that the component (A) contains 0.01 to 10%, particularly 0.05 to
3%, of the component (C). pH of the deterging solvent composition is
preferably controlled at 6 to 8 with an amine.
The deterging solvent composition of the present invention may contain, in
addition to the above-described stabilizer, an assistant stabilizer
selected from the group consisting of those usually used as the
stabilizers for chlorinated hydrocarbons such as phenols, e.g. phenol and
o-cresol; aminoalchols, e.g. monoethanolamine, diethanolamine and
triethanolamine; acetylene alcohols, e.g. methylbutynol, methylpentynol
and propargyl alcohol; and triazoles, e.g. benzotriazole,
(2-hydroxyphenyl)benzotriazole and chlorobenzotriazole.
The deterging solvent and deterging solvent composition of the present
invention containing the component (A) has excellent degreasing and
deterging properties and is usable as a substitute for the flon and
chlorine solvents. By incorporating the specified stabilizer into the
composition, metals can be effectively and stably degreased and deterged
with the composition for a long period of time without being corroded. In
particular, by incorporating the components (B) and (C) into the
composition, metals can be effectively and stably degreased and deterged
with the composition for a long period of time without being corroded.
The deterging solvent composition is very suitable for deterging processed
metal products and electronic parts. For example, an article or substrate
made from metal or plastics can be washed with the deterging solvent or
deterging solvent composition, for example, in order to remove grease or
oil from the article or substrate. In this connection, such an article or
substrate can be immersed in the deterging solvent or deterging solvent
composition while heated.
The following Examples and Comparative Examples will further illustrate the
present invention.
EXAMPLE 1
Deterging solvent compositions given in Table 1 were prepared. Aluminum
pieces (JIS-H-4000, A 1100P) were arranged in the liquid phase and gas
phase of the composition, and the corrosion of the metal pieces was
observed after 48 h according to JIS-K 1600. The results were evaluated
according to the following criteria:
Criteria of Corrosion
.largecircle.: no change
x: corroded.
The results are given in Table 1 together with the results of Comparative
Examples. In the Table, nPB represents n-propyl bromide (1-Bromo propane),
IPB represents isopropyl bromide (2-Bromo propane), and the amounts of
them are given in terms of the weight ratio in the parentheses.
The degreasing/deterging power was determined by a method described below:
Degreasing/deterging Power Test
A press oil (trade name: Nippon Kosaku-yu #640) was applied to previously
cleaned SPCC mild steel plates (50.times.100.times.0.3 mm) and the plates
were left to stand in a room for 3 days to obtain the test pieces (amount
of oil remaining on the pieces: 200 to 300 mg/dm.sup.2).
The test pieces were immersed in a sample solution at room temperature for
2 min and then dried. The amount of the remaining oil was determined by a
gravimetric method.
When the amount of the remaining oil was 2 mg/dm.sup.2 or below, the
degreasing/deterging power was evaluated to be good, the amount 2
mg/dm.sup.2 being equal to that of trichloroethane.
x: The amount of remaining oil was above 2 mg/dm.sup.2.
.largecircle.: The amount of remaining oil was 2 mg/dm.sup.2 or below.
TABLE 1
______________________________________
No. Deterging solvent composition
Corrosion D.D. power
______________________________________
1 nPB (99.5)/nitromethane (0.5)
.largecircle.
.largecircle.
2 IPB (99)/nitromethane (1)
.largecircle.
.largecircle.
3 nPB (95)/1,2-dimethoxyethane
.largecircle.
.largecircle.
(5)
4 IPB (97)/epichlorohydrin (3)
.largecircle.
.largecircle.
5 nPB (95)/diisopropylamine (5)
.largecircle.
.largecircle.
6 IPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
phenol (1)
7 nPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
triethanolamine (1)
8 IPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
methylbutynol (1)
9 IPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
benzotriazole (1)
10 nPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
1,2-dimethoxyethane (1)
11 IPB (97)/nitromethane (2)/
.largecircle.
.largecircle.
diisopropylamine (1)
12 nPB (100) X .largecircle.
13 IPB (100) X .largecircle.
______________________________________
Note:
D.D. power means degreasing/deterging power (as the same in the below)
EXAMPLE 2
The effect on the aluminum pieces was examined by varying the relative
amounts of nitroethane and methyl "Cellosolve" added to n-propyl bromide
(1-Bromo propane) as given in Table 2 by methods which will be described
below. pH of the deterging solvent composition comprising n-propyl bromide
(1-Bromo propane), nitroethane and methyl "Cellosolve" was previously
adjusted to 7.5 with diisopropylamine.
Evaluation Method (1)
The corrosion of the metal pieces was observed in the same manner as that
of Example 1.
Evaluation method (2)
The deterging solvent composition was prepared and fed into a flask
provided with a reflux condenser. After reflux in a hot water bath at
70.degree. to 80.degree. C. for 2 h, the aluminum pieces were scratched
with a sharp stainless steel knife, and the state of corrosion of the
surface of each aluminum piece was observed. The results were evaluated
according to the following criteria:
.largecircle.: no change.
x: corrosion.
TABLE 2
______________________________________
Nitro- Methyl Evaluation
Evaluation
ethane "Cellosolve" method (1)
method (2)
______________________________________
0.5% -- .largecircle.
X
3% -- .largecircle.
X
-- 3% X X
-- 4% X X
0.5% 2% .largecircle.
.largecircle.
2% 1% .largecircle.
.largecircle.
______________________________________
EXAMPLE 3
The effect on the aluminum pieces was examined by varying the relative
amounts of nitromethane and methyl "Cellosolve" added to isopropyl bromide
(2-Bromo propane) as given in Table 3 in the same manner as that of
Example 2. The pH of the deterging solvent composition comprising
isopropyl bromide (2-Bromo propane), nitromethane and methyl "Cellosolve"
was previously adjusted to 6.5 with diisopropylamine.
TABLE 3
______________________________________
Nitro- Methyl Evaluation
Evaluation
methane "Cellosolve" method (1)
method (2)
______________________________________
3% -- .largecircle.
X
-- 3% X X
0.5% 2% .largecircle.
.largecircle.
2% 1% .largecircle.
.largecircle.
______________________________________
EXAMPLE 4
The effect on the aluminum pieces was examined by varying the relative
amounts of nitroethane and 1,4-dioxane added to n-propyl bromide (1-Bromo
propane) as given in Table 4 in the same manner as that of Example 2. pH
of the deterging solvent composition comprising n-propyl bromide (1-Bromo
propane), nitroethane and 1,4-dioxane was previously adjusted to 6.5 with
diisopropylamine.
TABLE 4
______________________________________
Nitro- Evaluation
Evaluation
ethane 1,4-Dioxane method (1)
method (2)
______________________________________
3% -- .largecircle.
X
-- 3% X X
2% 1% .largecircle.
.largecircle.
______________________________________
EXAMPLE 5
The deterging solvent compositions given in Table 5 were prepared, and the
corrosion of these compositions and degreasing and deterging powers of
them were examined in the same manner as that of Example 1. The results
are given in Table 5.
TABLE 5
______________________________________
No. Deterging solvent composition
Corrosion D.D. power
______________________________________
1 n-Butyl bromide (99.5)/
.largecircle.
.largecircle.
nitromethane (0.5)
2 Isobutyl bromide (99)/
.largecircle.
.largecircle.
nitromethane (1)
3 n-Amyl bromide (95)/
.largecircle.
.largecircle.
1,2-dimethoxyethane (5)
4 n-Hexyl bromide (97)/
.largecircle.
.largecircle.
epichlorohydrin (3)
5 n-Heptyl bromide (95)/
.largecircle.
.largecircle.
diisopropylamine (5)
6 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)/phenol (1)
7 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)/
triethanolamine (1)
8 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)
/methylbutynol (1)
9 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)
/benzotriazole (1)
10 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)
/1,2-dimethoxyethane (1)
11 n-Butyl bromide (97)/
.largecircle.
.largecircle.
nitromethane (2)/
/diisopropylamine (1)
12 Allyl bromide (99)/
.largecircle.
.largecircle.
nitromethane (1)
13 n-Butyl bromide (100)
X .largecircle.
14 Isobutyl bromide (100)
X .largecircle.
______________________________________
In the Table, n-Butyl bromide is 1-Bromo butane, Isobutyl bromide is
1-Bromo-2-methyl propane, n-Amyl bromide is 1-Bromo pentane, n-Hexyl
bromide is 1-Bromo hexane, n-Heptyl bromide is 1-Bromo heptane and Allyl
bromide is CH.sub.2 .dbd.CHCH.sub.2 Br.
* * * * *
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