FIELD OF THE INVENTION
[0001] The present invention relates to a liquid detergent composition comprising a surfactant
and an aminopolycarboxylic add-based organic builder. More specifically, the present
invention relates to a high concentration liquid detergent composition having excellent
compatibility with a surfactant, superior resistance against white turbidity and good
biodegradability.
BACKGROUND OF THE INVENTION
[0002] In liquid detergents, particularly in liquid detergents used as a household detergent
a nonionic surfactant and/or an anionic surfactant are used as the surfactant and
a builder of various types is added to increase detergency. Various types of organic
or inorganic builders can be used but almost all builders have a Na salt structure.
[0003] In recent years, from the standpoint of environmental conservation, studies are aggressively
being made on the use of an aminopolycarboxylic acid having excellent biodegradability,
particularly an amino acid diacetic acid-type chelating agent as the builder. Aminopolycarboxylic
acids including amino add diacetic acid chelating agents are used in the form of a
synthetic reaction solution as it is on account of the cost. Therefore, in almost
all cases, these are Na salts which cause strong alkalinity. For example, JP-A-10-25494
(the term "JP-A" as used herein means an "unexamined published Japanese patent application")
disdoses a liquid detergent for dishes, comprising an aspartic acid diacetic acid
builder, where an alkali metal salt is used. JP-A-10-36888 discloses a liquid detergent
comprising an aminopolycarboxylic acid builder, where an amine salt is disclosed on
the same level with an alkali metal salt and in Examples, a Na salt is used. Moreover,
the maximum concentration of the surfactant in this composition is as low as 10 wt%,
thus, the problem of white turbidity on the high concentration side is not solved.
[0004] The use of a builder has a problem in that the solubility or clouding point of the
surfactant as the main agent decreases and thereby the compatibility is deteriorated
to cause, for example, white turbidity or separation of the white turbidity into two
layers with the elapse of time. In order to prevent these, a technique of diluting
the liquid detergent composition with water to reduce the concentration of the surfactant
or a technique of adding a solubilizing agent has been heretofore used. However, the
former case of diluting the liquid detergent composition with water inevitably results
in an increase in the cost of transporting the detergent and this is commercially
disadvantageous. In the latter case, it is known to newly add a surfactant as a solubilizing
agent or add urea, an ether alcohol or a lower alcohol. However, the effect is not
sufficiently high for obtaining a high concentration liquid detergent composition.
SUMMARY OF THE INVENTION
[0005] An object of the present invention is to obtain a liquid detergent which has excellent
biodegradability, which does not assume strong alkalinity, which has excellent compatibility
even if the surfactant concentration is increased, and which is free of white turbidity.
[0006] As a result of extensive investigations to solve the above-described problems, the
present inventors have found that when a nonionic surfactant and/or anionic surfactant
is used at a high concentration as the main surfactant of a liquid detergent and an
aminopolycarboxylic acid chelating agent is used as a builder, by using an amine salt
or an alkali metal-amine mixed salt as the counter ion of the builder and at the same
time, adding an alcohol thereto, the compatibility is increased and the white turbidity
can be prevented. The present invention has been accomplished based on this finding.
[0007] The present invention relates to the liquid detergent composition described below.
[0008] In one embodiment, the invention provides a liquid detergent composition comprising:
(A) one or more surfactants selected from the group consisting of a nonionic surfactant
and an anionic surfactant,
(B) one or more builders selected from the group consisting of an amine salt and an
alkali metal-amine mixed salt of an aminopolycarboxylic acid chelating agent, and
(C) one or more solubilizing agents selected from the group consisting of alcohols,
with component (A) being present in a concentration of 20 wt% or more.
[0009] In another embodiment, the invention provides a liquid detergent composition comprising:
(A) from 20 to 60 wt% of one or more surfactants selected from the group consisting
of a nonionic surfactant and an anionic surfactant,
(B) from 0.1 to 15 wt% of one or more builders selected from the group consisting
of an amine salt and an alkali metal-amine mixed salt of aminopolycarboxylic acid
chelating agent,
(C) from 0.5 to 30 wt% of one or more solubilizing agents selected from the group
consisting of alcohols, and
(D) the balance of water.
[0010] A further embodiment comprises a liquid detergent composition as described in (1)
or (2), wherein the aminopolycarboxylic acid is an amino acid-N,N-diacetic acid.
[0011] An even further embodiment is a liquid detergent composition as described in (1)
or (2), wherein the aminopolycarboxylic acid is glutamic acid-N,N-diacetic acid, α-alanine-N,N-diacetic
acid. β-alanine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, glycine-N,N-diacetic
acid or serine-N,N-diacetic acid.
[0012] Additionally, another embodiment is a liquid detergent composition as described in
any one of (1) to (4), wherein the alcohol is a glycol.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The surfactant used as component (A) in the present invention is one or more selected
from a nonionic surfactant and an anionic surfactant. Among these, a nonionic surfactant
has a higher solubility than an anionic surfactant, accordingly, it is suitable for
preparing a high concentration liquid detergent composition. The surfactant is used
at a concentration of 20 wt% or more in the liquid detergent composition.
[0014] Examples of suitable nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene
alkyl phenyl ether, fatty acid diethanolamide, amine oxide and amidoamine oxide. Examples
of appropriate anionic surfactants include alkyl sulfate, alkylpolyoxyethylene sulfate,
alkylbenzenesulfonate, α-olefinsulfonate, fatty acid salts, ether carboxylates and
monoalkylphosphates. A number of these maybe commercially available.
[0015] The aminopolycarboxylic acid-based chelating agent used in the builder as component
(B) of the present invention is a chelating agent containing one or more, preferably
one or two amino groups and two or more, preferably three or four carboxyl groups,
and having a chelating action. The amino group may be a secondary amino group or a
tertiary amino group. The chelating agent is preferably an amino acid-N,N-diacetic
acid.
[0016] An amino acid-N,N-diacetic acid is a compound represented by the following formula
(1)
A-N-(CH
3COOH)
2 (1)
wherein A-NH
2 represents an amino acid, and -N represents an amino group in the amino acid.
[0017] Examples of amino acid-N,N-diacetic acids include glutamic acid-N,N-diacetic acid,
α-alanine-N,N-diacetic acid, β-alanine-N,N-diacetic acid, aspartic acid-N,N-diacetic
acid, glycine-N,N-diacetic acid and serine-N,N-diacetic acid. These amino acid-N,N-diacetic
acids may be synthesized by the known Strecker reaction using, for example, an amino
acid as the raw material or may be synthesized from a monochloroacetic acid.
[0018] Other than the amino acid-N,N-diacetic acid, examples of aminopolycarboxylic acid
chelating agents include ethylenediaminedisuccinic acid and iminodisuccinic acid.
These may also be synthesized by a known method and used. Examples of preferred aminopolycarboxylic
acid chelating agents are shown below by their structural formulae.

[0019] On account of the cost, amino acid-N,N-diacetic acids and other aminopolycarboxylic
acid-based chelating agents are generally obtained as an aqueous solution where all
carboxyl groups have a Na salt as the counter ion. However, in the present invention,
the aminopolycarboxylic acid for use in the builder as component (B) is used in the
form of an amine salt or an alkali metal-amine mixed salt. The effect may be obtained
using primary, secondary and tertiary amines, however, the amine salt used is preferably
an alkanolamine salt, more preferably triethanolanine salt or diethanolamine salt.
The alkali metal salt in the alkali metal-amine mixed salt is preferably a K salt
because it has a higher compatibility with the surfactant than an Na salt, however,
in view of the cost, a Na salt is more preferred.
[0020] In order to convert the aminopolycarboxylic acid chelating agent obtained in the
form of a Na salt into an alkali metal-amine mixed salt, the Na salt aqueous solution
obtained may be treated to remove Na using an H-type cation exchange resin or by electrodialysis,
or may be subjected to acid deposition to obtain a crystal having an H type carboxyl
group. Thereafter, the resulting solution as it is or in the case of a crystal, a
solution obtained by dissolving the crystals in water, is mixed with a mixture of
an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide with an
amine and thereby an aqueous solution of the objective salt can be obtained. Also,
after the removal of Na, the solution or crystal may be added to the formulation of
a liquid detergent and then an amine or another alkali metal hydroxide may be added
thereto so as to obtain the objective salt.
[0021] An aminopolycarboxylic acid-based chelating agent, particularly the aminodiacetic
acid-type chelating agent is known to exert a good chelate effect namely a builder
effect on the neutral to weakly alkali side at a pH of from 8 to 12. Therefore, the
amount of the amine or alkali metal hydroxide added is preferably controlled so that
the above-described pH region can be created. The larger the amount of the amine salt
is, the higher is the compatibility with the surfactant, however, the ratio in the
mixed salt of alkali metal and amine should be determined taking account of the cost
for the removal of Na or the cost of amine.
[0022] The alcohol used as the solubilizing agent in the present invention is not particularly
limited. However, a primary, secondary or tertiary alcohol, preferably a primary or
secondary alcohol, having from 1 to 5 carbon atoms, preferably from 2 to 4 carbon
atoms is preferred. The alcohol maybe a general alcohol such as ethanol and isopropyl
alcohol, however, since these are volatile and highly inflammable, a commonly used
and inexpensive glycol such as propylene glycol and ethylene glycol is preferably
used.
[0023] The liquid detergent composition of the present invention preferably has a composition
ratio such that the surfactant as component (A) is from 20 to 60 wt%, preferably from
30 to 50 wt%, the builder as component (B) is from 0.1 to 15 wt%, preferably from
1 to 10 wt%, the solubilizing agent as component (C) is from 0.5 to 30 wt%, preferably
from 1 to 20 wt%, and the balance is water as component (D). This composition ratio
is the proportion among four components (A) to (D). The ratio of builder as component
(B) based on the surfactant as component (A) is preferably from 2 to 20 wt%, more
preferably from 5 to 15 wt%, and the solubilizing agent as component (C) based on
the surfactant as component (A) is preferably from 5 to 40 wt%, more preferably from
10 to 30 wt%.
[0024] If the ratio of the surfactant as component (A) is less than the above-described
range, the cost for transportation or packaging of the liquid detergent increases
and this is commercially disadvantageous. If it exceeds the range, the desired compatibility
can be attained only within narrow limits. As a result, flexibility in the formulation
may decrease or the viscosity may increase and the handleability is disadvantageously
impaired.
[0025] If the ratio of the builder as component (B) is less than the above-described range,
the cleaning effect of the liquid detergent composition decreases, whereas if it exceeds
the range, the compatibility with the surfactant occurs only within narrow limits
and flexibility in formulation disadvantageously decreases.
[0026] If the ratio of the solubilizing agent as the component (C) is less than the above-descried
range, compatibility between components (A) and (B) is reduced, whereas if it exceeds
the range, flexibility in formulation disadvantageously decreases.
[0027] The liquid detergent composition of the present invention may contain, if desired,
other additives in any optional ratio, such as a viscosity controlling agent, a moisture
retaining agent, an antiseptic, an antifungal agent, a dye and a perfume.
[0028] The detergent composition of the present invention may be used for all uses as a
detergent. However, this is suitably used in particular as a home detergent for cleaning
dotes or household materials.
[0029] The detergent composition of the present invention may be used as it is or may be
used after diluting it with water because the concentration is high.
[0030] According to the present invention, a builder comprising an amine salt or amine-alkali
metal mixed salt of an aminopolycarboxylic add and a solubilizing agent comprising
an alcohol are mixed each in a specific ratio with a specific surfactant, therefore,
a high-concentration liquid detergent composition which does not have strong alkalinity,
which has excellent compatibility even if the surfactant concentration is increased,,
and which is free of white turbidity can be obtained.
EXAMPLES
[0031] The present invention is described below by referring to the Examples. In the Examples,
"%" is "% by weight (wt%)".
Examples 1 to 16 and Comparative Examples 1 to 18:
[0032] The following surfactant, builder and solubilizing agent comprising an alcohol were
added at the ratio shown in Tables 1 and 2, and the balance was water. The resulting
solutions each was thoroughly mixed and left standing at an ordinary temperature or
40°C. Then, compatibility was visually observed. Those underwent separation into two
layers after standing each was again mixed when observing and the solution state was
observed. The formulations and visual results are shown together in Tables 1 and 2
below.
[0033] The following compounds were used.
Surfactant:
Nonionic surfactant:
EMULGEN 108, produced by Kao Corporation (trademark, ethylene oxide alkyl ether nonionic)
Anionic surfactant:
LAS, reagent, sodium linear alkylbenzenesulfonate (free of sodium sulfate)
Builder:
- GLDA:
- glutamic acid-N,N-diacetic acid
- αAD:
- α-alanine-N,N-diacetic acid
- βAD:
- β-alanine-N,N-diacetic acid
- SDA:
- serine-N,N-diacetic acid
- ASDA:
- aspartic acid-N,N-diacetic acid
- NTA:
- glycine-N,N-diacetic acid
- EDDS:
- ethylenediaminedisuccininc acid
- IDS:
- iminodisuccininic acid
Amine:
- TEA:
- triethanolamine
- DEA:
- diethanolamine
- MEA:
- monoethanolamine
Solubilizing Agent:
- PG:
- propylene glycol
- IPA:
- isopropyl alcohol
[0034] In Tables 1 and 2, "-2Na2TEA" after "GLDA" indicates the counter ion of the carboxyl
group within the molecule and means a mixed salt of 2Na and 2TEA. "-2Na2H" means 2Na
salt in the low pH state. In either case, the concentration is the value calculated
when the carboxyl group is the Na salt.
Table 1
Example |
Surfactant |
Builder |
Solubilizing Agent |
Compatibility |
1 |
EMULGEN 108 40% |
GLDA-2Na2TEA 5% |
PG 12.5% |
ordinary temperature: clear 40°C: clear |
2 |
EMULGEN 108 40% |
GLDA-2Na2TEA 5% |
PG 6.9% |
ordinary temperature: clear 40°: clear |
3 |
EMULGEN 108 40% |
GLDA-1Na3TEA 5% |
PG 4.8% |
ordinary temperature: clear 40°C: clear |
4 |
EMULGEN 108 40% |
GLDA-2Na2DEA 5% |
PG 6.7% |
ordinary temperature: clear 40°C: clear |
5 |
EMULGEN 108 40% |
GLDA-1Na3DEA 5% |
PG 4.7% |
ordinary temperature: clear 40°C: clear |
6 |
EMULGEN 108 40% |
GLDA-1Na3DEA 5% |
IPA 4.7% |
ordinary temperature: clear 44°C: clear |
7 |
EMULGEN 108 40% |
GLDA-1Na3MEA 5% |
PG 5.0% |
ordinary temperature: clear 40°C: clear |
8 |
EMULGEN 108 40% |
GLDA-4TEA 5% |
PG 5.0% |
ordinary temperature: clear 40°C: clear |
9 |
EMULGEN 108 40% |
αAD-1Na2TEA 3% |
PG 10.0% |
ordinary temperature: clear 40°C: clear |
10 |
EMULGEN 108 40% |
βAD-1Na2TEA 3% |
PG 11.2% |
ordinary temperature: clear 40°C: clear |
11 |
EMULGEN 108 40% |
SDA-1Na2TEA 5% |
PG 5.0% |
ordinary temperature: clear 40°C: clear |
12 |
EMULGEN 108 40% |
ASDA-1Na3TEA 3% |
PG 12.1% |
ordinary temperature: clear 40°C: clear |
13 |
EMULGEN 108 40% |
NTA-1Na2TEA 3% |
PG 10.9% |
ordinary temperature: clear 40°C: clear |
14 |
EMULGEN 108 40% |
EDDS-2Na2TEA 2% |
PG 13.0% |
ordinary temperature: clear 4°C: clear |
15 |
EMULGEN 108 40% |
IDS-2Na2TEA 3% |
PG 12.0% |
ordinary temperature: clear 40°C: clear |
16 |
EMULGEN 108 40% |
GLDA-1Na3TEA 3% |
PG 12.0% |
ordinary temperature: clear 40°C: clear |
LAS 5% |
Table 2
Comparative Example |
Surfactant |
Builder |
Solubilizing Agent |
Compatibility |
1 |
EMULGEN 108 40% |
- |
- |
ordinary temperature: clear 40°C: clear |
2 |
EMULGEN 108 40% |
GLDA-4Na 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
3 |
EMULGEN 108 40% |
GLDA-4Na 5% |
IPA 12.5% |
ordinary temperature: white turbidity 40°C: white turbidity |
4 |
EMULGEN 108 40% |
GLDA-4Na 5% |
PG 12.5% |
ordinary temperature: white turbidity 40°C: white turbidity |
5 |
EMULGEN 108 40% |
GLDA-2Na2H 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
6 |
EMULGEN 108 40% |
GLDA-2Na2MEA 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
7 |
EMULGEN 108 40% |
GLDA-2Na2H 5% |
IPA 12.5% |
ordinary temperature: white turbidity 40°C: white turbidity |
8 |
EMULGEN 108 40% |
GLDA-2Na2TEA 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
9 |
EMULGEN 108 40% |
GLDA-4Na 5% |
PG 20.7% |
ordinary temperature: white turbidity 40°C: white turbidity |
10 |
EMULGEN 108 40% |
GLDA-2Na2TEA 5% |
TEA 15.1% |
ordinary temperature: white turbidity 40°C: white turbidity |
11 |
EMULGEN 108 40% |
GLDA-1Na3TEA 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
12 |
EMULGEN 108 40% |
αAD-3Na 3% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
13 |
EMULGEN 108 40% |
βAD-3Na 3% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
14 |
EMULGEN 108 40% |
SDA-3Na 5% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
15 |
EMULGEN 108 40% |
ASDA-4Na 3% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
16 |
EMULGEN 108 40% |
NTA-3Na 3% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
17 |
EMULGEN 108 40% |
IDS-4Na 3% |
- |
ordinary temperature: white turbidity 40°C: white turbidity |
18 |
EMULGEN 108 40% |
GLDA-4Na 3% |
PG 12.0% |
ordinary temperature: white turbidity 40°C: white turbidity |
LAS 5% |
[0035] It is seen from the results in Tables 1 and 2 that, when Example 1 was compared with
Comparative Examples 3, 4, 7, 8 and 10, the composition using an amine salt or an
alkali metal-amine mixed salt as the builder and using an alcohol as the solubilizing
agent had compatibility, whereas in the compositions using a Na salt as the builder,
using no solubilizing agent or using alkanolamine as the solubilizing agent, the compatibility
was poor and white turbidity occurred.
[0036] The same can be seen from a comparison between Example 3 and Comparative Example
11, Example 7 and Comparative Example 6, Example 9 and Comparative Example 12, Example
10 and Comparative Example 13, Example 11 and Comparative Example 14, Example 15 and
Comparative Example 17, and Example 16 and Comparative Example 18.
[0037] As verified in the foregoing, by mixing an amine salt or alkali metal-amine mixed
salt of an aminopolycarboxylic acid as the builder and an alcohol as the solubilizing
agent each in a specific amount with a high-concentration nonionic or anionic surfactant,
a high-concentration liquid detergent composition having excellent compatibility and
free of white turbidity can be obtained.
[0038] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.
1. A liquid detergent composition comprising:
(A) one or more surfactants selected from the group consisting of an nonionic surfactant
and an anionic surfactant,
(B) one or more builders selected from the group consisting of an amine salt and an
alkali metal-amine mixed salt of an aminopolycarboxylic acid-based chelating agent,
and
(C) one or more solubilizing agents selected from the group consisting of alcohols,
with component (A) being present in a concentration of 20 wt% or more.
2. A liquid detergent composition comprising:
(A) from 20 to 60 wt% of one or more surfactants selected from the group consisting
of a nonionic surfactant and an anionic surfactant,
(B) from 0.1 to 15 wt% of one or more builders selected from the group consisting
of an amine salt and an alkali metal-amine mixed salt of an aminopolycarboxylic acid-based
chelating agent,
(C) from 0.5 to 30 wt% of one or more solubilizing agents selected from the group
consisting of alcohols, and
(D) the balance water.
3. The liquid detergent composition as claimed in claim 1 or 2, where the aminopolycarboxylic
acid is an amino acid-N,N-diacetic acid.
4. The liquid detergent composition as claimed in claim 1 or 2, wherein the aminopolycarboxylic
acid is glutamic acid-N,N-diacetic acid, α-alanine-N,N-diacetic acid, β-alanine-N,N-diacetic
acid, aspartic acid-N,N-diacetic acid, glycine-N,N-diacetic acid or serine-N,N-diacetic
acid.
5. The liquid detergent composition as claimed in any of the claims 1 to 4, wherein the
alcohol is a glycol.