DESCRIPTION
Title of Invention
DETERGENT COMPOSITION
Technical Field
[0001 ]
The present invention relates to a detergent composition which is useful for
\vashing textile products such as clothes, particularly, for washing textile products by
10 hand.
Priority is claimed on Japanese Patent Application No. 2010-095382, filed April
16. 2010, the contents of which are incorporated ht:rein by reference.
Background Art
15 [0002]
For a detergent composition used for washing clothes and the like, an anionic
surfactant is generally mixed in as a cleaning component. In addition, for the purpose
of improving detergency and imparting various other kinds of performance, a detergency
builder is mixed in. An alkaline agent is one of the detergency builders mixed in for the
20 purpose of improving detergency, and in view of detergency, cost, and the like, a
carbonate or silicate of alkali metals are widely used.
As the anionic surfactant used for a detergent composition, a linear
alkylbenzenesulfonic acid salt (LAS salt) has been widely used in the related art, but in
recent years, an a-sulfo fatty acid alkyl ester salt has been used. The a-sulfo fatty acid
25 alkyl ester salt has advantages of having excellent detergency, particularly, exhibiting
2
strong detergency even when water with a high degree of hardness is used, of having
excellent biodegradability, and the like.
The a-sulfo fatty acid alkyl ester salt is generally made into surfactant powder
alone or by being granulated together with other surfactants, and then mixed with other
5 detergent components to form a detergent composition. For example, PTL 1 discloses a
method in which an aqueous slurry having a pH equal to or less than 10 that contains a
water-soluble salt of a-sulfo fatty acid alkyl ester, zeolite, and sodium sulfate in a
specific mass ratio is spray-dried, and the obtained spray-dried powder is stirred and
granulated along with an alkaline builder and a binder component. Moreover, PTL 2
10 discloses surfactant powder which contains equal to or more than 40% by mass of an
a-sulfo fatty acid alkyl ester salt and 0.001% by mass to 0.4% by mass of a chelating
agent and/or an antioxidant and has a pH equal to or more than 7.5 when made into a 1%
by mass aqueous solution, and a particle-like detergent composition in which the
surfactant powder is mixed.
15
Citation List
Patent Literature
[0003]
[PTL 1]
20 H4-348196
[PTL 2]
HI0-204479
Japanese Unexamined Patent Application, First Publication No.
Japanese Unexamined Patent Application, First Publication No.
Summary of Invention
Technical Problem
3
[0004]
In the respect of the above advantages, particularly, in the respect of exhibiting
strong detergency even when water with a high degree of hardness is used (a high degree
of hard water resistance), the a-sulfo farty acid alkyl ester salt is expected to be
5 increasingly widely used in the future in areas where water used for washing has a high
degree of hardness. However, a detergent composition in which the a-sulfo farty acid
alkyl ester salt is mixed tends to have a low degree of foaming performance. In addition,
compared to detergent compositions in which other anionic surfactants, for example LAS,
is mixed, the above detergent composition foams less during washing, and the foam
10 bursts easily (foam sustainability is low). There is a tendency that the harder the water,
the lower the foaming performance.
The low degree of foaming performance is advantageous for a case where a fully
automatic washing machine or a drum-type washing machine is used for washing, but
disadvantageous for a case where hand washing is performed for washing. That is,
15 when hand washing is performed, particularly, when washing is repeatedly performed
using the same washing liquid, the user tends to judge the detergency based on how well
the washing liquid foams and on the sustainability of the foam. Consequently, if the
foaming performance is low, there is a concern that the detergency is also considered to
be weak. Therefore, for such a use, improvement of foaming performance is required.
20 The present invention has been made in consideration ofthe above
circumstances, and an object thereof is to provide a detergent composition that exhibits
excellent detergency and foaming performance even if washing is performed using water
with a high degree of hardness, and which is useful for washing by hand.
25 Means for Solving the Problem
20
4
[0005]
The present inventors conducted thorough research, and as a result, they found
that by removing an alkaline agent, particularly, by removing a carbonate or silicate of
alkali metals as described above, the foaming performance of an a-sulfo fatty acid alkyl
5 ester salt can be improved. They further repeated examination based on this knowledge,
and consequently found that by mixing the a-sulfo fatty acid alkyl ester salt and specific
polymer compounds respectively in specific amounts, and by decreasing the amount of
the alkaline agent compared to the related art, and adjusting the pH of a 1% by mass
aqueous solution thereof to be in a specific range, the above problem is solved, thereby
10 completing the present invention.
The present invention solving the above problem includes the following
embodiments.
[1] A detergent composition containing (A) at least one kind of compound
selected from a-sulfo fatty acid alkyl esters and a salt thereof in an amount of 2.5% by
15 mass or more, and less than 40% by mass, (B) at least one kind of compound selected
from polymer compounds having a carboxy group with a weight average molecular
weight of more than 10,000 and 500,000 or less and a salt thereof in an amount of from
0.1% by mass to 4% by mass, wherein a pH at 25°C of a 1% by mass aqueous solution or
aqueous dispersion ofthe detergent composition is from 5.5 to 9.4.
[2] The detergent composition according to [1], further containing (C) zeolite in
an amount of from 0.5% by mass to 30% by mass.
[3] The detergent composition according to [1] or [2], not containing an alkaline
agent selected from carbonate and silicate of alkali metals.
[4] The detergent composition according to anyone of [1] to [3], wherein the
5
(A) at least one kind of compound selected from a-sulfo fatty acid alkyl esters and a salt
thereof is a compound represented by the following General Formula (a1).
I 2 R -CH(S03M)-CO-O-R ···(al)
[In the formula, RI represents an alkyl group or an alkenyl group having 6 to 20
5 carbon atoms, R2 represents an alkyl group having 1 to 6 carbon atoms, and M represents
a hydrogen atom or a counterion.]
[5] The detergent composition according to anyone of [1] to [4], wherein the
(8) at least one kind of compound selected from polymer compounds having a carboxy
group with a weight average molecular weight of more than 10,000 and 500,000 or less
10 and a salt thereof is at least one kind of compound selected from polycarboxylic acids
and a salt thereof as well as carboxylic acid-modified saccharides and a salt thereof.
[6] The detergent composition according to anyone of[l] to [5], which is
granulated.
[7] The detergent composition according to anyone of [1] to [6], which is for
I 5 washing by hand.
Effects of the Invention
[0006]
According to the present invention, it is possible to provide a detergent
20 composition that exhibits excellent detergency and foaming performance even if washing
is performed using water with a high degree of hardness and is useful for washing by
hand.
Description of Embodiments
25 [0007]
6
«A) component: at least one kind selected from a-sulfo fatty acid alkyl esters
and a salt thereof>
The detergent composition of the present invention contains an (A) component
(at least one kind selected from a-sulfo fatty acid alkyl esters and a salt thereot).
Examples of the (A) component include a compound represented by the
following General Formula (a1).
···(a1)
[In the formula, R) represents an alkyl group or an alkenyl group having 6 to 20
carbon atoms, R2 represents an alkyl group having 1 to 6 carbon atoms, and M represents
lOa hydrogen atom or a counterion.]
[0008]
The alkyl group or alkenyl group represented by R1 may be linear or branched.
In view of detergency, the number of carbon atoms that R1 has is 6 to 20,
preferably 8 to 18, and more preferably 10 to 16. R1 may be one kind of group or may
15 he a mixture of two or more kinds of groups.
The alkyl group represented by R2 may be linear or branched, and in view of
detergency, the number of carbon atoms thereof is 1 to 6, preferably 1 to 3, and more
preferably 1.
The counterion represented by M may be a counterion that can form a
20 \vater-soluble salt along with RICH(COOR2)S03-, and examples thereof include alkali
metals, alkaline earth metals, protonated amine, ammonium, and the like.
Examples of the alkali metals include sodium, potassium, and the like.
Examples of the alkaline earth metals include calcium, magnesium, and the like.
In the protonated amine, the amine may be anyone of primary to tertiary amines
25 and preferably has 1 to 6 carbon atoms in total. The amine mayor may not have a
7
hydroxyl group. However, in view of low-temperature solubility at the time of washing,
formulation, and the like, the amine preferably has a hydroxy group. Examples of the
amine include alkanolamine, and the alkanol group preferably has 1 to 3 carbon atoms.
Specific examples of the alkanolamine include monoethanolamine, diethanolamine,
5 triethanolamine, and the like.
M is preferably an alkali metal or alkanolamine, and more preferably an alkali
metal.
[0009]
One kind or two or more kinds of the (A) component may be contained in the
10 detergent composition.
The amount of the component (A) contained in the detergent composition is
2.5% by mass or more and less than 40% by mass, preferably from 3% by mass to 35%
by mass, and more preferably from 5% by mass to 30% by mass, based on the total
amount of the detergent composition. If the above proportion is 2.5% by mass or more,
15 the effect produced by the (A) component is sufficiently exhibited, and the detergency
becomes excellent. If the proportion is less than 40% by mass, foaming performance,
rinsing properties, and the like become excellent.
[0010]
As the (A) component, commercially available products may be used, or those
20 prepared by known preparation methods disclosed in Pamphlet of PCT International
Publication No. W02004-111166, Pamphlet of PCT International Publication No.
W02009-054406, and the like can also be used. For example, an a-sulfo fatty acid
alkyl ester can be obtained by sulfonating a fatty acid alkyl ester, and by neutralizing the
sulfo group of the a-sulfo fatty acid alkyl ester with an alkali, an a-sulfo fatty acid alkyl
ester salt obtained.
10
8
The alkali used for neutralization corresponds to the counterion represented by
M.
In the above preparation method, after sulfonation, esterification may optionally
be performed using an alcohol such as methanol before neutralization. If the
5 esterification process is performed, when an adduct of two S03 molecules remains in the
reaction product, esterification of an alkoxy portion in the adduct of two S03 molecules
progresses, whereby elimination of S03 is further promoted. Consequently, generation
of by-products is inhibited, so the purity of a-sulfo fatty acid alkyl ester in the reaction
product is improved.
In the preparation method, before or after the neutralization process described
above, for example, bleaching treatment may optionally be performed using a bleach
such as hydrogen peroxide so as to make the color of the a-sulfo fatty acid alkyl ester
salt to be a color close to white.
The product obtained after the neutralization process or bleaching process is
15 generally like paste containing about 50 to 80% by mass of solids. Treatment such as
concentration, pulverization, or the like may optionally be further performed on the
product. Pulverization can be performed by known granulation methods such as a
granulation method using kneading and extruding (kneading·extruding·pulverization), a
granulation method using stirring, and a granulation method using rolling.
20 [0011 ]
Generally, in the a-sulfo fatty acid alkyl ester salt obtained by the preparation
method described above, an a-sulfo fatty acid dialkyl salt (for example, a salt obtained
by substituting R2 in the General Formula (al) with the counterion represented by M,
hereinafter, referred to as a disodium salt in some cases) and the like are included in
9
addition to the a-sulfo fatty acid alkyl ester salt itself. The disodium salt is inferior to
the a-sulfo fatty acid alkyl ester salt in terms of the function, but functions as a surfactant.
Accordingly, the amount of an active component (AI) as a surfactant contained in the
a-sulfo fatty acid alkyl ester salt prepared as described above is determined as a total
5 amount of the a-sulfo fatty acid alkyl ester salt (pure content) and the disodium salt.
The amount ofAI contained in the a-sulfo fatty acid alkyl ester salt is preferably 10 to
80% by mass, more preferably 3 to 80% by mass, and even more preferably 60 to 70%
by mass, based on the total mass of the a-sulfo fatty acid alkyl ester salt. If the amount
is 10% by mass or more, the preparation efficiency is improved, and if the amount is
10 80% by mass or less, the handleability becomes excellent.
In addition, in the a-sulfo fatty acid alkyl ester salt, methyl sulfate, ethyl sulfate,
propyl sulfate, lower/intermediate carboxylic acids or esters of thereof, organic
substances such as ketone and aldehyde, and inorganic substances such as sodium sulfate
are included as by-products, in addition to the a-sulfo fatty acid alkyl ester salt and
15 disodium salt. The amount of these by-products is generally minute, so they do not
particularly affect the effects of the present invention.
[0012]
«B) component: at least one kind selected from polymer compounds having a
carboxy group with a weight average molecular weight of more than 10,000 and 500,000
20 or less and a salt thereof>
The detergent composition of the present invention contains a (B) component (at
least one kind selected from polymer compounds having a carboxy group with a weight
average molecular weight of more than 10,000 and 500,000 or less and a salt thereof) as
well as the (A) component.
15
10
The weight average molecular weight of the (B) component is preferably 12,000
or more and less than 500,000, more preferably from 15,000 to 300,000, and even more
preferably from 15,000 to 100,000. If the weight average molecular weight is more
than 10,000, foaming performance (foaming power and foam sustainability), particularly,
5 foam sustainability becomes excellent. If the weight average molecular weight is
500.000 or less, the detergent composition dissolves excellently in water.
In the present specification, the "weight average molecular weight" refers to a
value obtained by the analysis based on Gel Permeation Chromatography (GPC) using
sodium polyacrylate or polyethylene glycol as a reference material. In addition, when
10 the (B) component is a polymer of a monomer (unsaturated carboxylic acid or the like)
having a carboxy group or a salt thereof, sodium polyacrylate is used as the reference
material, and when the (B) component is carboxylic acid-modified polysaccharides,
polyethylene glycol is used as the reference material.
[0013]
The polymer compound having a carboxy group or a salt thereof used as the (B)
component is not particularly limited as long as the weight average molecular weight
thereof is in the above range, and can be appropriately selected from known compounds.
Examples of compounds preferable as the polymer compound include a polymer of
unsaturated carboxylic acid (hereinafter, also referred to as polycarboxylic acid) and a
.20 salt thereof, polyacetal carboxylate such as polyglyoxylic acid and a salt thereof (for
example, those described in Japanese Unexamined Patent Application, First Publication
No. S54-52196), oxidized polysaccharides and a salt thereof, carboxylic acid-modified
polysaccharides and a salt thereof, and the like. Among these, at least one kind selected
from polycarboxylic acid and a salt thereof as well as carboxylic acid-modified
25 polysaccharides and a salt thereof is preferable since this component produces the
11
excellent effect of the present invention.
[0014]
In the polycarboxylic acid, examples of unsaturated carboxylic acid include
acrylic acid, methacrylic acid, hydroxyacrylic acid, hydroxymethacrylic acid, maleic acid,
5 fumaric acid, itaconic acid, and the like.
One kind or two or more kinds of the unsaturated carboxylic acid unit may
constitute the polycarboxylic acid. Herein, the "unit" refers to a repeating unit
constituting the polymer. For example, an acrylic acid unit refers to a repeating unit
formed by the cleavage of an unsaturated double bond of acrylic acid.
10 The polycarboxylic acid may have a monomer unit other than the unsaturated
carboxylic acid. The monomer other than the unsaturated carboxylic acid may be
copolymerizable with the unsaturated carboxylic acid, and examples thereof include
maleic anhydride, amide acrylate, amide methacrylate, alkyl acrylate, alkyl methacrylate,
vinyl alcohol, allyl alcohol, and the like.
15 Specific examples of the polycarboxylic acid include polyacrylic acid,
polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, an
acrylic acid-maleic acid copolymer, an acrylic acid-amide acrylate copolymer, an acrylic
acid-allyl alcohol copolymer, and the like.
Among the above, polycarboxylic acid having an acrylic acid unit is preferable,
20 and polyacrylic acid (homopolymer of acrylic acid), an acrylic acid-maleic acid
copolymer are particularly preferable. In addition, the salt of polycarboxylic acid is not
particularly limited, and examples thereof include an alkali metal salt, an alkaline earth
metal salt, a protonated amine salt, an ammonium salt, and the like. Examples of each
of the alkali metal, alkaline earth metal, and protonated amine include the same ones as
25 exemplified as M in the Formula (al).
12
In the acrylic acid-maleic acid copolymer, the higher the proportion of the
maleic acid unit, the more preferable, since the detergency is improved. Here, if the
proportion of maleic acid unit is too high, it is difficult to increase the weight average
molecular weight. In this respect, the ratio (molar ratio) of the maleic acid unit lacrylic
) acid unit in the acrylic acid-maleic acid copolymer is preferably 20/80 to 80/20, more
preferably 30/70 to 60/40, and even more preferably 40/60 to 50/50.
As the polycarboxylic acid, commercially available products or those
synthesized by known methods may be used. For example, specific products named
"Sokalan (registered trademark) PA40", "Sokalan (registered trademark) CP-7", and
10 "Sokalan (registered trademark) CP-9" (all manufactured by BASF, Japan), "Aqualic
(registered trademark) TL-500" and "Aqualic (registered trademark) TL-400"
(manufactured by NIPPON SHOKUBAI CO., LTD.) can be used with excellent results.
[0015]
The oxidized polysaccharides are polysaccharides into which a carboxy group
15 has been introduced by oxidation treatment (for example, polysaccharides in which
-CH20H is converted into -COOH by oxidation). Examples ofthe polysaccharides
include cellulose, starch, amylose, pectin, and the like.
The carboxylic acid-modified polysaccharides are polysaccharides into which a
carboxy group has been introduced by modification treatment using carboxylic acid.
20 Examples of the carboxylic acid used in the modification treatment include halides of
monocarboxylic acid such as monochloroacetic acid, unsaturated carboxylic acid such as
(meth)acrylic acid, and the like.
Examples of the polysaccharides include the same ones as described above, and
particularly, cellulose is preferable since the cellulose produces the excellent effect of the
25 present invention.
5
13
Examples of the carboxylic acid-modified cellulose include carboxyalkyl
cellulose, a salt thereof, and the like. Among these, in view of the detergency, foaming
performance and the like, at least one kind selected from carboxyalkyl cellulose and a
salt thereof is preferable.
The carboxyalkyl cellulose or a salt thereof is a substance that is obtained when
a portion or all of hydroxyl groups (hydroxyl groups directly bonded to a glucopyranose
ring and hydroxyl groups bonded to the ring via an alkylene group) in a cellulose
molecule is etherified and becomes -O-R5-COOZ (R5 represents an alkylene group, and
Z represents a hydrogen atom or a counterion). For example, a cellulose raw material
10 such as pulp is treated with caustic soda and then reacted with monochloroacetic acid,
whereby the carboxyalkyl cellulose or a salt thereof can be prepared.
The alkylene group represented by R5 is preferably a linear or branched alkylene
group, and the number of carbon atoms thereof is preferably 1 to 3. As the alkylene
group, a methylene group is particularly preferable. That is, carboxymethyl cellulose is
15 particularly preferable as the carboxyalkyl cellulose.
The counterion represented by Z is not particularly limited, and examples
thereof include an alkali metal, an alkaline earth metal, protonated amine, ammonium,
and the like. Examples of these include the same ones as exemplified as M in the
Formula (a I) respectively.
20 As the carboxylic acid-modified cellulose, commercially available products or
those synthesized by known methods may be used. For example, as the carboxymethyl
cellulose, a specific product named "CMC DAICEL product number: 1105" (Daicel
Corporation) and the like can be used with excellent results.
A degree of etherification of the carboxyalkyl cellulose or a salt thereof is
preferably 0.2 to 1.3 and more preferably 0.2 to 0.8. In addition, in the present
14
invention, the degree of etherification refers to the average number of hydroxyl groups
substituted with a carboxyalkyl group or a salt thereof (_R5-COOl) per glucopyranose
ring unit. That is, the degree of etherification indicates how many hydroxyl groups
among three hydroxyl groups included in the glucopyranose ring have been substituted
5 \vith a carboxyalkyl group or a salt thereof, and the highest degree is 3.
[0016]
One kind or two or more kinds of the (B) component may be contained in the
detergent composition.
As the (B) component, polycarboxylic acid having an acrylic acid unit is
10 preferable, and particularly, an acrylic acid-maleic acid copolymer is preferable.
The amount of the (B) comp'onent contained in the detergent composition is
from 0.1% by mass to 4% by mass, preferably from 0.3% by mass to 3% by mass, more
preferably from 0.4% by mass to 2.5% by mass, and even more preferably from 0.5% by
mass to 2% by mass, based on the total amount of the detergent composition. If the
15 proportion is 0.1% by mass or more, the foaming performance becomes excellent. If
the proportion is 4% by mass or less, the detergent composition dissolves excellently in
\vater.
The ratio (mass ratio) of (A) component/(B) component is preferably rages from
5/1 to 20/1 in terms of amount. The ratio is more preferably 5/1 to 10/1. If the ratio is
20 in this range, a foam-increasing effect and a cleaning effect becomes excellent.
[0017]
«C) component: zeolite>
The detergent composition of the present invention preferably further contains
(C) zeolite.
-,.
c.) In this case, the amount of the (C) component contained in the detergent
15
composition is preferably from 0.5% by mass to 30% by mass based on the total amount
of the detergent composition. If the detergent composition contains the (C) component
in a predetermined proportion, the foaming performance (foaming power and foam
sustainability) are further improved.
5 The amount of the (C) component contained is preferably from 5% by mass to
330% by mass and more preferably 8% by mass to 30% by mass, based on the total
amount of the detergent composition.
Zeolite is crystalline aluminosilicate, and examples thereof include A-type
zeolite, X-type zeolite, V-type zeolite, P-type zeolite, and the like. All of these can be
lOused as the (C) component. In terms of the cleaning performance, A-type zeolite is
preferable as the (C) component.
The average particle size of the (C) component is preferably 2 to 10 /.lm and
more preferably 3 to 8 /.lm. If the average particle size is 2 /.lm or more, the cleaning
performance becomes excellent, and if it is 10 /.lm or more, the cleaning performance
15 deteriorates.
[0018]
In the present specification, the "average particle size" refers to a value
(diameter based on 50% mass) measured by the following measurement methods.
When the average particle size exceeds 149 /.lm, a measurement method (1) for average
20 particle size is used, and when the average particle size is 149 /.lm or less, a measurement
method (2) for average particle size is used.
[Measurement method (1) for average particle size]
First, an object (sample) to be measured is classified using 9 levels of sieves
having openings of 1680 /.lm, 1410 /.lm, 1190 /.lm, 1000 /.lm, 710 /.lm, 500 /.lm, 350 /.lm,
16
250 ~lm, and 149 /lm and a tray. In the classification, sieves are stacked on the tray in
an order from a sieve having a small opening to a sieve having a large opening, and 100 g
of the sample is added from the top of the uppermost sieve having an opening of 1680
~lm. Thereafter, the sieve is capped and mounted on a low-tap sieve shaker
5 (manufactured by Iida-seisakusho Japan Corporation, tapping: 156 times/min, rolling:
290 times/min), followed by shaking for 10 minutes under atmospheric conditions of a
temperature of 25°C and a relative humidity of 40%, and then the sample remaining on
the respective sieves and the tray is collected for each size of sieve opening.
By repeating the above operation, classified samples with the respective particle
10 sizes including 1410 to 1680 /lm (1410 /lm. on), 1190 to 1410 /lm (1190 /lm. on), 1000
to 1190 /lm (1000 /lm. on), 1000 to 710 /lm (710 /lm. on), 500 to 710 /lm (500 /lm. on),
350 to 500 /lm (350 /lm. on), 250 to 350 /lm (250 /lm. on), 149 to 250 /lm (149 /lm. on),
and tray to 149 /lm (149 /lm. pass) are obtained, and the mass frequency (%) is
calculated.
15 Subsequently, the opening of a first sieve in which the calculated mass
frequency becomes 50% or more is set to a /lm, the opening of a sieve that is larger by
one level than the sieve of a /lm is set to b /lm, the mass frequency accumulated from the
tray to the sieve of a /lm is set to c%, and the mass frequency on the sieve of a /lm is set
to d%, thereby calculating average particle size (diameter based on 50% mass) by the
20 following formula.
[0019]
[Formula 1]
A . I . (d' b d 500 / ) 10[50- f c-dl(logb-logaj xloa verage partlc e SIze lameter ase on /0 mass=' "
h: II: d/(log b-log a):
10
20
17
[0020]
[Measurement method (2) for average particle size]
The average particle size is measured using a laser diffraction/scattering type
particle size distribution analyzer. The measurement is performed by a wet method
5 using LA-920 manufactured by HORIBA, Ltd. under conditions of a measurement
temperature: room temperature, a dispersion medium: deionized water, a circulation
speed: 8, stirring time: 5 min, ultrasonic intensity: 7, and a relative refractive index
(\vater): 1.20.
[0021 ]
One kind or two or more kinds of the (C) component may be contained in the
detergent composition.
The amount of the (C) component contained in the detergent composition is
preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to
27% by mass, and even more preferably from 2 % by mass to 25% by mass, based on the
15 total amount of the detergent composition. If the proportion is less than 0.5% by mass,
the effect produced by the (C) component is not sufficiently exhibited. On the other
hand, if the proportion exceeds 30% by mass, there is a concern that the foaming
performance and detergency will be insufficient.
[0022]
«D) component: higher alcohol>
The detergent composition of the present invention preferably further contains a
(D) higher alcohol. In this manner, the foaming power is further improved.
The "higher alcohol" in the present invention refers to an alcohol having 10 to
16 carbon atoms. The number of carbon atoms of the (D) component is more preferably
25 12to14.
18
The (0) component may be a monoalcohol or a polyalcohol, and is preferably a
monoalcohol.
Hydrocarbon groups constituting the alcohol as the (0) component may be any
of linear, branched, and cyclic. The hydrocarbon group is preferably linear or branched,
5 and more preferably linear. In addition, the hydrocarbon group may be saturated or
unsaturated, and is preferably saturated.
One kind or two or more kinds of the (D) component may be contained in the
detergent composition.
As the (D) component, commercially available products or those synthesized by
10 known methods may be used. Specific examples ofthe commercially available
products include Conol20P (trade name, manufactured by New Japan Chemical Co., Ltd.,
linear C12 higher alcohol (lauryl alcohol)), Diadol13 (trade name, manufactured by
Mitsubishi Chemical Corporation, C13 higher alcohol (containing an alcohol (2-methyl
alcohol) having a branched carbon chain and 49% of a linear alcohol)), CO-1270 (trade
15 name, manufactured by P&G Chemicals, linear C12/14 higher alcohol (containing 68 to
74% by mass of a higher alcohol having 12 carbon atoms and 24 to 30% by mass of a
higher alcohol having 14 carbon atoms)), Conol 1495 (trade name, manufactured by New
Japan Chemical Co., Ltd., linear C14 higher alcohol (myristyl alcohol)), and the like.
The amount of the (D) component contained in the detergent composition is
20 preferably 0.1% by mass or more and less than 2% by mass, more preferably from 0.2%
by mass to 1.5% by mass, and even more preferably from 0.3% by mass to 0.7% by mass,
based on the total amount of the detergent composition. If the proportion is 0.1% by
mass or more, the effect produced by the (D) component is obtained sufficiently, and if
the proportion is 2% by mass or more, there is a concern that rinsing properties will be
,.
e.) insufficient.
5
19
The ratio (mass ratio) of (D) component/surfactants (A+E+F) preferably ranges
from 1/15 to 1/100 in terms of the amount, and more preferably is 1/40 to 1/30. If the
ratio is in this range, a foam-increasing effect and a cleaning effect become excellent.
[0023]
«E) component: anionic surfactant other than (A) component>
The detergent composition ofthe present invention may optionally contain an
(E) component (anionic surfactant other than the (A) component).
The anionic surfactant other than the (A) component is not particularly limited
as long as the surfactant has been used for a detergent in the related art, and various
I 0 anionic surfactants can be used.
Examples of the anionic surfactant include the following.
(1) Linear or branched alkylbenzene sulfonate (LAS or ABS) including an alkyl
group having 8 to 18 carbon atoms and a salt thereof: in view of the cleaning
performance, the number of carbon atoms of the alkyl group is particularly preferably 10
15 to 14.
(2) Alkane sulfonate having 10 to 20 carbon atoms and a salt thereof
(3) a-Olefin sulfonate (AOS) having 10 to 20 carbon atoms and a salt thereof
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms and a salt
thereof: in view of the cleaning performance and foaming performance, the number of
20 carbon atoms of the alkyl group or alkenyl group is particularly preferably 10 to 14.
(5) Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or
alkenyl) group having 10 to 20 carbon atoms to which any of alkylene oxides having 2 to
4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO=0.1/9.9 to
9.9/0.1) are added in an amount of 0.5 mol to 10 mol on average, and a salt thereof
(6) Alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or
10
20
alkenyl) group having 10 to 20 carbon atoms to which any of alkylene oxides having 2 to
4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO=0.1/9.9 to
9.9 to 0.1) are added in an amount of 3 mol to 30 mol on average, and a salt thereof
(7) Alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or
5 alkenyl) group having 10 to 20 carbon atoms to which any of alkylene oxides having 2 to
4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO=0.1/9.9 to
9.9/0.1) are added in an amount of 0.5 mol to 10 mol on average, and a salt thereof
(8) Alkyl polyalcohol ether sulfate such as alkyl glyceryl ether sulfonate having
IOta 20 carbon atoms, and a salt thereof
(9) Long-chain monoalkyl, dialkyl, or sesquialkyl phosphate and a salt thereof
(10) Polyoxyethylene monoalkyl, dialkyl, or sesquialkyl phosphate and a salt
thereof
( 11) Higher fatty acid having 10 to 20 carbon atoms and a salt thereof (soap)
[0024]
I5 The form of the salt in these surfactants is not particularly limited, and examples
thereof include an alkali metal salt, an alkaline earth metal salt, a protonated amine salt,
an ammonium salt, and the like. Examples of each of the alkali metal, alkaline earth
metal, and protonated amine include the same ones as exemplified as M in the Formula
(al). Among these, an alkali metal salt is preferable.
20 Anyone kind of the (E) component may be used alone, or two or more kinds
thereof may be used concurrently. Among the above, in view of improving the foaming
performance, formulation, and the like, the (E) component preferably includes at least
one kind selected from LAS and AS, and more preferably includes LAS.
The amount of the (E) component contained in the detergent composition is not
25 particularly limited as long as the amount is within the range that does not diminish the
20
21
effects of the present invention. In view of the cleaning performance and foaming
performance, such an amount that the ratio (mass ratio) of (A) component/(E) component
falls within a range of 1% to 1/9 is preferable. The ratio is more preferably 8/2 to 2/8
and even more preferably 5/5 to 1/2.
:' The total amount of the (A) component and the (E) component in the detergent
composition is 2.5% by mass or more, more preferably from 2.5% by mass to 45% by
mass, even more preferably 3.0% by mass to 42% by mass, and still more preferably
from 5% by mass to 40% by mass, based on the total amount ofthe detergent
composition. If the proportion is less than 2.5% by mass, there is a concern that
I () detergency will be insufficient. If the proportion exceeds 45% by mass, there is a
concern that the foaming performance, rinsing properties, and the like will be
insufficient.
[0025]
«F) component: surfactant other than anionic surfactant>
IS The detergent composition ofthe present invention may optionally further
contain an (F) component (surfactant other than the anionic surfactant). The (F)
component is not particularly limited and can be appropriately selected from known
surfactants such as nonionic surfactants, cationic surfactants, and amphoteric surfactants.
[0026]
[Nonionic surfactant]
The nonionic surfactant is not particularly limited as long as it has been used for
a detergent in the related art, and various nonionic surfactants can be used.
Examples of the nonionic surfactant include the following
(I) Polyoxyalkylene alkyl (or alkenyl) ethers obtained by adding alkylene oxide
25 having 2 to 4 carbon atoms in an amount of 3 to 30 mol, preferably 4 to 20 mol, and
10 ester bonds of long-chain fatty acid alkyl ester
5
15
20
22
more preferably 5 to 17 mol on average to an aliphatic alcohol having 10 to 18 carbon
atoms and preferably having 12 to 14 carbon atoms
Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene
polyoxypropylene alkyl (or alkenyl) ether are preferable.
Examples of the aliphatic alcohol used herein include primary and secondary
alcohols. Moreover, an alkyl group thereof may have a branched chain. As the
aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether
(3) Fatty acid alkyl ester alkoxylate obtained by adding alkylene oxide between
(4) Polyoxyethylene sorbitan fatty acid ester
(5) Polyoxyethylene sorbitol fatty acid ester
(6) Polyoxyethylene fatty acid ester
(7) Polyoxyethylene hydrogenated castor oil
(8) Glycerin fatty acid ester
(9) Fatty acid alkanolamide
(10) Polyoxyethylene alkyl amine
(11) Alkyl glycoside
(12) Alkyl amine oxide
[0027]
Examples of the above (3) fatty acid alkyl ester alkoxylate include a compound
represented by the following General Formula (3-1).
In Formula (3-1), R9CO represents a fatty acid residue having 6 to 22 carbon
atoms and preferably having 8 to 18 carbon atoms.
5
10
23
OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms and
preferably having 2 to 3 carbon atoms, and is preferably ethylene oxide, propylene oxide,
or the like. When n is 2 or greater, two or more OAs in the formula may be the same as
or different from each other.
n represents the average number of moles of alkylene oxide added, and is
generally 3 to 30 and preferably 5 to 20.
RIO represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
that may have a substituent.
[0028]
Anyone kind of these nonionic surfactants may be used alone, or two or more
kinds thereof may be used concurrently. Among the above, in view of detergency,
manufacturability, and the like, the detergent composition preferably contains at least one
kind selected from the (1) polyoxyalkylene alkyl (or alkenyl) ethers and the (3) fatty acid
alkyl ester alkoxylate. Examples of preferable surfactant among these include
15 polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene
polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty
acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl
ester. fatty acid methyl ester ethoxy propoxylate obtained by adding ethylene oxide and
propylene oxide to a fatty acid methyl ester, and the like.
20 The melting point of the nonionic surfactant is preferably 50°C or lower and
more preferably 40°C or lower.
The melting point herein refers to a value measured by the method of measuring
a melting point disclosed in lIS K0064-1992 "Test methods for melting point and melting
range of chemical products".
In addition, HLB of the nonionic surfactant is preferably 7 to 16 and more
5
24
preferably 8 to 14.
HLB refers to a value obtained by the method of Griffin ("Surfactant handbook,
new edition" jointly edited by Yoshida, Shinto, Ogaki, and Yamanaka, Kogyo Tosho Co.,
Ltd" 1991, see p. 234).
[0029]
[Cationic surfactant]
The cationic surfactant is not particularly limited as long as it has been used as a
detergent in the related art, and various cationic surfactants can be used.
As the cationic surfactant, for example, mono-, di-, or trialkyl cations having 1
10 to 3 long-chain (preferably having 8 or more carbon atoms) hydrocarbon groups can be
used. Particularly, cationic surfactants having 1 to 2 ester groups and 1 to 2 long-chain
hydrocarbon groups in a molecule is preferable.
Specific examples ofthe usable cationic surfactant include mono long-chain
alkyl trimethyl ammonium chloride including one long-chain alkyl or alkenyl group
IS having 8 to 22 carbon atoms, long-chain dialkyl dimethyl ammonium chloride including
two long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms, long-chain trialkyl
methyl ammonium chloride including three long-chain alkyl or alkenyl groups having 8
to 22 carbon atoms, N-acyloxyethyl-N,N-dimethyl-N-hydroxyethyl ammonium chloride
including one long-chain alkyl or alkenyl group having 8 to 22 carbon atoms,
20 N.N-diacyloxyethyl-N,N-dimethyl ammonium chloride including two long-chain alkyl or
alkenyl groups having 8 to 22 carbon atoms, and the like.
[0030]
[Amphoteric surfactant]
The amphoteric surfactant is not particularly limited as long as it has been used
25 in a detergent in the related art, and various amphoteric surfactants can be used.
25
As the amphoteric surfactant, for example, sulfobetaine and carboxybetaine
having one or two long-chain (preferably having 8 or more carbon atoms) hydrocarbon
groups can be used.
The long-chain hydrocarbon group may include an ester group, an amide group,
5 or an ether group, and may be a single-chain type or a double-chain type. In addition,
the ratio of saturated type/unsaturated type in the long-chain hydrocarbon group,
distribution of carbon chain length, and the ratio of cis isomer/trans isomer of the
unsaturated group, and the like are not particularly limited. Moreover, the long-chain
hydrocarbon group may be derived from fatty acid as a raw material for preparing the
10 cationic surfactant or from a fatty acid methyl ester. Specific examples of the
amphoteric surfactant include betaines such as N,N-diacyloxyethyl-N-methyl
ammonioethyl sulfate and N,N-diacyloxyethyl-N-methylammonioethyl carboxylate;
N-acyloxyethyl-N-hydroxyethyl-N-methyl ammoniobetaines;
N-acylamidopropyl-N,N-dimethyl ammoniobetaines;
15 N-acylamidopropyl-N,N' -dimethyl-N'-P-hydroxypropyl ammoniobetaine; and the like.
The above amphoteric surfactant may include compounds in which nitrogen
atoms thereof are not quatemarized, alkanolamine as a raw material, a neutralized
substance thereof, or amino betaine of a quartemarized substance thereof.
[0031]
20 Anyone kind of the (F) component may be used alone, or two or more kinds
thereof may be used concurrently.
Among the above, the detergent composition preferably contains a nonionic
surfactant as the (F) component since the cleaning performance thereof is excellent.
The amount of the (F) component contained in the detergent composition may
be appropriately set in consideration ofthe amount of the (A) and (F) components
5 improved, and if it exceeds 45% by mass, the rinsing properties deteriorate.
20 ultraviolet absorber, clay mineral, and the like. Specific examples of these will be
15 and can be optionally selected appropriately from various additives that have been mixed

The detergent composition of the present invention may contain components
[0032]
[0033]
26
inorganic and organic builders. Anyone kind of these can be used alone, or two or
[Detergency builder]
by mass to 45% by mass, more preferably from 6% by mass to 43% by mass, and even
more preferably from 7% by mass to 42% by mass, based on the total amount of the
in a detergent composition in the related art. Examples of such additives include a
In addition, the mixing ratio (mass ratio) of the (F) component to the sum of the
foaming performance.
Detergency builders are roughly classified into alkaline agents and other
shown below.
detergent composition. If the proportion is 5% by mass or more, the detergency is
contained. The total amount of the (A), (E), and (F) components is preferably from 5%
component=lO/O to 4/1, and more preferably ranges from 50/1 to 4/1, in view of the
scavenger, a pH adjustor, a bleach, a bleaching activator, a bleaching catalyst, an
effect of the present invention. Other components as above are not particularly limited,
detergency builder, a fragrance, a colorant, a fluorescent brightener, an enzyme, an
(A) and (E) components is preferably sum of (A) and (E) components/(F)
other than the above components (A) to (F), within a range that does not diminish the
enzyme stabilizer, other polymers, an anti-caking agent, a reductant, a metal ion
10
27
more kinds thereof can be used by being appropriately combined.
In the present specification and claims, the "alkaline agent" refers to a
component having an action of increasing pH of a detergent solution and a specific
pH-buffering action.
5 Examples of the alkaline agent include carbonate or bicarbonate of alkali metals,
silicate of alkali metals, amine, and the like.
Specific examples of the carbonate of alkali metals include sodium carbonate,
potassium carbonate, potassium sodium carbonate, sodium sesquicarbonate, sodium
hydrogen carbonate, and the like.
10 Specific examples of the bicarbonate of alkali metals include sodium
bicarbonate, potassium bicarbonate, and the like.
Specific examples of the silicate of alkali metals include sodium silicate,
lamellar sodium silicate, sodium metasilicate, sodium orthosilicate, and the like.
Specific examples of the amine include monoethanolamine, diethanolamine,
IS triethanolamine, and the like.
One kind of the alkaline agent can be used alone, or two or more kinds thereof
can be used by being appropriately combined.
, Here, in the present invention, the carbonate and silicate of alkaline metals
negatively affect the foaming performance. Therefore, the amount of the mixed
20 alkaline agent selected from the carbonate and silicate of alkali metals is preferably as
small as possible, and it is particularly preferable that the detergent composition do not
contain the alkaline agent.
[0034]
The inorganic builder is not particularly limited as long as it has been used for
25 detergent compositions for clothes and the like in the related art. Examples ofthe
28
inorganic builder include amorphous aluminosilicate; phosphates such as orthophosphate,
pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate; and
crystalline silicate and complexes of carbonate and amorphous alkali metal silicate.
The form of salt is not particularly limited, and examples thereof include an
5 alkali metal salt, an alkaline earth metal salt, a protonated amine salt, an ammonium salt,
and the like. Examples of each of the alkali metal salt, alkaline earth metal salt, and
protonated amine include the same ones as exemplified as M in the Formula (al).
Among these, an alkali metal salt is preferable.
One kind of these inorganic builders can be used alone, or two or more kinds
10 thereof can be used concurrently.
[0035]
Examples of the organic builder include aminocarboxylates such as
nitrilotriacetate, ethylenediamin tetraacetate, p-alaninediacetate, aspartic acid diacetate,
methylglycine diacetate, and iminodisuccinate; hydroxyaminocarboxylates such as serine
IS diacetate, hydroxyiminodisuccinate, hydroxyethyl ethylene diaminotriacetate, and a
dihydroxyethyl glycine salt; hydroxycarboxylate such as hydroxyacetate, tartrate, citrate,
and gluconate; cyclocarboxylates such as a pyromellitic acid salt, benzopolycarboxylate,
and cyclopentane tetracarboxylate; ether carboxylates such as carboxymethyl tartronate,
carboxymethyloxysuccinate, oxydisuccinate, and tartaric acid mono- or disuccinate;
20 polymers having a weight average molecular weight of 10,000 or less and a carboxy
group; and the like. Examples of the polymers include the same ones as the (A)
component, except that the weight average molecular weight of the polymers is 10,000 or
less.
One kind of these organic builders can be used alone, or two or more kinds
25 thereof can. be used concurrently.
5
29
[0036]
As the detergency builder, the inorganic builders are particularly preferable.
Among these, in terms of the cleaning performance, phosphate is preferable, and
tripolyphosphate is particularly preferable.
The amount of the tripolyphosphate contained in the detergent composition is
preferably such an amount that the ratio (mass ratio) between the (C) component and the
tripolyphosphate falls within a range of (C) component/tripolyphosphate=19/l to 1/19.
The ratio is preferably 3/1 to 1/9 and more preferably 13/7 to 3/17.
The amount of the detergency builder contained in the detergent composition is
10 preferably from 5% by mass to 25% by mass, and more preferably from 6% by mass to
20% by mass, based on the total amount of the detergent composition. If the amount of
the detergency builder contained is equal to or more than the lower limit of the above
range, the foaming performance and the like are improved. In addition, if the amount is
equal to or more than the upper limit, the solubility of the detergent composition in water
I 5 deteriorates.
[0037]
[Fragrance]
The fragrance is not particularly limited, and for example, the fragrance
components or fragrance compositions disclosed in Japanese Laid-Open Patent
20 Application No. 2002-146399 or Japanese Laid-Open Patent Application No.
2003-89800 can be used.
In addition, the fragrance composition is a mixture including fragrance
components, a solvent, a fragrance stabilizer, and the like.
One kind of the fragrance can be used alone, or two or more kinds thereof can be
25 used by being appropriately combined.
5
30
When the fragrance is mixed in the detergent composition, the mixing amount is
preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass, based on the
total amount of the detergent composition.
[0038]
[Colorant]
15
Various colorants can be mixed in so as to create good appearance of the
detergent composition.
As the colorant, any of dyes and pigments can be used. In terms of storage
stability, pigments are preferable, and compounds having oxidation resistance, such as
10 oxides, are particularly preferable. Examples of such compounds include titanium
oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, iron blue,
cyanine blue, cyanine green, and the like.
One kind of the colorant can be used alone, or two or more kinds thereof can be
used by being appropriately combined.
[0039]
[Fluorescent brightener]
Examples of the fluorescent brightener include a
4.4' -bis-(2-sulfostyryl)-biphenyl salt, a 4,4' -bis-(4-chloro-3-sulfostyryl)-biphenyl salt, a
2-( styrylphenyl)naphthothiazole derivative, a 4,4' -bis(triazol-2-yl)stilbene derivative, and
20 a bis-(triazinylaminostilbene)disulfonate derivative, and the like.
Examples of commercially available fluorescent brighteners include Whitex
(registered trademark) SA and Whitex (registered trademark) SKC (all trade names;
manufactured by Sumitomo Chemical Co., Ltd.), Tinopal (registered trademark)
AMS-GX, Tinopal (registered trademark) DBS-X, and Tinopal (registered trademark)
25 CBS-X (all trade names; manufactured by Ciba Specialty Chemicals K. K.), Lemonite
31
CBUS-3B (trade name; manufactured by Khyati Chemicals Pvt. Ltd.), and the like.
Among these, Tinopal (registered trademark) CBS-X and Tinopal (registered trademark)
AMS-GX are preferable.
One kind of the fluorescent brightener can be used alone, or two or more kinds
:; thereof can be used by being appropriately combined.
The amount of the fluorescent brightener mixed is preferably from 0.001% by
mass to 1% by mass, based on the total amount of the detergent composition.
[0040]
[Enzyme]
10 Examples of enzymes classified based on enzyme reactivity include hydrolases,
oxidoreductases, lyases, transferases, and isomerases, and any of these can be applicable
in the present invention. Among these, protease, esterase, lipase, nuclease, cellulase,
amylase, pectinase, and the like are preferable.
Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase,
""
15 keratinase, elastase, subtilisin, papain, promelain, carboxypeptidase A or B,
aminopeptidase, aspergillo peptidase A or B, and the like. Examples of commercially
available protease include Savinase (registered trademark), Alcalase (registered
trademark), Kannase (registered trademark), Everlase (registered trademark), and
Deozyme (registered trademark) (all trade names; manufactured by Novozymes); API21
20 (trade name; manufactured by SHOWA DENKO K.K.); Maxacal and Maxapem (all trade
names; manufactured by Genencor); Protease K-14 or K-16 (protease disclosed in
Japanese Unexamined Patent Application, First Publication No. H5-25492); and the like.
Examples of the esterase include gastric lipase, pancreatic lipase, plant lipases,
phospholipases, cholinesterases, phosphotases, and the like.
Examples of the lipase include commercially available lipases such as Lipolase
).
32
(registered trademark) and Lipex (registered trademark) (all trade names; manufactured
by Novozymes), Lipotherm (trade name; manufactured by SHOWA DENKO K.K.), and
the like.
Examples of the cellulase include Celluzyme (trade name; manufactured by
5 Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534,
alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline
cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase
K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, alkaline
cellulase E-III (all cellulases disclosed in Japanese Unexamined Patent Application, First
10 Publication No. S63-264699), and the like.
Examples of the amylase include commercially available Stainzyme (registered
trademark), Termamyl (registered trademark), Duramyl (registered trademark) (all trade
names; manufactured by Novozymes), and the like.
One kind of the above enzymes can be used alone, or two or more kinds thereof
15 may be used by being combined appropriately.
In addition, as the enzyme, an enzyme separately granulated as stabilized
particles is preferably used in a state of being dry-blended with a detergent material
(particles).
The amount of the enzyme mixed in the detergent composition is preferably
20 from 0.05% by mass to 5% by mass, based on the total amount of the detergent
composition.
[0041]
[Enzyme stabilizer]
As the enzyme stabilizer, for example, a calcium salt, a magnesium salt,
polyalcohol, formic acid, a boron compound, and the like can be mixed in. Among
33
these. sodium tetraborate, calcium chloride, and the like are preferable.
One kind of the enzyme stabilizer can be used alone, or two or more kinds
thereof can be used by being combined appropriately.
The amount of the enzyme stabilizer mixed in is preferably from 0.05% by mass
5 to 2% by mass, based on the total amount of the detergent composition.
[0042]
[Other polymers]
As a binder or a powdery agent used in a case of increasing density of the
surfactant-containing particles, and to impart an effect of preventing recontamination of
10 hydrophobic fine particles, polyethylene glycol, polyvinyl alcohol, and the like can be
mixed in.
In addition, as a dirt-releasing agent, a copolymer, a terpolymer, and the like of
terephthalic acid with an ethylene glycol and/or propylene glycol unit can be mixed in.
Moreover, in order to impart an effect of preventing color migration, polyvinyl
15 pyrrolidone and the like can be mixed in.
Among the above, polyethylene glycol is preferable, and an average molecular
weight thereof is preferably 200 to 200,000 and more preferably 1500 to 7000. Herein,
the average molecular weight of polyethylene glycol is a value measured by GPC.
One kind of the polymers can be used alone, or two or more kinds thereof can be
20 used by being combined appropriately.
When the polymers are mixed in the detergent composition, the mixing amount
is preferably from 0.05% by mass to 5% by mass, based on the total amount of the
detergent composition.
[0043]
[Anti-caking agent]
34
Examples of the anti-caking agent include para-toluene sulfonate, xylene
sulfonate, acetate, sulfosuccinate, talc, fine silica powder, clay, magnesium oxide, and the
like.
One kind of the anti-caking agent can be used alone, or two or more kinds
5 thereof can be used by being combined appropriately.
[0044]
[Reductant]
Examples ofthe reductant include sodium sulfite, potassium sulfite, and the like.
[0045]
10 [Metal ion scavenger]
The metal ion scavenger has the effect of capturing trace mineral ions in tap
\vater to inhibit the metal ions from being adsorbed onto fiber (substance to be cleaned).
Examples of the metal ion scavenger that can be mixed in the detergent
composition include those included in the detergency builder described above and
15 aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and
glycol ethylenediamine hexaacetate; organic phosphonic acid derivatives or a salt thereof
such as I-hydroxyethane-l, I-diphosphonic acid (HEDP-H), ethane-I, I-diphosphonic
acid, ethane-I, 1,2-triphosphoinc acid, hydroxyethane-l,1,2-triphosphonic acid,
ethane-l ,2-dicarboxy-l ,2-diphosphonic acid, hydroxymethanephosphonic acid,
20 ethylenediaminetetra(methylenephosphonic acid), nitrilotri(methylenephosphonic acid),
2-hydroxyethyliminodi(methylenephosphonic acid),
hexamethylenediaminetetra(methylenephosphonic acid), and
diethylenetriaminepenta(methylenephosphonic acid); organic acids or a salt thereof such
as diglycolic acid, tartaric acid, oxalic acid, and gluconic acid; and the like.
One kind of the metal ion scavenger can be used alone, or two or more kinds
20 during washing. One kind of these pH adjustors can be used alone, or two or more
15 potassium hydroxide; acidic compounds such as the above metal ion scavenger, alkali
10 the pH becomes a desired value by using only the respective components described
[0046]
[pH adjustor]
As described later, when the detergent composition of the present invention is

kinds thereof can be used by being combined appropriately.
[0047]
When the detergent composition of the present invention is made into a 1% by
linear alkyl benzene sulfonate; and the like. It is also possible to use a buffer for
metal dihydrogen phosphoric acid salts like potassium dihydrogen phosphate, lactic acid,
mass aqueous solution or aqueous dispersion (obtained by dissolving or dispersing 1 g of
monoethanolamine, diethanolamine, and triethanolamine), sodium hydroxide, and
preventing a decrease in the pH caused by acid components derived from dirt of fiber
Examples of the pH adjustor include alkaline compounds such as the alkaline
made into an aqueous solution or an aqueous dispersion with a solid content
35
needs to be considerately set within such a range that the performance is not impaired.
The amount of the metal ion scavenger contained in the detergent composition
above, the pH adjustor may not be necessarily mixed in.
to set the pH to a desired value, a pH adjustor may be optionally mixed in. Here, when
succinic acid, malic acid, gluconic acid, sulfuric acid, hydrochloric acid, citric acid, and
agents exemplified above as the detergency builder (for example, alkanolamines such as
thereof can be used by being combined appropriately.
concentration of I% by mass, pH thereof at 25°C is from 5.5 to 9.4. Therefore, in order
5
36
the detergent composition in 99 g of water), pH at 25°C thereof is from 5.5 to 9.4,
preferably 6.0 to 9.2, and more preferably 6.5 to 9.1. If the pH is equal to or higher than
5.5. the detergency becomes excellent. If the pH is equal to or lower than 9.4, the
foaming performance become excellent, and the washing liquid at the time of performing
5 hand washing becomes mild to the skin of hands.
[0048]
In the present invention, the words that "a pH at 25°C of a 1% by mass aqueous
solution or aqueous dispersion (obtained by dissolving or dispersing 1 g of the detergent
composition in 99 g of water) is from 5.5 to 9.4" mean that the pH of the 1% by mass
10 aqueous solution or aqueous dispersion (obtained by dissolving or dispersing 1 g of the
detergent composition in 99 g of water) is within the above range, based on a temperature
of 25°C. That is, when the aqueous solution or aqueous dispersion is prepared at
temperature other than 25°C, the range ofpH is corrected according to the temperature.
The aqueous solution or aqueous dispersion within the corrected pH range is also
15 included in the scope of the present invention.
In other words, though not within the range of from 5.5 to 9.4 at a certain
temperature, if the pH of the aqueous solution or aqueous dispersion is corrected to be in
a range of from 5.5 to 9.4 based on 25°C, the aqueous solution or aqueous dispersion is
included in the scope ofthe present invention.
20 [0049]
The detergent composition of the present invention may be in the form of solid
such as particles (powder and granules), a tablet, a briquette, a sheet, or a bar, and may be
in the form of liquid. The solid is preferable, and the particles are more preferable.
When the detergent composition of the present invention is in the form of
'. 37
particles, the average particle size of the detergent composition is preferably 200 pm to
1500 pm, more preferably 300 pm to 800 pm, and even more preferably 400 pm to 700
pm. If the average particle size is equal to or larger than the lower limit, dusting at the
time of use is inhibited, and if it is equal to or smaller than the upper limit, solubility in
5 water becomes excellent.
The bulk density of the detergent composition is preferably 0.3 g/cm3 to 1.5
g/cm3 and more preferably 0.4 g/cm3 to 1.0 g/cm3
. The bulk density is a value
measured based on lIS 3362: 1998.
In addition, if the detergent composition is a liquid, a moisture content thereof is
1() preferably less than 10.0% by mass.
[0050]
The method of preparing the detergent composition of the present invention is
not particularly limited. The detergent composition can be prepared based on common
methods according to the form of detergent composition to be prepared.
15 For example, when the detergent composition is in the form of particles,
examples of the preparation method include a method of preparing slurry that contains a
detergent raw material and performing spray drying; a method of granulating the
spray-dried powder and the detergent raw material by a granulation method using
kneading and extruding (kneading·extruding·pulverization), a granulation method using
20 stirring, or a granulation method using rolling, and the like; a method of preparing the
detergent composition by mechanically mixing the powder-like detergent raw material
(powder blending); and the like. Anyone kind of these methods may be used alone, or
two or more kinds thereof may be used by being combined appropriately.
In view of the production efficiency, at least (A) component among the
38
components mixed in the detergent composition is preferably made into powder alone
and then subjected to powder blending together with other powder-like detergent raw
materials.
Examples of preferable preparation methods include:
5 a method ofhomogenously mixing a portion or all ofthe detergent raw materials
other than the (A) component with water to prepare slurry, and performing powder
blending on spray-dried particles obtained by performing spray drying on the slurry
along with the powder-like (A) component and the remaining detergent raw materials
(powder-like materials);
lOamethod of mixing a portion or all of the components other than the (A)
component, granulation the resultant by a granulation method using stirring, a
granulation method using pulverization (kneading·extruding·pulverization), a granulation
method using rolling, and the like, and performing powder blending on the obtained
particles, the powder-like (A) component, and the remaining raw materials (powder-like
15 materials); and
a method of performing powder blending by using powder-like materials as the
respective components; and the like.
In each of the methods, after powder blending, a step of coating the surface of
particles with the (C) component, a nonionic surfactant, a fragrance, a colorant, or the
20 like may be further performed.
When the detergent composition is a tablet, the particle-like detergent
composition obtained in the above manner may be tableted using a tableting machine,
whereby the tablet can be prepared.
When the detergent composition is a liquid, the respective components described
25 above may optionally be mixed with water, whereby the liquid can be prepared.
39
[0051 ]
The detergent composition of the present invention exhibits excellent detergency
and foaming performance even if washing is performed using water with a high degree of
hardness. Accordingly, the detergent composition is useful for washing in water with a
5 high degree of hardness (for example, 10° DH). In addition, having high foaming
performance, the detergent composition is useful for hand washing. Moreover, since the
pH of a I% aqueous solution or aqueous dispersion thereof is within the above range, the
washing liquid at the time of performing hand washing becomes mild to the skin of
hands, and in this respect, the detergent composition is also useful for washing by hand.
10 By combining the (A) component with the (B) component, particularly, a high
cleaning performance and foaming performance is exhibited particularly even under a
high degree of hardness. Supposedly, the reason is that since the (A) component is not
easily precipitated under a high degree of hardness and acts as an activator, the high
cleaning performance is obtained, or that since the (B) component stabilizes the film of
15 formed foam, foam sustainability is improved, for example.
In addition, the (C) component is considered to produce a foam-stabilizing effect
by reducing the speed at which the liquid present in the foam film is drained, thereby
improving the foam sustainability.
Moreover, the (D) component is considered to stabilize the foam film, thereby
20 improving foaming power.
Furthermore, by using the (E) component such as LAS or AS concurrently,
excellent foaming or cloth slippage property is exhibited during washing by hand.
[0052]
A subject to be washed with the detergent composition of the present invention
may be the same as those generally regarded as the subject to be washed (substance to be
40
washed) with a detergent composition, and examples thereof include textile products
such as clothes, towels, sheets, and curtains.
The washing method using the detergent composition of the present invention is
not particularly limited, and may be the same as the known washing methods. Specific
5 examples thereof include a method of putting the detergent composition into water and
washing the substance to be washed in the water (washing liquid). At this time, the
amount of the detergent composition put varies with the amount of the (A) component
and other surfactants mixed in. However, generally, the concentration of the detergent
composition in the washing liquid is preferably 0.1% by mass to 10% by mass (more
10 preferably 0.2% by mass to 1% by mass) in a case of hand washing, and 0.01% by mass
to 2% by mass (more preferably 0.02% by mass to 1% by mass) in the case of using a
'vvashing machine. The substance to be washed may be washed by hand or by a washing
machine (a twin tub washing machine, a fully automatic washing machine, a drum-type
washing machine, or the like). However, in the respect of effectiveness of the present
IS invention, for example, washing by hand is preferable in which water is poured into a tub,
and a detergent composition is dissolved in the water to wash clothes.
Examples
[0053]
The present invention will be described in more detail by illustrating examples,
20 but the present invention is not limited thereto.
In the present examples, "%" represents "% by mass" unless otherwise
specified.
Measurement methods and raw materials used in the following respective
examples will be shown below.
[0054]
41
[Measurement method]
[pH]
For pH measurement, pH of 1% aqueous solution (25°C) of various detergent
compositions was measured using a pH meter (HM-30S) manufactured by DKK-TOA
5 CORPORATION, based on JIS Z8802-1984.
[Measurement of weight average molecular weight of polymer compound
having carboxy group]
The weight average molecular weight of the polymer compound having a
carboxy group was measured by gel permeation chromatography by using polyethylene
10 glycol as a reference material.
[0055]
[Measurement method for average particle size]
First, an object (sample) to be measured was classified using 9 levels of sieves
having openings of 1680 flm, 1410 flm, 1190 flm, 1000 flm, 710 flm, 500 flm, 350 flm,
15 250 flm, and 149 flm and a tray. In the classification, sieves were stacked on the tray in
an order from a sieve having a small opening to a sieve having a large opening, and 100 g
of the sample was added from the top of the uppermost sieve having an opening of 1680
~lIn. Thereafter, the sieve was capped and mounted on a low-tap sieve shaker
(manufactured by Iida-seisakusho Japan Corporation, tapping: 156 times/min, rolling:
20 290 times/min), followed by shaking for 10 minutes under an atmospheric conditions of a
temperature of 25°C and a relative humidity of 40%, and then the sample remaining on
the respective sieves and the tray is collected for each size of sieve opening.
By repeating the above operation, classified samples with the respective particle
sizes including 1410 flm to 1680 flm (1410 flm. on), 1190 flm to 1410 flm (1190 flm. on),
5
42
1000 ~lm to 1190 ~m (1 000 ~m. on), 1000 ~m to 71 0 ~m (71 0 ~m. on), 500 ~m to 710
pm (500 ~m. on), 350 ~m to 500 ~m (350 ~m. on), 250 ~m to 350 ~m (250 ~m. on), 149
~lIn to 250 ~m (149 ~m. on), and tray to 149 ~m (149 ~m. pass) were obtained, and mass
frequency (%) was calculated.
Subsequently, the opening of a first sieve in which the calculated mass
frequency became 50% or more was set to a pm, the opening of a sieve that is larger by
one level than the sieve of a ~m was set to b ~m, the mass frequency accumulated from
the tray to the sieve of a pm was set to c%, and the mass frequency on the sieve of a ~m
was set to d%, thereby calculating average particle size (diameter based on 50% mass) by
10 the following formula.
[0056]
[Formula 2]
Average particle size (diameter based on 50% mass)=10[50- ic-dl(log b-Iog a)xlog
h: II: d/(Iog h-log a):
15 [0057]
[Measurement method for moisture content]
The moisture content was measured using Kett (MOISTURE
PETERMINATION BALANCE FD-600). The sample amount was set to 5 g, and the
change in weight caused after heating was performed at 140°C for 20 minutes was taken
20 as the moisture content.
[0058]
[Raw materials]
(Raw materials of a-sulfo fatty acid methyl ester (salt) (hereinafter, also
described as MES in some cases))
43
·Methyl palmitate: trade name "Pastel M-16", manufactured by Lion
Corporation
.Methyl stearate: trade name "Pastel M-180", manufactured by Lion Corporation
·Methanol: industrial grade methanol, containing 500 ppm or less of moisture,
5 manufactured by Sumitomo Chemical Co., Ltd.
·35% Hydrogen peroxide: 35% hydrogen peroxide for industrial use,
manufactured by MITSUIBISHI GAS CHEMICAL COMPANY, INC.
·Sodium hydroxide: caustic soda, industrial grade, manufactured by DAISO.
10
[0059]
(Anionic surfactants (excluding (A) component))
·Sodium lauryl sulfate ester (hereinafter, also described as AS-Na in some
cases): trade name "SLS", manufactured by PEPMACO MANUFACTRURING
CORPORATION
·Sodium linear alkylbenzenesulfonate (hereinafter, also described as LAS-Na in
15 some caess): a surfactant obtained by neutralizing linear alkyl (having 10 to 14 carbon
atoms) benzenesulfonate (hereinafter, also described as LAS-H in some cases) (trade
name "Lipon LH-200", manufactured by Lion Corporation, a pure content of 96%) with
NaOH at the time of preparing slurry for spray-drying or at the time of granulating: the
mixing amount in Tables 1 to 3 indicates % by mass of this surfactant as LAS-Na.
20 [0060]
(Nonionic surfactant)
·Polyoxyethylene alkyl ether (hereinafter, also described as AE in some cases): a
surfactant obtained by adding ethylene oxide in an amount of 9 mol on average to an
alcohol (trade name "CO-1214" manufactured by P&G Chemicals) including an alkyl
5
44
group having 12 to 16 carbon atoms (a pure content of 90%, manufactured by Lion
Corporation)
[0061 ]
(Zeolite and other detergency builders)
·Zeolite: A-type zeolite, trade name "Zeolite Na-4A", manufactured by THAI
CILICATE CHEMICALS
·Sodium tripolyphosphate (hereinafter, also described as STPP in some cases):
manufactured by Central Glass Co., Ltd.
·Sodium carbonate: particle-like ash, manufactured by ASAHI GLASS CO.,
10 LTD.
15
20
·Sodium silicate: a mixture including sodium silicate no. l/sodium silicate no. 2
in a mass ratio of 46:54, manufactured by Nippon Chemical Industrial Co., LTD.
·Sodium sulfate: neutral anhydrous sodium sulfate, manufactured by Nippon
Chemical Industrial Co., LTD.
[0062]
(Polymer compounds having carboxy group)
.Macromolecular polymer 1: a sodium salt of a powder-like acrylic acid/maleic
acid copolymer, trade name "Sokalan (registered trademark) CP-7 Granules NL", a
weight average molecular weight of 50,000, manufactured by BASF, Japan
·Macromolecular polymer 2: a sodium salt of an acrylic acid/maleic acid
copolymer, trade name "Aqualic (registered trademark) TL-500", a weight average
molecular weight of 15000, manufactured by NIPPON SHOKUBAI CO., LTD.
·Macromolecular polymer 3: sodium polyacrylate, trade name "Sokalan
(registered trademark) PA40", a weight average molecular weight of 15000,
5
45
manufactured by BASF, Japan
·Macromolecular polymer 4: sodium polyacrylate, trade name "Sokalan
(registered trademark) PA25", a weight average molecular weight of 4000, manufactured
by BASF, Japan
.Macromolecular polymer 5: sodium carboxymethyl cellulose, trade name
"eMC Daicel", product number: 1105, a weight average molecular weight of 60,000, a
degree of etherification of 0.6 to 0.8, manufactured by Daicel Corporation
[0063]
10
(Other components)
·Higher alcohol: an alcohol mixture including an alkyl group having 12 to 16
carbon atoms, trade name "CO-1214", manufactured by P&G Chemicals
·CBS: a fluorescent brightener, trade name "Tinopal (registered trademark)
CBS-X", manufactured by Ciba Specialty Chemicals K. K.
·AMS: a fluorescent brightener, trade name "Tinopal (registered trademark)
15 AMS-GX", manufactured by Ciba Specialty Chemicals K. K.
.Enzyme: a mixture of protease (Savinase (registered trademark) 12T)/amylase
(Stainzyme (registered trademark) 12T)/lipase (LIPEX (registered trademark)
IOOT)/cellulase (Celluclean 4500T)/glucosidase (Mannaway 4.0T) (all manufactured by
Novozymes, Japan)=6/21211/4 (mass ratio)
20 .Fragrance: the fragrance composition A shown in [Table 11] to [Table 18] in
Japanese Laid-Open Patent Application No. 2002-146399
·Colorant: ultramarine, manufactured by Dainichiseika Color & Chemicals Mfg.
Co.. Ltd., Ultramarine Blue
[0064]
46

[1. Preparation of paste-like MES]
330 kg of a fatty acid methyl ester mixture (a mixture obtained by mixing in
advance methyl palmitate (trade name "Pastel M-16" manufactured by Lion Corporation)
5 with methyl stearate (trade name "Pastel M-180" manufactured by Lion Corporation) at a
mass ratio of 9: 1) was injected into a stirrer-mounted reactor having a capacity of 1 kL,
and anhydrous sodium sulfate as a coloring inhibitor was injected into the reactor in an
amount of 5% by mass based on the fatty acid methyl ester mixture under stirring.
Thereafter, while stirring is being continued, 110 kg (1.2-fold mol based on the fatty acid
10 methyl ester mixture) of S03 gas (sulfonation gas) diluted with nitrogen gas to yield 4%
by volume was blown into the reactor under bubbling at a reaction temperature of 80°C
over 3 hours at a constant speed. Subsequently, the resultant was matured for 30
minutes while being kept at 80°C.
Thereafter, 14 kg of methanol as a lower alcohol was supplied thereto to esterify
15 the resultant. The esterification temperature was 80°C and the maturation time was 30
minutes.
20
Subsequently, an aqueous sodium hydroxide solution was added to the esterified
substance extracted from the reactor in an equivalent amount by using a line mixer,
thereby continuously neutralizing the esterified resultant.
Then the neutralized substance was injected into a bleach mixing line, and 35%
aqueous hydrogen peroxide was supplied thereto in a proportion of 1% converted in
terms of a pure content, based on the concentration of an anionic surfactant (a-sulfo fatty
acid methyl ester sodium salt (MES-Na) and an a-sulfo fatty acid disodium salt (di-Na
salt), followed by mixing. The resultant was bleached while being kept at 80°C,
47
thereby obtaining paste-like MES.
[0065]
[2. Concentration ofMES paste]
The MES paste obtained as above was introduced at 35 kg/h into a vacuum
5 thin-film evaporator (heat-transfer surface: 0.5 cm2
, inner diameter of cylindrical
treatment portion: 205 mm, clearance between the heat-transfer surface and the end of
blade as means for scraping up: 3 mm, trade name "Exeva (registered trademark),
manufactured by Shinko Pantec Co., Ltd.) rotating at a rotation frequency of 1,060 rpm
and at a speed of the end of blade of 11 mis, followed by concentration performed under
10 conditions of a heating temperature of inner wall (temperature of heat-transfer surface) of
135°C and a degree of vacuum (internal pressure of treatment portion) of 0.007 MPa to
0.014 MPa.
The temperature of the obtained concentrate was 115°C, and the moisture
content thereof was 2.5%.
15 [0066]
[3. Preparation ofMES solid]
The MES paste obtained by concentration was cooled by being continuously
supplied at 222 kg/h to a double-belt type belt cooler (NR3-Lo. Cooler) manufactured by
NIPPON BELTING CO., LTD. wherein the clearance between injection pulleys was
20 adjusted to be 2 mm. At this time, a movement speed of the belt was 6 mis, flow rates
of the cooling water were 1500 Llh for the upper belt (cooling water was caused to flow
on the back surface of the belt for cooling) and 1800 Llh for the lower belt (cooling water
\vas sprayed to the back surface of the belt for cooling), and the temperature of the
cooling water supplied was 20°C. A sheet of a surfactant-containing substance obtained
by being discharged from the cooling belt was crushed at a rotation frequency of 200 rpm
5
20
48
by an accessory crusher installed near a discharge pulley, thereby obtaining flaky MES
solids at 25°C.
[0067]
[4. Preparation of particles for MES detergent]
The obtained flaky MES solids (at a temperature of 25°C) were continuously
supplied at a rate of 100 kg/h to a screw extraction-type granulating machine
(manufactured by Hosokawa Micron Group, Extrud-O-Mix EM-6 model, rotation
frequency of main axis of 70 rpm) through a raw material-injecting port thereof.
Thereafter, the screw axes were rotated so as to rotate first and second paddles at 100
I 0 rpm. whereby the MES solids were kneaded and extracted from holes of a third orifice
plate, and noodle-like MES solids were obtained.
The noodle was cooled to 30°C at room temperature, and then injected into a
crusher (manufactured by OKADA SEIKO CO., LTD., Speed mill ND-I0 model, a
rotation frequency of blade of 840 rpm, a screen ~ of 4 mm) at a rate of 1 kg/min together
15 with zeolite (in the examples and comparative examples described later, zeolite was not
added in a case of particles for MES detergent used in a zeolite-unmixed composition),
followed by crushing, thereby obtaining particles for MES detergent having an average
particle size of 500 Ilm.
The obtained MES detergent particles had the following properties.
·A case where zeolite was mixed in: the MES pure content was 86.6%, the
zeolite content was 4%, the moisture content was 3.4%, the sodium sulfate content was
2.2%, and the methyl sulfate was 3.8%
.A case where zeolite was not mixed in: the MES pure content was 91.1 %, the
moisture content was 2.5%, the sodium sulfate content was 2.4%, and the methyl sulfate
,L
49
content was 4.0%
[0068]

By the following preparation method A, particle-like detergent compositions
5 consisting of the composition (%) shown in Tables 1 and 2 were prepared. In Tables 1
to 2. "Bal" in the section of sodium sulfate indicates the balance amount (an amount in
which the total amount of the particle-like detergent composition becomes 100%).
[Preparation method A for particle-like detergent composition: spray drying]
First, water was poured into a jacket-attached mixing tank provided with a
I 0 stirring device, and the temperature thereof was adjusted to SO°C.
Sodium sulfate and fluorescent brighteners (CBS and AMS) were added thereto,
followed by stirring for 10 minutes. Subsequently, anionic surfactants (LAS-Na
(obtained by neutralizing LAS-H with NaOH) and AS-Na), detergency builders (STPP,
sodium carbonate, sodium silicate), a higher alcohol, and macromolecular polymers 1 to
IS 5 were added thereto, followed by stirring for 10 minutes, and then a portion ofA-type
zeolite powder was added thereto. Thereafter, the resultant was further stirred for 30
minutes. thereby preparing a slurry for spray drying. The temperature of the obtained
slurry for spray drying was SO°C. The slurry for spray drying was spray-dried by a
countercurrent-type spray drying device including a pressure spray nozzle, thereby
20 obtaining spray-dried particles.
The obtained spray-dried particles were mixed with a portion ofA-type zeolite
powder and enzymes (protease, amylase, lipase, cellulase, and glucosidase) by a
V-blender, and the particles for MES detergent were further added thereto. Thereafter, a
fragrance and a nonionic surfactant (AE) were sprayed thereto, and for coloring a portion
of the spray-dried particles, while the particles were being transferred by a belt conveyor
5
50
at a rate of 0.5 m/s (layer of the spray-dried particles on the belt conveyor had a height of
30 mm and a width of 300 mm), a 20% by mass aqueous dispersion of a colorant was
sprayed onto the surface thereof, thereby obtaining a particle-like detergent composition
having a moisture content of 6%.
A 1% aqueous solution of the obtained particle-like detergent composition was
prepared, and the pH thereof was measured. The resultants were shown in Tables 1 and
[0069]
10

By the following preparation method B, the particle-like detergent compositions
consisting of the composition (%) shown in Table 2 were prepared. In Table 2, "Bal" in
the section of sodium sulfate indicates a balance amount (an amount in which the total
amount of the particle-like detergent composition becomes 100%).
[Preparation method B for particle-like detergent composition: powder blending]
15 By using FS-1200 high-speed mixer/granulator manufactured by Fukae Kogyo
Co.. Ltd., detergents were prepared in the following sequence according to the
composition shown in Table 2.
STPP, sodium sulfate, fluorescent brighteners (CBS and AMS), and a portion of
zeolite were dry-blended for 60 seconds by a mixer at a stirrer speed of 100 rpm and a
20 shearer speed of2000 rpm. Water (in an amount equivalent to 0.375% by mass) was
added thereto, and the mixer was operated for 90 seconds at the same stirrer speed and
shearer speed. The temperature thereof was maintained at 50°C or lower by means of
the cooling jacket through which water passed.
Water (in an amount equivalent to 1.4% by mass) as a binder, a nonionic
25 surfactant (AE) and a macromolecular polymer 1 were added to the mixer, and
51
granulating treatment was performed for 180 seconds at a stirrer speed of 100 rpm and a
shearer speed of 2000 rpm. The temperature thereof was maintained at 50°C or lower
by means of a cooling jacket through which water passed. The product obtained by this
step was particle-like solids. The shearer of the mixer was stopped, and while stirring
5 was being performed by the stirrer for 120 seconds at a speed of 90 rpm, enzymes and
the particles for MES detergent were added thereto. Zeolite (in an amount equivalent to
2% by mass) was further added thereto to modify the surface, and a fragrance was
sprayed thereto, thereby obtaining surfactant-containing particles. In order to color a
portion of the obtained surfactant-containing particles, a 20% by mass aqueous
10 dispersion of a colorant was sprayed thereto in the same manner as in the preparation
method A, thereby obtaining a particle-like detergent composition of which the moisture
content was adjusted to 4%.
A 1% aqueous solution of the obtained particle-like detergent composition was
prepared, and the pH thereof was measured. The results are shown in Table 2.
15
20
In addition, only in Example 13 and Comparative Example 4, the amount of
sodium hydroxide used as a neutralizer was adjusted in preparing a detergent
composition such that pH of the 1% aqueous solution of the particle-like detergent
composition became the pH shown in the table.
[0070]
The obtained particle-like detergent compositions of Examples 1 to 16 and
Comparative Examples 1 to 5 were evaluated as below. The results are also shown in
Tables 1 and 2.
[Evaluation method]
[Evaluation of foaming power during hand washing]
A wash basin (an inner diameter 30 cm~, a depth 10 cm) was prepared, and 3 L
20
52
of water having been adjusted in terms of hardness and temperature was poured into the
basin. For adjusting the hardness of water, first, 262.5 g of calcium chloride dihydrate
was dissolved in 10 L of deionized water to prepare hard water of 1000° DH, and then
the water was diluted with deionized water so as to yield the hardness in Tables 1 and 2
5 (1 ° DH=lO mg (calcium chloride)/L (water)). In addition, the temperature of the water
was set to 30°C.
The particle-like detergent composition was put in the water in a predetermined
amount (an amount in which the concentration of the particle-like detergent composition
becomes the amount (giL) of detergent used shown in Tables 1 and 2), followed by
10 stirring by hand for 30 seconds. Thereafter, as a test cloth, a sheet (about 150 g) of
cloth obtained by impregnating a cotton shirt with 0.1% by weight of staining oil
composed as below was put in the basin, and the test cloth was washed by hand for 1
minute by being rubbed 20 times with both hands on the front and back sides.
Subsequently, the hand-washed test cloth was wrung, and the height of foam on
I 5 the surface of water in the wash basin was measured with a gauge line-marked test tube.
The measurement was performed for three sites, and the average thereof was taken as the
foam height. the foam height (mm) measured after the first test cloth was washed was
taken as a value of foaming power, and the foam height of 35 mm or more was regarded
as a pass.
In addition, the ratio of the measured foam height to the foam height of
Comparative Example 1 (foam height of any of Examples 1 to 16 and Comparative
Examples 1 to 5/foam height of Comparative Example 1x100) was calculated. The
results are also described in Tables 1 and 2 as the foam-increasing rate (%).
[0071]
10
53
[Evaluation of foam sustainability during hand washing]
During the evaluation of the foaming power during hand washing, the step of
hand-washing the test cloth was repeated with the test cloth being replaced with a new
one each time. A point in time when the foam height measured after washing was 3 mm
5 was taken as an end point, and the number of sheets of the test cloth that could be washed
at that time was evaluated as the foam sustainability. The foam sustainability in which
8 sheets or more of the test cloth could be washed was taken as pass.
(Composition of staining oil)
·Oleic acid: 45%
·Triolein: 25%
·Cholesterololeate: 19.5%
·Liquid paraffin: 4%
·Squalene: 4%
·Cholesterol: 2.5%
15 [0072]
[Evaluation of cleaning performance]
An artificially stained cloth (manufactured by Sentakukagaku Kyokai) prepared
by impregnating a petrochemical cloth (unstained cloth) with an artificial stain was cut in
5x5 em, thereby preparing contaminated cloths. Terg-O-tometor (manufactured by
20 UNITED STATES TESTING) was used as the cleaning tester.
900 mL of washing liquid (at a temperature of 30°C) in which the concentration
of the particle-like detergent composition and the hardness of water were, respectively,
the amount of a detergent used (giL) and the hardness (0 DH) shown in Tables 1 and 2
was prepared.
54
The washing liquid, 10 sheets of the contaminated cloth, and a knitted cloth for
washing were put in the cleaning tester and cleaned for 10 minutes at 120 rpm and 30°C,
at a bath ratio of 30-times Thereafter, the cloths were transferred to a twin tub washing
machine (manufactured by Mitsubishi Electric Corporation, product number:
5 CW-C30AI-Hl) and spin-dried for 1 minute, and then rinsed for 3 minutes in 30 L of tap
water (15°C, 4° DH), followed by drying with air.
Ret1ectance of the contaminated cloth before cleaning and the contaminated
cloth after cleaning was respectively measured using a color-difference meter (trade
name: SE200 model) manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.,
10 and the cleaning rate (%) was calculated by the following formula.
Cleaning rate (%)=(K1S of contaminated cloth before cleaning-K1S of
contaminated cloth after cleaning)/(K1S of contaminated cloth before cleaning-K1S of
unstained cloth)x 100
[In the formula, K1S=(I-R/l00)2/(2R/I00), and R represents a ret1ectance (%).]
15 The cleaning rate (%) of 10 sheets of the contaminated cloth was calculated, and
if the average thereof exceeds 75% in a detergent composition, the composition was
considered to be passed.
[0073]
[Table 1]
e
Example
1 2 3 4 5 6 7 8 9 10
Composition MES 10 15 10 10 10 10 10 10 10 10
(%) LAS-Na 10 10 10 10 10 10 10 10 10 10
AS-Na 0 0 0 0 0 0 0 0 0 0
AE 1 0 1 1 1 1 1 1 1 1
STPP 10 10 10 10 10 10 10 10 10 10
Zeolite 10 10 0 10 0 10 10 10 10 10
Sodium 0 0 0 0 0 0 0 0 0 0
carbonate
Sodium silicate 0 0 0 0 0 0 0 0 0 0
Sodium sulfate Bal Bal Bal Bal Bal Bal Bal Bal Bal Bal
Macromolecular 2 2 2 0.5 0.5 0 0 0 1 2
polymer 1
Macromolecular 0 0 0 0 0 2 0 0 0 0
polymer 2
Macromolecular 0 0 0 0 0 0 2 0 0 0
polymer 3
Macromolecular 0 0 0 0 0 0 0 0 0 0
polymer 4
Macromolecular 0 0 0 0 0 0 0 2 1 0
polymer 5
Higher alcohol 0 0 0 0 0 0 0 0 0 1
CBS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
AMS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
VI
VI
e
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Fragrance 0.5 0.5 0.5 0.5 0.5 0.5 0.5 n.5 0.5 0.5
Ultramarine 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 6 6 6 6 6 6 6 6 6 6
pH (l% aqueous solution) 9.1 9.1 8.7 9.2 8.6 9.1 9.2 9.1 9.2 9.1
Foaming power (mm) 50 49 46 43 40 45 43 44 48 56
Foam-increasing rate (%: with 280 270 260 240 220 250 240 240 270 310
respect to Comparative
Example 1)
Foam sustainability (sheet) 10 10 9 9 8 10 10 9 10 10
Cleaning rate (%) 86 88 84 84 82 84 84 80 86 86
Hardness 5°DH
Amount of detergent used 3g/L
Preparation method A
Vl
0[0074]
[Table 2]
e
Example Comparative Example
11 12 13 14 15 16 1 2 3 4 5
Composition MES 3 10 10 5 35 10 10 10 10 10 35
(%) LAS-Na 10 5 10 10 0 10 10 10 10 10 0
AS-Na 0 5 0 0 0 0 0 0 0 0 0
AE 1 1 1 1 1 1 1 ·1 1 1 1
STPP 10 10 10 0 10 16 10 10 10 10 10
Zeolite 10 10 10 20 10 4 10 10 10 10 10
Sodium 0 0 0 0 0 0 10 0 0 0 0
carbonate
Sodium silicate 0 0 0 0 0 0 0 5 0 0 0
Sodium sulfate Bal Bal Bal Bal Bal Bal Bal Bal Bal Bal Bal
Macromolecular 2 2 2 2 2 2 2 2 0 2 5
polymer 1
Macromolecular 0 0 0 0 0 0 0 0 0 0 0
polymer 2
Macromolecular 0 0 0 0 0 0 0 0 0 0 0
polymer 3
Macromolecular 0 0 0 0 0 0 0 0 2 0 0
polymer 4
Macromolecular 0 0 0 0 0 0 0 0 0 0 0
polymer 5
Higher alcohol 0 0 0 0 0 0 0 0 0 0 0
CBS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
AMS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
VI
-....l
e
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Fragrance 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Ultramarine 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 6 6 6 6 4 6 6 6 6 6 4
pH (1% aqueous solution) 9.2 9.1 6.2 8.9 9.1 9.3 11.1 10.9 9.1 4.8 8.9
Foaming power (mm) 48 53 49 52 38 46 18 20 34 31 34
Foam-increasing rate (%: with 270 290 270 290 210 260 100 110 190 170 190
respect to Comparative
Example 1)
Foam sustainabi1ity (sheet) 9 10 10 10 8 10 6 6 7 7 7
Cleaning rate (%) 80 86 84 82 90 88 88 88 86 71 91
Hardness 5°DH
Amount of detergent used 3 giL
Preparation method A B A B
VI
00
59
[0075]
As shown in Tables 1 and 2, the particle-like detergent compositions of
Examples 1 to 16 satisfied the level of pass (foaming power (foam height) of 35 mm or
more, foam sustainability of8 sheets or more, and a cleaning rate of75% or more) in of
5 the evaluation of all of foaming power, foam sustainability, and cleaning performance.
Particularly, Example 1 in which zeolite was mixed exhibited a higher degree of foaming
power, foam sustainability, and cleaning performance, compared to Example 3 composed
in the same manner as Example 1 except that zeolite was not mixed in. The same
results were confirmed even if Example 1 was compared with Examples 4 and 5. In
1() addition, in Example lOin which a higher alcohol was mixed, the foaming power was
improved compared to Example 1 composed in the same manner as Example 10 except
that a higher alcohol was not mixed in.
On the other hand, each of Comparative Examples 1 and 2 of which the pH of a
1% aqueous solution was 11.1 and 10.9 respectively, Comparative Example 3 in which
15 the macromolecular polymer 4 having a weight average molecular weight of 4000 was
mixed, and Comparative Example 5 in which the macromolecular polymer 1 was mixed
in an amount of 5% by mass exhibited an excellent cleaning performance, but both the
foaming power and foam sustainability of these failed to pass the evaluation. In
addition, Comparative Example 4 of which the pH of a 1% aqueous solution was 4.8
20 failed to pass the evaluation in terms of all of the foaming power, foam sustainability, and
cleaning performance.
[0076]

By the following preparation method C, particle-like detergent compositions
consisting of the composition (%) shown in Table 3 were prepared. In Table 3, "Bal" in
5
60
the section of sodium sulfate indicates a balance amount (an amount in which the total
amount of the particle-like detergent composition becomes 100%).
[Preparation method C for particle-like detergent composition: granulation by
stirring]
LAS-Na, STPP, sodium sulfate, a fluorescent brightener, sodium silicate, a
higher alcohol, macromolecular polymers I to 3 and 5, and a portion of zeolite were
dissolved or dispersed in water, thereby preparing slurry containing 38% by mass of
moisture. Thereafter, the slurry was spray-dried using a countercurrent-type spray
drying tower under a condition of a hot-air temperature of 300°C, thereby obtaining
10 spray-dried particles.
The obtained spray-dried particles were injected (filling rate of 50% by volume)
into a Lodige mixer (manufactured by MATSUBO Corporation, M20 model) provided
with a spade-like shovel and having a clearance between the shovel and a wall surface of
5 mm, and started to be stirred at a main axis speed of 200 rpm and a chopper speed of
15 200 rpm. A nonionic surfactant (AE) was injected into the mixer for over 2 minutes,
followed by stirring for 5 minutes. Thereafter, a portion (in an amount equivalent to 1%
by mass) ofA-type zeolite powder was injected into the mixer, followed by stirring for 2
minutes, thereby obtaining surfactant-containing particles.
The obtained surfactant-containing particles, a portion (in an amount equivalent
20 to 2% by mass) ofA-type zeolite powder, enzymes, and particles for MES detergent were
mixed by a V-blender, and a fragrance was sprayed thereto. In order to color a portion
of the obtained surfactant-containing particles, a 20% by mass aqueous dispersion of a
colorant was sprayed thereto in the same manner as in preparation method A, thereby
obtaining a particle-like detergent composition of which the moisture content was set to
1.
c.) 7%.
61
A 1% aqueous solution of the obtained particle-like detergent composition was
prepared, and the pH thereof was measured. The results are shown in Table 3.
The same evaluation (foaming power, foam sustainability, and cleaning
performance) as in Example 1 was performed on the obtained particle-like detergent
5 composition. Here, for the foam-increasing rate (%) in the evaluation of foaming power,
the ratio of foam height not to Comparative Example 1 but to Comparative Example 6
was calculated. The results are also described in Table 3.
[0077]
[Table 3]
Example Comparative Example
17 18 19 20 21 22 23 6 7 8
Composition MES 20 20 20 20 20 20 20 20 20 0
(%) LAS-Na 20 20 20 20 20 20 20 20 20 40
AE 2 2 2 2 2 2 2 2 2 2
STPP 20 20 20 20 20 20 20 10 20 20
Zeolite 20 0 20 20 20 20 20 20 20 20
Sodium silicate 0 0 0 0 0 0 0 5 0 0
Sodium sulfate Bal Bal Bal Bal Bal Bal Bal Bal Bal Bal
Macromolecular 2 2 0.5 0 0 1 2 2 0 2
polymer 1
Macromolecular 0 0 0 2 0 0 0 0 0 0
polymer 2
Macromolecular 0 0 0 0 2 0 0 0 0 0
polymer 3
Macromolecular 0 0 0 0 0 1 0 0 0 0
polymer 5
Higher alcohol 0 0 0 0 0 0 0.5 0 0 0
CBS 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
AMS 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Enzyme 3 3 3 3 3 3 3 3 3 3
Fragrance 1 1 1 1 1 1 1 1 1 1
Ultramarine 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
Moisture 7 7 7 7 7 7 7 7 7 7
•
0N
pH (I% aqueous solution) 9.1 8.7 8.6 9.1 9.2 9.1 9.1 10.5 9.1 9.2
Foaming power (mm) 44 42 37 41 39 42 48 22 34 47
Foam-increasing rate (%: with 200 190 170 190 180 190 220 100 160 210
respect to Comparative
Example 6)
Foam sustainability (sheet) 9 8 8 8 8 8 8 6 7 8
Cleaning rate (%) 80 77 75 77 76 77 77 82 73 71
Hardness lOoDH
Amount of detergent used 1.5 giL
Preparation method C
•
0\ w
64
[0078]
As shown in Table 3, the particle-like detergent compositions of Examples 17 to
23 satisfied the level of pass (foaming power (foam height) of 35 mm or more, foam
sustainability of 8 sheets or more, and a cleaning rate of 75% or more) in evaluations of
5 all of foaming power, foam sustainability, and cleaning performance. Particularly,
Example 17 in which zeolite was mixed exhibited a higher degree of foaming power,
foam sustainability, and cleaning performance, compared to Example 18 composed in the
same manner as Example 17 except that zeolite was not mixed therein. In addition, in
Example 23 in which a higher alcohol was mixed, the foaming power was improved
10 compared to Example 16 composed in the same manner as Example 23 except that a
higher alcohol was not mixed in.
On the other hand, Comparative Example 6 of which the pH of a 1% aqueous
solution was 10.5 exhibited excellent cleaning performance, but failed to pass the
evaluation in terms of both the foaming power and foam sustainability. In addition,
15 Comparative Example 7 in which the macromolecular polymer was not mixed failed to
pass the evaluation in terms of all of the foaming power, foam sustainability, and
cleaning performance. Moreover, Comparative Example 8 in which LAS-Na was
mixed instead of MES exhibited excellent foaming power and foam sustainability, but
failed to pass the evaluation in terms of the cleaning performance, so this composition
20 was inappropriate for washing using water with a high degree of hardness.
Industrial Applicability
[0079]
The detergent composition of the present invention exhibits excellent detergency
7....
) and foaming performance even if washing is performed using water with a high degree of
65
hardness. Accordingly, the detergent composition may be applicable as a detergent for
washing by hand and the like.

CLAIMS
1. A detergent composition comprising:
(A) at least one compound selected from a-sulfo fatty acid alkyl esters and a salt
5 thereof in an amount of2.5% by mass or more and less than 40% by mass; and
(8) at least one compound selected from polymer compounds having a carboxy
group with a weight average molecular weight of more than 10,000 and 500,000 or less
and a salt thereof in an amount of from 0.1% by mass to 4% by mass,
wherein a pH at 25°C of a 1% by mass aqueous solution or aqueous dispersion
10 of the detergent composition is from 5.5 to 9.4.
2. The detergent composition according to Claim 1, further comprising (C) zeolite
in an amount of from 0.5% by mass to 30% by mass.
15 The detergent composition according to Claim 1 or 2, not comprising an alkaline
agent selected from carbonate and silicate of alkali metals.
4. The detergent composition according to anyone of Claims 1 to 3,
wherein the (A) at least one compound selected from a-sulfo fatty acid alkyl
20 esters and a salt thereof is a compound represented by the following General Formula
(a1):
[In the formula, RI represents an alkyl group or an alkenyl group having 6 to 20
carbon atoms, R2 represents an alkyl group having 1 to 6 carbon atoms, and M represents
67
a hydrogen atom or a counterion].
5. The detergent composition according to anyone of Claims I to 4,
wherein the (B) at least one compound selected from polymer compounds
::; having a carboxy group with a weight average molecular weight of more than 10,000 and
500,000 or less and a salt thereof is at least one compound selected from polycarboxylic
acids and a salt thereof as well as carboxylic acid-modified saccharides and a salt thereof.
6. The detergent composition according to anyone of Claims 1 to 5, which is
10 granulated.
7. The detergent composition according to anyone of Claims 1 to 6, which is for
washing by hand.