BACKGROUND OF THE INVENTION
Field of the Invention:
[0001] This invention relates to an aqueous solution of a strong alkali and a nonionic surface
active agent, and, more particularly to an aqueous solution composition of a strong
alkali and a nonionic surface active agent having an HLB value of 3 - 18 at high concentrations
and stably.
Description of the Background:
[0002] Strong alkalis, for example, sodium hydroxide, potassium hydroxide, sodium orthosilicate,
and sodium metasilicate, are used for such applications as neutralization of an acid,
saponification reactions of oils and fats (triglycerides), and the like. Also, these
alkalis are useful in various industrial applications because of their good electric
conductivity. Nonionic surface active agents, on the other hand, are very useful as
effective ingredients or detergency improvers of various kinds of detergent compositions
owing to their emulsifying, dispersing, and foaming capabilities, as well as to their
permeability. They are also effective as wettability promoting agents of glass, fiber,
metal, and earthenware surfaces. Because of these characteristics, nonionic surface
active agents are widely used in industries in general and for various toiletry products.
[0003] Therefore, a combination of a strong alkali and a nonionic surface active agent is
expected to produce a composition which is strongly alkaline and at the same time
exhibits a high degree of functionality in terms of emulsifying, dispersing, and foaming
capabilities, and of permeability.
[0004] Preparing an aqueous solution containing both a strong alkali and a nonionic surface
active agent at high concentrations, however, has been extremely difficult. Because
of this, when a strong alkali and a nonionic surface active agent have to be used
together, it has been necessary to supply a solid material in a powdery or flaky form
containing a strong alkali and a nonionic surface active agent, or to first supply
a strong alkali and a nonionic surface active agent separately as liquids, and then
blend the two liquids together when used.
[0005] Handling a strong alkali in a powdery or flaky form, however, involves difficulties
in actual operation. For example, there is the risk of splashing or generating a mist
of the strong alkali in the air. The splashing or misting causes problems in view
of human safety and sanitation. For instance, they produce considerable irritation
when coming into contact with the skin. Blending liquids of a strong alkali and a
nonionic surface active agent is a cumbersome task in itself. In addition, adjusting
the concentration of each component requires complicated control.
[0006] Due to this situation, the development of an aqueous solution containing both a strong
alkali and a nonionic surface active agent at high concentrations has been strongly
desired.
[0007] A certain action due to a salting-out effect owing to loss of hydration water necessary
for dissolving a nonionic surface active agent, which results from dissociated ions
of an inorganic strong alkali, has generally been considered to be the cause of the
difficulty in preparing this type of strong alkali-nonionic surface active agent aqueous
solution.
[0008] The present inventors have undertaken extensive studies to eliminate the occurrence
of this kind of action, and found that the use of a specific type of carboxylic acid
or the salts thereof, as a solubilizing agent, is effective in achieving this target.
Such a finding has led to the completion of this invention.
SUMMARY OF THE INVENTION
[0009] Accordingly, an object of this invention is to provide an aqueous solution composition
of a strong alkali and a nonionic surface active agent comprising: (a) a strong alkali,
(b) a nonionic surface active agent having an HLB value of 3 - 18, and, as a solubilizing
agent, (c) a carboxylic acid represented by the following formula (I):
R₁COOM₁ (I)
in which R₁ represents a C₄₋₁₈ linear aliphatic hydrocarbon group, C₄₋₁₈ branched
aliphatic hydrocarbon group, or C₅₋₁₈ aromatic hydrocarbon group, and M₁ represents
a hydrogen atom, an alkali metal, an aliphatic amine having a C₁₋₄ carbon atom content,
ammonia, or an alkanolamine; or a carboxylic acid formula (I) and a carboxylic acid
of the following formula (II):
R₂-X-(CH₂)
m1COOM₂ (II)
in which R₂ represents a C₄₋₁₈ linear aliphatic hydrocarbon group, C₄₋₁₈ branched
aliphatic hydrocarbon group, or C₅₋₁₈ aromatic hydrocarbon group, X represents a group
>NH, >N(CH₂)
n1COOM₂, or >CHCOOM₂, M₂ represents a hydrogen atom, an alkali metal, an aliphatic amine
having a C₁₋₄ carbon atom content, ammonia, or an alkanolamine, and m1 and n1 independently
indicate integers of 1 - 3.
[0010] Other objects, features and advantages of the invention will hereinafter become more
readily apparent from the following description.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
[0011] Any strong alkalis may be used as the (a) component of this invention, so long as
the same is water soluble. Specific examples may include sodium hydroxide, potassium
hydroxide, sodium silicates such as sodium orthosilicate and sodium metasilicate,
sodium phosphates such as sodium tripolyphosphate, sodium orthophosphate, and sodium
metaphosphate, aqueous ammonium, ethylenediamine, alkanolamines having a C₂₋₁₀ carbon
atom content, and the like. The amount of this (a) component to be formulated in the
aqueous solution composition of this invention is 3 - 50% by weight (hereinafter
designated simply as "%"), with the especially preferable range being 5 - 30%. It
is desirable that the formulated amount bring the pH of the composition to at least
10.
[0012] Any type of nonionic surface active agent having an HLB value of between 3 and 18
may be used as the (b) component. Given as examples of such nonionic surface active
agents are polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene
alkylamino ether, sorbitane fatty acid ester, polyoxyethylene sorbitane fatty acid
ester, polyoxyethylene fatty acid ester, glycerol fatty acid mono- or diester, and
the like. Especially preferred nonionic surface active agents are those represented
by the following formula (III):
R₃-O-(CH₂CH₂O)
n2(CH₂CH₂CH₂O)
m2H (III)
in which R₃ represents a hydrogen, a C₁₋₁₈ linear aliphatic hydrocarbon group, C₁₋₁₂
branched aliphatic hydrocarbon group, or alkylphenyl group with alkyl group(s) having
an aggregate C₁₋₁₂ carbon atom content, and n2 and m2 independently denote integers
of 0 - 60, provided that n2 plus m2 is not less than 1.
[0013] Enumerated as specific examples of this type of nonionic surface active agents are
polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether,
polyoxyethylene lauryl ether, polyoxyethylene palmityl ether, polyoxyethylene myristyl
ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene
tolyl ether, polyoxyethylene xylenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene
nonylphenyl ether, polyoxyethylene decylphenyl ether, polyoxyethylene dodecylphenyl
ether, polyoxypropylene, polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene-polyoxypropylene
octylphenyl ether, polyoxyethylene-polyoxypropylene nonylphenyl ether, polyoxyethylene-polyoxypropylene
decylphenyl ether, polyoxyethylene-polyoxypropylene dodecylphenyl ether, polyoxypropylene
octylphenyl ether, polyoxypropylene nonylphenyl ether, polyoxypropylene decylphenyl
ether, polyoxypropylene dodecylphenyl ether, polyoxypropylene butyl ether, polyoxypropylene
hexyl ether, polyoxypropylene octyl ether, polyoxypropylene dodecyl ether, polyoxypropylene
lauryl ether, and the like.
[0014] Since nonionic surface active agents must have HLB values of 3 - 18 in this invention,
among the compounds listed above only those having the number of added moles of oxyethylene
or oxypropylene meeting this criteria are usable for the purpose of this invention.
For instance, polyoxyethylene (50) lauryl ether having 50 moles of added polyoxyethylene
is outside the scope of this invention, since this compound has an HLB value of 18.6.
[0015] These nonionic surface active agents, which are the (b) component of the aqueous
solution composition of this invention, are formulated into the composition in the
amount of 0.01 - 10%, and particularly preferably 0.1 - 30%.
[0016] The carboxylic acid or the salt thereof represented by formula (I) is formulated
into the composition of this invention as the solubilizing agent, the (c) component.
Alternatively, this carboxylic acid or salt may be used in conjunction with the carboxylic
acid or the salt thereof represented by formula (II). Named as examples of carboxylic
acids represented by formula (I) are linear saturated fatty acids such as caproic
acid, enathic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid,
lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, lactic acid,
valeric acid, and the like; branched saturated fatty acids such as 2-butyl-5-methylpentanoic
acid, 2-isobutyl-5-methylpentanoic acid, 4,6-dimethyloctanoic acid, 4,7-dimethyloctanoic
acid, 2,3-dimethyloctanoic acid, 2,3-dimethylononanoic acid, 4,8-dimethylononanoic
acid, 2-butyl-5-methylhexanoic acid, 2-methylundeccanoic acid, 10-methylundeccanoic
acid, 4,4-dimethyldeccanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic
acid, 2-methyldocosanoic acid, 3-methyldocosanoic acid, (+)-3D-methyldocosanoic acid,
2-propyl-3-methylnonanoic acid, 12-methyltridecanoic acid, 2,2-dimethyldodecanoic
acid, 2,3-dimethyldodecanoic acid, 4,10-dimethyldodecanoic acid, 2-butyl-3-methylnonanoic
acid, and the like; linear unsaturated fatty acids such as caproleic acid, oleic acid,
9-undecylenic acid, elaidic acid, 10-undecylenic acid, 2-lauroleic acid, pasenic acid,
linderic acid, obtusilic acid, 5-lauroleic acid, 11-lauroleic acid, 2-palmitoleic
acid, 7-palmitoleic acid, cis-9-palmitoleic acid, zoomaric acid, trans-9-palmitoleic
acid, tsuzuic acid, 5-myristleic acid, myristleic acid, petroselinic acid, petrosenilaidic
acid, and the like; and branched unsaturated fatty acids such as trans-2-methyl-2-pentenoic
acid, trans-4-methyl-3-pentenoic acid, cis-2-methyl-2-hexenoic acid, trans-2-methyl-2-hexenoic
acid, 2-methylhexanoic acid, 3,4-dimethyl-3-pentenoic acid, trans-2-methyl-2-heptenoic
acid, 3-methyl-2-nonenoic acid, 3-methyl-3-nonenoic acid, 5-methyl-2-undecenoic acid,
2,4-dimethyl-2-decenoic acid, 5,9-dimethyl-2-decenoic acid, 2-methyl-2dodecenoic
acid, (-)-5-methyl-2-tridecenoic acid, L (+)-2,4dimethyl-2-dodecenoic acid, L(+)-2,5-dimethyl-2-tridecenoic
acid, and the like. In addition, carboxylic acids having an aromatic group are included
in the formula (I) type carboxylic acids. These are phenylacetic acid, β-phenylpropionic
acid, γ-phenylacetic acid, δ-phenylvaleric acid, ε-phenylcapronic acid, ζ-phenylenatic
acid, η -phenylcaprylic acid, ϑ-phenylpelargonic acid,

-phenylcapric acid, naphthenic acid, toluic acid, and the like.
[0017] Given as examples of carboxylic acids of formula (II) are the compounds represented
by the following formulae:

in which M₂ has the same meaning as defined before.
[0018] Specific examples of M₁ and M₂ in formulae (I) and (II) are methylamine, ethylamine,
propylamine, butylamine, ethylenediamine, diethylenetriamine, ammonia, monoethanolamine,
diethanolamine, and triethanolamine, as well as other alkanolamines having a C₂₋₁₀
carbon atom content, sodium, and potassium.
[0019] Preferable amounts of these solubilizing agents to be formulated into the composition
of the present invention are between 0.01 - 30%, with the optimum range being 0.1
- 20%.
[0020] Even though there is no specific limitation as to the proportion of the solubilizing
agents of formulae (I) and (II) to be formulated when these are used in combination,
the preferred range of the proportion in terms of a ratio by weight (I)/(II) is 9/1
- 1/9, with the optimum ratio being 7/3 - 3/7.
[0021] Aqueous solutions of neutral salts such as sodium sulfate, sodium chloride, hydrosulfite,
hypo (sodium thiosulfate), and the like also exhibit salting-out effects on nonionic
surface active agents, and thus a single aqueous solution of these compounds is frequently
difficult to obtain. use of the solubilizing agent, however, makes it possible to
produce such a single aqueous solution. The action or mechanism of formation of a
strong alkali-nonionic surface active agent solution mentioned above applies to the
formation of this neutral salt solution.
[0022] Formulating an organic chelating-type builder, in addition to the above-mentioned
components, is effective in order to promote the detergency capability and other characteristics
of the composition of this invention. Included as examples of such organic chelating-type
builders are aminocarboxylic acids, inclusive of alkali metal salts or lower amine
salts of glycine, nitrilotriacetic acid, ethylenediaminetetracetic acid, diethylenetriaminepentaacetic
acid, ethylenediaminediacetic acid, iminodiacetic acid, triethylenetetraminehexaacetic
acid, metaphenylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid,
norleucineaminobutylic acid, and the like, and oxycarboxylic acid-type chelating builders
such as alkali metal salts or lower amine salts of malic acid, citric acid, gluconic
acid, glucoheptonic acid, mucic acid, and the like.
[0023] According to the present invention, a strong alkali and nonionic surface active agent
can be supplied as a single aqueous solution at a high concentration. This solution
is easy and safe to handle, and can provide a strong alkali and nonionic surface active
agent having a varied concentration.
[0024] Specifically, since the composition is a single aqueous solution, its handling can
be performed only through valve manipulation with the fluid being transferred by means
of a pump. This eliminates tasks involves danger and improves working conditions.
[0025] Other features of the invention will become apparent in the course of the following
description of the exemplary embodiments which are given for illustration of the invention
and are not intended to be limiting thereof.
EXAMPLES
Example 1
[0026] The following formula (I) compounds were provided to the test as solubilizing agents:
(a) Caproic acid
(b) Caprylic acid
(c) Capric acid
(d) Lauric acid
(e) Myristic acid
(f) 2-Ethylhexanoic acid
(g) Isostearic acid
[0027] The capability of each solubilizing agent to solubilize 2% of the nonylphenol ethyleneoxide
(9 mols) addition compound and 2% of ethylenediaminetetraacetic acid into a 20% sodium
hydroxide (95% first grade reagent) aqueous solution was evaluated. A group of compositions,
with amounts of solubilizing agent varied by 0.1%, were prepared for each solubilizing
agent. Each composition was stirred for 30 minutes at 30 - 40°C and observed to confirm
the presence or absence of turbidity or precipitate to determine the minimum amount
of solubilizing agent necessary to inhibit production of any turbidity or precipitant.
The results are listed in Table 1.
Table 1
| |
Solubilizing Agents |
Solubilizing Capability |
| |
(a) |
(b) |
(c) |
(d) |
(e) |
(f) |
(g) |
- |
|
| Example 1a |
1.2 |
|
|
|
|
|
|
|
Good |
| Example 1b |
|
1.2 |
|
|
|
|
|
|
Good |
| Example 1c |
|
|
1.0 |
|
|
|
|
|
Good |
| Example 1d |
|
|
|
1.0 |
|
|
|
|
Good |
| Example 1e |
|
|
|
|
0.9 |
|
|
|
Good |
| Example 1f |
|
|
|
|
|
1.3 |
|
|
Good |
| Example 1g |
|
|
|
|
|
|
1.3 |
|
Good |
| Comparative * Example |
|
|
|
|
|
|
|
|
None |
| * No solubilizing agent was added to the Comparative Example composition. |
[0028] The test proves that the additions of the solubilizing agent in the amounts exceeeding
those indicated in Table l provide a homogeneous and transparent liquid composition.
[0029] As is clear from the results, solubilizing agents (a) - (g), even at very small
amounts, ensure solubilization of a nonionic surface active agent in an aqueous solution
of a strong alkali. In contrast, the alkali and nonionic surface active agent separate
and form precipitates without producing a solution when no solubilizing agent is added.
Example 2
[0030] Table 2 lists values similar to those in Table 1 for solubilizing agents (a) - (g),
which designate the minimum amount of each solubilizing agent required to solubilize
2% of the nonylphenol ethyleneoxide (9 mols) addition compound and 2% of ethylenediaminetetraacetic
acid into a 20% sodium orthosilicate (90% first grade reagent) aqueous solution.
Table 2
| |
Solubilizing Agents |
Solubilizing Capability |
| |
(a) |
(b) |
(c) |
(d) |
(e) |
(f) |
(g) |
- |
|
| Example 2a |
1.1 |
|
|
|
|
|
|
|
Good |
| Example 2b |
|
1.0 |
|
|
|
|
|
|
Good |
| Example 2c |
|
|
0.8 |
|
|
|
|
|
Good |
| Example 2d |
|
|
|
0.7 |
|
|
|
|
Good |
| Example 2e |
|
|
|
|
0.7 |
|
|
|
Good |
| Example 2f |
|
|
|
|
|
1.2 |
|
|
Good |
| Example 2g |
|
|
|
|
|
|
1.2 |
|
Good |
| Comparative * Example 2 |
|
|
|
|
|
|
|
|
None |
| * No solubilizing agent was added to the Comparative Example composition. |
[0031] The values in Table 2 demonstrates that the addition of very small amounts of solubilizing
agents (a) - (g) produce a homogeneous aqueous solution of a nonionic surface active
agent and sodium orthosilicate.
Example 3
[0032] The following compounds were provided for testintg as solubilizing agents:
(h) Sodium N-lauryl-β-alanine (a compound of formula (II))
(i) Sodium N-lauryl-β-dialanine (a compound of formula (II))
(j) Caproic acid
(k) Caprylic acid
(l) Capric acid
(m) Lauric acid
(n) Myristic acid
(o) 2-Ethylhexanoic acid
(p) Isostearic acid
(q) γ-Phenylbutylic acid
[0033] The capability of each solubilizing agent to solubilize 2% of polyoxyethylene nonylphenyl
ether (20 mols) addition compound and 2% of ethylenediaminetetraacetic acid into a
30% sodium hydroxide (95% first grade reagent) aqueous solution was evaluated. A group
of compositions, with amounts of solubilizing agents varied by 0.1%, were prepared
for each solubilizing agent. Each composition was stirred for 30 minutes at 50°C and
observed to confirm the presence or absence of turbidity or precipitate to determine
the minimum amount of solubilizing agent necessary to inhibit production of any turbidity
or precipitate. The results are listed in Table 3.
Table 3
| Composition |
Solubilizing Agents (%) |
Solution * Conditions |
| |
(h) |
(i) |
(j) |
(k) |
(l) |
(m) |
(n) |
(o) |
(p) |
(q) |
|
| No. 1 |
6.0 |
|
|
|
|
|
|
|
|
|
X |
| No. 2 |
|
5.0 |
|
|
|
|
|
|
|
|
X |
| No. 3 |
1.2 |
|
0.4 |
|
|
|
|
|
|
|
O |
| No. 4 |
1.2 |
|
|
0.4 |
|
|
|
|
|
|
O |
| No. 5 |
1.2 |
|
|
|
0.3 |
|
|
|
|
|
O |
| No. 6 |
1.2 |
|
|
|
|
0.3 |
|
|
|
|
O |
| No. 7 |
1.2 |
|
|
|
|
|
0.2 |
|
|
|
O |
| No. 8 |
1.2 |
|
|
|
|
|
|
0.5 |
|
|
O |
| No. 9 |
1.2 |
|
|
|
|
|
|
|
0.5 |
|
O |
| No. 10 |
1.2 |
|
|
|
|
|
|
|
|
0.5 |
O |
| No. 11 |
|
0.8 |
0.3 |
|
|
|
|
|
|
|
O |
| No. 12 |
|
0.8 |
|
0.3 |
|
|
|
|
|
|
O |
| No. 13 |
|
0.8 |
|
|
0.3 |
|
|
|
|
|
O |
| No. 14 |
|
0.8 |
|
|
|
0.2 |
|
|
|
|
O |
| No. 15 |
|
0.8 |
|
|
|
|
0.2 |
|
|
|
O |
| No. 16 |
|
0.8 |
|
|
|
|
|
0.5 |
|
|
O |
| No. 17 |
|
0.8 |
|
|
|
|
|
|
0.5 |
|
O |
| No. 18 |
|
0.8 |
|
|
|
|
|
|
|
0.5 |
O |
| No. 19 |
|
|
|
|
|
|
|
|
|
|
X |
| * In the Table "O" designates that the solution is homogeneous and transparent, and
"X" designates that the solution is separated. |
Example 4
[0034] The minimum amounts of solubilizing agent required to solubilize 2% of the polyoxyethylene
nonylphenyl ether (20 mols) addition compound and 2% of ethylenediaminetetraacetic
acid into 30% sodium orthosilicate (90% first grade reagent) aqueous solution were
measured for each solubilizing agent used in Example 3 following the same manner as
in Example 3. The results are shown in Table 4.
Table 4
| Composition |
Solubilizing Agents (%) |
Solution * Conditions |
| |
(h) |
(i) |
(j) |
(k) |
(l) |
(m) |
(n) |
(o) |
(p) |
(q) |
|
| No. 20 |
5.5 |
|
|
|
|
|
|
|
|
|
X |
| No. 21 |
|
4.5 |
|
|
|
|
|
|
|
|
X |
| No. 22 |
1.0 |
|
0.4 |
|
|
|
|
|
|
|
O |
| No. 23 |
1.0 |
|
|
0.4 |
|
|
|
|
|
|
O |
| No. 24 |
1.0 |
|
|
|
0.3 |
|
|
|
|
|
O |
| No. 25 |
1.0 |
|
|
|
|
0.3 |
|
|
|
|
O |
| No. 26 |
1.0 |
|
|
|
|
|
0.2 |
|
|
|
O |
| No. 27 |
1.0 |
|
|
|
|
|
|
0.5 |
|
|
O |
| No. 28 |
1.0 |
|
|
|
|
|
|
|
0.5 |
|
O |
| No. 29 |
1.0 |
|
|
|
|
|
|
|
|
0.4 |
O |
| No. 30 |
|
0.7 |
0.3 |
|
|
|
|
|
|
|
O |
| No. 31 |
|
0.7 |
|
0.3 |
|
|
|
|
|
|
O |
| No. 32 |
|
0.7 |
|
|
0.2 |
|
|
|
|
|
O |
| No. 33 |
|
0.7 |
|
|
|
0.2 |
|
|
|
|
O |
| No. 34 |
|
0.7 |
|
|
|
|
0.2 |
|
|
|
O |
| No. 35 |
|
0.7 |
|
|
|
|
|
0.5 |
|
|
O |
| No. 36 |
|
0.7 |
|
|
|
|
|
|
0.4 |
|
O |
| No. 37 |
|
0.7 |
|
|
|
|
|
|
|
0.3 |
O |
| No. 38 |
|
|
|
|
|
|
|
|
|
|
X |
| * In the Table "O" designates that the solution is homogeneous and transparent, and
"X" designates that the solution is separated. |
[0035] Obviously, numerous modifications and variations of the present invention are possible
in light of the above teachings. It is therefore to be understood that the scope of
the appended claims, the invention may be practiced otherwise than as specifically
described herein.