JP6148008B2 - Detergent composition for hand washing and washing method - Google Patents

Description

The present invention relates to a detergent composition useful for laundering textile products such as clothing, particularly hand washing.
This application claims priority based on Japanese Patent Application No. 2010-095382 for which it applied to Japan on April 16, 2010, and uses the content here.

In detergent compositions used for washing clothes and the like, an anionic surfactant is usually blended as a cleaning component. In addition, a detergency builder is blended for the purpose of improving detergency and imparting various other performances. Alkali agents are one of the detergency builders formulated for the purpose of improving detergency, and alkali metal carbonates and silicates are widely used from the viewpoints of detergency and cost.
Conventionally, linear alkylbenzene sulfonate (LAS salt) has been widely used as an anionic surfactant used in detergent compositions, but in recent years, α-sulfo fatty acid alkyl ester salts have been used. The α-sulfo fatty acid alkyl ester salt has advantages such as excellent detergency, particularly high detergency even when high hardness water is used, and good biodegradability.
The α-sulfo fatty acid alkyl ester salt is generally granulated alone or with other surfactants to form a surfactant powder, and then blended with other detergent ingredients to form a detergent composition. . For example, Patent Document 1 discloses spray-dried powder obtained by spray-drying an aqueous slurry containing a water-soluble salt of α-sulfo fatty acid alkyl ester, zeolite, and sodium sulfate at a specific mass ratio and having a pH of 10 or less. A method of granulating the body with an alkali builder and a binder component is disclosed. Patent Document 2 includes 40% by mass or more of α-sulfo fatty acid alkyl ester salt and 0.001 to 0.4% by mass of a chelating agent and / or an antioxidant. A surfactant powder having a pH of 7.5 or higher and a granular detergent composition containing the surfactant powder are disclosed.

JP-A-4-348196 JP-A-10-204479

The α-sulfo fatty acid alkyl ester salt has the above advantages, in particular, the high hardness of water used for washing in the future because it exhibits a high detergency even when high hardness water is used (high water resistance). Expansion in the area is expected. However, detergent compositions containing an α-sulfo fatty acid alkyl ester salt tend to have low foam performance, and less foaming during washing than other anionic surfactants such as LAS. , The bubbles are easy to disappear (low bubble persistence). These foam performances tend to decrease as the water hardness increases.
The low foam performance is advantageous when washing is performed using a fully automatic washing machine or a drum type washing machine, but is disadvantageous when washing is performed by hand washing. That is, in the case of hand-washing, especially when repeatedly washing with the same washing liquid, the user tends to judge the cleaning power by the good foaming and the persistence of the foam, so the foam performance is low, Detergency may be considered low. Therefore, improvement of foam performance is required for such applications.
The present invention has been made in view of the above circumstances, and provides a detergent composition useful for hand-washing washing, which exhibits excellent detergency and foam performance even when washing is performed using high-hardness water. For the purpose.

As a result of intensive studies, the present inventors have found that the foam performance of the α-sulfo fatty acid alkyl ester salt can be improved by removing the alkali agent, particularly the aforementioned alkali metal carbonates and silicates. As a result of further investigation based on this knowledge, the α-sulfo fatty acid alkyl ester salt and the specific polymer compound are blended in specific amounts, respectively, and the amount of the alkali agent is reduced as compared with the conventional one. The inventors have found that the above-mentioned problems can be solved by setting the pH of the solution within a specific range, and have completed the present invention.
The present invention for solving the above problems has the following aspects.
[1] A detergent composition, (A) 2.5 mass% or more and less than 40 mass% of at least one compound selected from α-sulfo fatty acid alkyl ester and a salt thereof, and (B) polyacrylic acid, It is at least one selected from polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, acrylic acid-maleic acid copolymer, acrylic acid-acrylic acid amide copolymer, and acrylic acid-allyl alcohol copolymer. Containing 0.1% by mass or more and 4% by mass or less of at least one compound selected from a polymer compound having a carboxy group having a weight average molecular weight of 12,000 to 100,000 and salts thereof;
A detergent composition for hand-washing laundry, wherein the pH at 25 ° C. of a 1% by mass aqueous solution or aqueous dispersion of the detergent composition is from 5.5 to 9.4.
[2] The detergent composition for hand-washing laundry according to [1], further comprising (C) 0.5% by mass to 30% by mass of zeolite.
[3] The detergent composition for hand-washing laundry according to [1] or [2], further comprising a tripolyphosphate.
[4] further containing tripolyphosphate,
Wherein (C) mass ratio of the zeolite and the tripolyphosphate ((C) Zeolite / tripolyphosphate) is 19 / 1-1 / 19, the detergent composition for hand-washing according to [2].
[5] does not include the alkali metal carbonates and silicates, [1] to detergent compositions for hand-washing according to any one of [4].
[6] Any one of [1] to [5], wherein at least one compound selected from the (A) α-sulfo fatty acid alkyl ester and a salt thereof is a compound represented by the following general formula (a1): The detergent composition for hand-washing laundry according to one item.
R ¹ —CH (SO ₃ M) —CO—O—R ² (a1)
[Wherein, R ¹ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, and M is a hydrogen atom or a counter ion. ]
[7 ] The detergent composition for hand-washing laundry according to any one of [1] to [ 6 ], which is granular.
[ 8 ] A washing method in which the hand washing laundry detergent composition according to any one of [1] to [ 7 ] is poured into water to wash and wash the laundry.

  ADVANTAGE OF THE INVENTION According to this invention, even if it wash | cleans using high hardness water, the outstanding cleaning power and foam performance are exhibited, and the detergent composition useful as an object for hand-washing washing can be provided.

<(A) component: at least one selected from α-sulfo fatty acid alkyl esters and salts thereof>
The detergent composition of the present invention contains component (A) (at least one selected from α-sulfo fatty acid alkyl esters and salts thereof).
Examples of the component (A) include compounds represented by the following general formula (a1).
R ¹ —CH (SO ₃ M) —CO—O—R ² (a1)
[Wherein, R ¹ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, and M is a hydrogen atom or a counter ion. ]

The alkyl group or alkenyl group for R ¹ may be linear or branched.
The carbon number of R ¹ is 6 to 20, preferably 8 to 18, and more preferably 10 to 16 from the viewpoint of detergency. R ¹ may be one kind of group, or two or more kinds of groups may be mixed.
The alkyl group for R ² may be linear or branched, and the carbon number thereof is 1 to 6, preferably 1 to 3, and more preferably 1 from the viewpoint of detergency. .
Any counter ion of M may be used as long as it can form a water-soluble salt with R ¹ CH (COOR ² ) SO ₃ ^— , such as an alkali metal, an alkaline earth metal, a protonated amine, and ammonium. Is mentioned.
Examples of the alkali metal include sodium and potassium.
Examples of the alkaline earth metal include calcium and magnesium.
In the protonated amine, the amine may be any of 1 to 3 grades, and preferably has 1 to 6 carbon atoms in total. The amine may or may not have a hydroxyl group, but preferably has a hydroxy group from the viewpoints of low-temperature solubility during washing, formulation, and the like. Examples of such amines include alkanolamines, and the alkanol group preferably has 1 to 3 carbon atoms. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
As M, an alkali metal or an alkanolamine is preferable, and an alkali metal is more preferable.

The component (A) contained in the detergent composition may be one type or two or more types.
The content of the component (A) in the detergent composition is 2.5% by mass or more and less than 40% by mass with respect to the total amount in the detergent composition, preferably 3% by mass or more and 35% by mass or less, and preferably 5% by mass. % To 30% by mass is more preferable. When the ratio is 2.5% by mass or more, the effect of the component (A) is sufficiently exhibited and the cleaning power is excellent. When it is less than 40% by mass, the foam performance and the rinsing property are excellent.

(A) A commercially available thing may be used for a component, and what was manufactured by the well-known manufacturing method as described in international publication 2004-111166 pamphlet, international publication 2009-054406 pamphlet, etc. may be used. For example, an α-sulfo fatty acid alkyl ester can be obtained by sulfonating a fatty acid alkyl ester, and an α-sulfo fatty acid alkyl ester salt can be obtained by neutralizing the sulfo group of the α-sulfo fatty acid alkyl ester with an alkali. It is done.
The alkali used for neutralization corresponds to the M counter ion.
In the said manufacturing method, you may esterify using alcohol, such as methanol, after sulfonation and before neutralization as needed. By performing the esterification step, when the SO ₃ bimolecular adduct remains in the reaction product, the esterification of the alkoxy moiety of the SO ₃ bimolecular adduct proceeds, further promoting the elimination of SO _3. Is done. As a result, the production of by-products is suppressed, and the purity of the α-sulfo fatty acid alkyl ester in the reaction product is improved.
In the above production method, if necessary, before or after the neutralization step described above, a bleaching agent such as hydrogen peroxide is used to make the color tone of the α-sulfo fatty acid alkyl ester salt close to white. Bleaching treatment may be performed using
The product after the neutralization step or the bleaching step is usually a paste having a solid content of about 50 to 80% by mass. The product may be further subjected to treatment such as concentration or pulverization as necessary. The pulverization can be performed by a known granulation method such as a kneading / extrusion granulation method (kneading / extrusion / pulverization), a stirring granulation method, or a rolling granulation method.

In the α-sulfo fatty acid alkyl ester salt obtained by the production method as described above, usually, in addition to the α-sulfo fatty acid alkyl ester salt itself, an α-sulfo fatty acid dialkali salt (for example, R in the above general formula (a1)) ² is substituted with a counter ion of M. Hereinafter, it may be referred to as a di-salt. The di-salt has a function as a surfactant, although its function is lower than that of the α-sulfo fatty acid alkyl ester salt. Therefore, in the α-sulfo fatty acid alkyl ester salt produced as described above, the content of the active ingredient (AI) as the surfactant is the sum of the α-sulfo fatty acid alkyl ester salt (pure component) and the di-salt. Calculated as content. The AI content in the α-sulfo fatty acid alkyl ester salt is preferably 10 to 80% by mass, more preferably 35 to 80% by mass, and more preferably 60 to 70% by mass with respect to the total mass of the α-sulfo fatty acid alkyl ester salt. % Is more preferable. Manufacturing efficiency improves that it is 10 mass% or more, and it is excellent in handling property in it being 80 mass% or less.
In addition to α-sulfo fatty acid alkyl ester salts and di-salts, α-sulfo fatty acid alkyl ester salts include methyl sulfate, ethyl sulfate, propyl sulfate, lower / intermediate carboxylic acids or their esters, ketones, aldehydes, etc. Organic substances and inorganic substances such as sodium sulfate are included as by-products. The amount of these by-products is usually very small and does not particularly affect the effect of the present invention.

<Component (B): at least one selected from polymer compounds having a carboxy group having a weight average molecular weight of more than 10,000 and not more than 500,000 and salts thereof>
The detergent composition of the present invention contains the component (B) (at least one selected from a polymer compound having a carboxy group having a weight average molecular weight of more than 10,000 and 500,000 or less and a salt thereof) together with the component (A). .
The weight average molecular weight of the component (B) is preferably 12,000 or more and less than 500,000, more preferably 15,000 or more and 300,000 or less, and further preferably 15,000 or more and 100,000 or less. When the weight average molecular weight is greater than 10,000, the foam performance (foaming power and foam sustainability), particularly the foam sustainability is excellent. If it is 500,000 or less, the solubility of the detergent composition in water will be good.
In the present specification, “weight average molecular weight” indicates a value obtained by analysis by gel permeation chromatography (GPC) using sodium polyacrylate or polyethylene glycol as a standard substance. In addition, as a standard substance, when (B) component is a polymer of a monomer having a carboxy group (unsaturated carboxylic acid or the like) or a salt thereof, sodium polyacrylate, and (B) component is a carboxylic acid-modified polysaccharide Uses polyethylene glycol.

  The polymer compound having a carboxy group or a salt thereof used as the component (B) is not particularly limited as long as the weight average molecular weight is within the above range, and can be appropriately selected from known compounds. Preferred examples of the polymer compound include polymers of unsaturated carboxylic acids (hereinafter referred to as polycarboxylic acids) and salts thereof, polyacetal carboxylic acids such as polyglyoxylic acid and salts thereof (for example, JP-A-54-52196). Those described in the publication), oxidized polysaccharides and salts thereof, and carboxylic acid-modified polysaccharides and salts thereof. Among these, at least one selected from polycarboxylic acids and salts thereof, and carboxylic acid-modified polysaccharides and salts thereof is preferable because of excellent effects of the present invention.

In the polycarboxylic acid, examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, hydroxyacrylic acid, hydroxymethacrylic acid, maleic acid, fumaric acid, and itaconic acid.
The unsaturated carboxylic acid unit constituting the polycarboxylic acid may be one type or two or more types. Here, the “unit” means a repeating unit constituting the polymer. For example, an acrylic acid unit is a repeating unit formed by cleavage of an unsaturated double bond of acrylic acid.
The polycarboxylic acid may have a monomer unit other than the unsaturated carboxylic acid. The monomer other than the unsaturated carboxylic acid may be any monomer that can be copolymerized with the unsaturated carboxylic acid, such as maleic anhydride, acrylic acid amide, methacrylic acid amide, alkyl acrylate, alkyl methacrylate, vinyl alcohol. And allyl alcohol.
Specific examples of the polycarboxylic acid include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, acrylic acid-maleic acid copolymer, acrylic acid-acrylic acid amide copolymer, and acrylic Examples include acid-allyl alcohol copolymers.
Among the above-mentioned polycarboxylic acids, those having an acrylic acid unit are preferable, and polyacrylic acid (a homopolymer of acrylic acid) and an acrylic acid-maleic acid copolymer are particularly preferable. The salt of the polycarboxylic acid is not particularly limited, and examples thereof include alkali metal salts, alkaline earth metal salts, protonated amine salts, and ammonium salts. Examples of the alkali metal, alkaline earth metal, and protonated amine are the same as those exemplified as M in the formula (a1).
Acrylic acid-maleic acid copolymer is preferable because the higher the ratio of maleic acid units, the better the detergency. However, if the ratio of maleic acid units is too high, it is difficult to increase the weight average molecular weight. From this viewpoint, the ratio (molar ratio) of maleic acid units / acrylic acid units in the acrylic acid-maleic acid copolymer is preferably 20/80 to 80/20, more preferably 30/70 to 60/40, 40 / 60-50 / 50 is more preferable.
As the polycarboxylic acid, a commercially available one may be used, or one synthesized by a known method may be used. For example, specific product names include “Socaran (registered trademark) PA40”, “Socaran (registered trademark) CP-7”, “Socaran (registered trademark) CP-9” (above BASF Japan Ltd.), “Aquaric ( (Registered Trademark) TL-500 "" Aquaric (Registered Trademark) TL-400 "(manufactured by Nippon Shokubai Co., Ltd.) can be used favorably.

An oxidized polysaccharide is a polysaccharide into which a carboxy group has been introduced by an oxidation treatment (for example, a product obtained by converting —CH ₂ OH to —COOH by oxidation). Examples of the polysaccharide include cellulose, starch, amylose, and pectin.
A carboxylic acid-modified polysaccharide is a polysaccharide into which a carboxy group has been introduced by a modification treatment using a carboxylic acid. Examples of the carboxylic acid used for the modification treatment include a monocarboxylic acid halide such as monochloroacetic acid and an unsaturated carboxylic acid such as (meth) acrylic acid.
Examples of the polysaccharide include the same ones as described above. In particular, cellulose is preferable because of excellent effects of the present invention.
Examples of the carboxylic acid-modified cellulose include carboxyalkyl cellulose and salts thereof. Among these, at least one selected from carboxyalkyl cellulose and salts thereof is preferable from the viewpoints of detergency, foam performance, and the like.
Carboxyalkyl cellulose or a salt thereof is obtained by etherifying a part or all of hydroxyl groups (hydroxyl group directly bonded to a glucopyranose ring and hydroxyl groups bonded through an alkylene group) in a cellulose molecule, to form —O—R ⁵ —COOZ. [R ⁵ is an alkylene group, and Z is a hydrogen atom or a counter ion. For example, it can be prepared by reacting a cellulose raw material such as pulp with caustic soda and then reacting with monochloroacetic acid.
R ⁵ is preferably a linear or branched alkylene group as the alkylene group, and preferably has 1 to 3 carbon atoms. As the alkylene group, a methylene group is particularly preferable. That is, carboxymethyl cellulose is particularly preferable as the carboxyalkyl cellulose.
The counter ion in Z is not particularly limited, and examples thereof include alkali metals, alkaline earth metals, protonated amines, ammonium, and the like, respectively, the same as those exemplified as M in the formula (a1). Can be mentioned.
As the carboxylic acid-modified cellulose, a commercially available one may be used, or one synthesized by a known method may be used. For example, “CMC Daicel product number: 1105” (Daicel Chemical Industries, Ltd.) or the like can be favorably used as a specific trade name of carboxymethylcellulose.
The degree of etherification of the carboxyalkyl cellulose or a salt thereof is preferably 0.2 to 1.3, more preferably 0.2 to 0.8. In the present invention, the degree of etherification means the average number of hydroxyl groups substituted with a carboxyalkyl group or a salt thereof (—R ⁵ —COOZ) per glucopyranose ring unit. That is, it indicates how many of the three hydroxyl groups possessed by the glucopyranose ring are substituted by a carboxyalkyl group or a salt thereof, and is a maximum of three.

The component (B) contained in the detergent composition may be one type or two or more types.
As the component (B), a polycarboxylic acid having an acrylic acid unit is preferable, and an acrylic acid-maleic acid copolymer is particularly preferable.
The content of the component (B) in the detergent composition is 0.1% by mass or more and 4% by mass or less, preferably 0.3% by mass or more and 3% by mass or less, based on the total amount of the detergent composition. It is more preferably 4% by mass or more and 2.5% by mass or less, and further preferably 0.5% by mass or more and 2% by mass or less. When the ratio is 0.1% by mass or more, the foam performance is excellent. When the content is 4% by mass or less, the detergent composition has excellent solubility in water.
The amount that the ratio (mass ratio) of the component (A) / component (B) is within the range of 5/1 to 20/1 is preferable. The ratio is more preferably 5/1 to 10/1. Within this range, the foam increasing effect and the cleaning effect are excellent.

<(C) component: zeolite>
The detergent composition of the present invention preferably further contains (C) zeolite.
In this case, it is preferable that content of (C) component in a detergent composition is 0.5 to 30 mass% with respect to the whole quantity in the said detergent composition. By containing the component (C) at a predetermined ratio, the foam performance (foaming power and foam sustainability) is further improved.
5 mass% or more and 330 mass% or less are more preferable with respect to the whole quantity in the said detergent composition, and, as for content of the said (C) component, 8 mass% or more and 30 mass% or less are more preferable.
Zeolite is a crystalline aluminosilicate, and examples include A-type zeolite, X-type zeolite, Y-type zeolite, and P-type zeolite. Any of these can be used as the component (C). As the component (C), A-type zeolite is preferable from the viewpoint of cleaning performance.
(C) 2-10 micrometers is preferable and the average particle diameter of a component has more preferable 3-8 micrometers. When the average particle size is 2 μm or more, the cleaning performance is good, and when it is 10 μm or more, the cleaning performance is lowered.

In the present specification, “average particle diameter” is a value (mass 50% diameter) measured by the following measuring method. When the average particle size exceeds 149 μm, the average particle size measurement method (1) is used, and when the average particle size is 149 μm or less, the average particle size measurement method (2) is used.
[Measurement method of average particle diameter (1)]
First, the measurement object (sample) is classified using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and a 100 g sample is put on the top 1680 μm sieve, and a lid is put on a low-tap sieve shaker (Iida Co., Ltd.). (Manufactured by Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes under atmospheric conditions of a temperature of 25 ° C. and a relative humidity of 40%, and then the samples remaining on the respective sieves and trays Is recovered for each sieve mesh.
By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) , 350-500 μm (350 μm.on), 250-350 μm (250 μm.on), 149-250 μm (149 μm.on), and saucer-149 μm (149 μm.pass). %).
Next, the opening of the first sieve with a calculated mass frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the integration of the mass frequency from the tray to the sieve of a μm is c The average particle diameter (mass 50% diameter) is determined by the following formula, where d is the mass frequency on the sieve of% and a μm.

[Measurement method of average particle diameter (2)]
Measurement is performed using a laser diffraction / scattering particle size distribution analyzer. The measurement conditions were LA-920 wet method manufactured by Horiba, Ltd., measurement temperature: normal temperature, dispersion medium: ion-exchanged water, circulation rate: 8, stirring time: 5 minutes, ultrasonic intensity: 7, relative Refractive index (water): 1.20.

The component (C) contained in the detergent composition may be one type or two or more types.
The content of the component (C) in the detergent composition is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 27% by mass or less with respect to the total amount of the detergent composition, and 2% by mass. % To 25% by mass is more preferable. When the ratio is less than 0.5% by mass, the effect of the component (C) is not sufficiently exhibited. On the other hand, when it exceeds 30% by mass, the foam performance and the detergency may be insufficient.

<(D) component: higher alcohol>
The detergent composition of the present invention preferably further contains (D) a higher alcohol. Thereby, foaming power further improves.
In the present invention, the “higher alcohol” is an alcohol having 10 to 16 carbon atoms. (D) As for carbon number of a component, 12-14 are more preferable.
Component (D) may be a monohydric alcohol, a polyhydric alcohol, or a monohydric alcohol.
The hydrocarbon group constituting the alcohol of component (D) may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The hydrocarbon group may be saturated, unsaturated, or saturated.
1 type or 2 types or more may be sufficient as (D) component contained in a detergent composition.
(D) As a component, a commercially available thing may be used and what was synthesize | combined by the well-known method may be used. Specifically, as a commercially available product, Conol 20P (trade name, manufactured by Shin Nippon Chemical Co., Ltd., linear C12 higher alcohol (lauryl alcohol)), Diadol 13 (trade name, manufactured by Mitsubishi Chemical Corporation, C13 higher alcohol (carbon) The chain contains branched ones (2-methyl) (straight chain is 49%)), CO-1270 (trade name, manufactured by P & G Chemicals, linear C12 / 14 higher alcohol (with 12 carbon atoms) For example, those having 68 to 74% by mass and those having 14 carbon atoms are 24 to 30% by mass)), Conol 1495 (trade name, manufactured by Shin Nippon Chemical Co., Ltd., linear C14 higher alcohol (myristyl alcohol)), and the like.
The content of the component (D) in the detergent composition is preferably from 0.1% by weight to less than 2% by weight, more preferably from 0.2% by weight to 1.5% by weight, based on the total amount of the detergent composition. Preferably, 0.3 mass% or more and 0.7 mass% or less are more preferable. When the ratio is 0.1% by mass or more, the effect of the component (D) is sufficiently obtained, and when it is 2% by mass or more, the rinsing property may be insufficient.
The ratio (mass ratio) of component (D) / surfactant (A + E + F) is preferably in the range of 1/15 to 1/100, more preferably 1/40 to 1/30. Within this range, the foam increasing effect and the cleaning effect are excellent.

<(E) component: anionic surfactant other than (A) component>
The detergent composition of the present invention may contain a component (E) (anionic surfactant other than the component (A)) as necessary.
The anionic surfactant other than the component (A) is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used.
Examples of the anionic surfactant include the following.
(1) A linear or branched alkylbenzenesulfonic acid (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms and a salt thereof. From the viewpoint of cleaning performance, the alkyl group preferably has 10 to 14 carbon atoms.
(2) Alkanesulfonic acid having 10 to 20 carbon atoms and salt thereof.
(3) C-C20 alpha olefin sulfonic acid (AOS) and its salt.
(4) C10-20 alkyl sulfate or alkenyl sulfate (AS) and salts thereof. From the viewpoints of cleaning performance and foam performance, the alkyl group or alkenyl group preferably has 10 to 14 carbon atoms.
(5) Any one 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) with an average of 0.5 Alkyl (or alkenyl) ether sulfuric acid (AES) having a C10-20 linear or branched alkyl (or alkenyl) group to which 10 mol has been added and a salt thereof.
(6) Any one 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) on average 3 to 30 Alkyl (or alkenyl) phenyl ether sulfuric acid having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by mole and its salt.
(7) Any one 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) with an average of 0.5 10. Alkyl (or alkenyl) ether carboxylic acid having a C10-20 linear or branched alkyl (or alkenyl) group to which 10 mol has been added and a salt thereof.
(8) Alkyl polyhydric alcohol ether sulfuric acid such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms and salts thereof.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphoric acid and salts thereof.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphoric acid and salts thereof.
(11) A higher fatty acid having 10 to 20 carbon atoms and a salt thereof (soap).

The form of the salt in these surfactants is not particularly limited, and examples thereof include alkali metal salts, alkaline earth metal salts, protonated amine salts, and ammonium salts. Examples of the alkali metal, alkaline earth metal, and protonated amine are the same as those exemplified as M in the formula (a1). Of these, alkali metal salts are preferred.
As the component (E), any one type may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of improving foam performance and formulation, it is preferable to include at least one selected from LAS and AS, and more preferable to include LAS.
The content of the component (E) in the detergent composition is not particularly limited as long as it does not impair the effects of the present invention. However, from the viewpoint of cleaning performance and foam performance, the component (A) / (E) The amount that the ratio (mass ratio) of the components is within the range of 10/0 to 1/9 is preferable. The ratio is more preferably 8/2 to 2/8, and further preferably 5/5 to 1/2.
The total amount of the component (A) and the component (E) in the detergent composition is 2.5% by mass or more, preferably 2.5% by mass or more and 45% by mass or less, based on the total amount of the detergent composition. 3.0 mass% or more and 42 mass% or less are more preferable, and 5 mass% or more and 40 mass% or less are more preferable. If the ratio is less than 2.5% by mass, the cleaning power may be insufficient. When the ratio is more than 45% by mass, the foam performance or the rinsing property may be insufficient.

<(F) component: surfactant other than anionic surfactant>
The detergent composition of the present invention may contain a component (F) (a surfactant other than an anionic surfactant) as necessary. (F) It does not specifically limit as a component, It can select suitably from well-known surfactants, such as a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

[Nonionic surfactant]
The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used.
Examples of nonionic surfactants include the following.
(1) An average of 3 to 30 moles, preferably 4 to 20 moles, more preferably 5 to 17 moles of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether.
Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
(9) Fatty acid alkanolamide.
(10) Polyoxyethylene alkylamine.
(11) Alkyl glycoside.
(12) Alkylamine oxide.

Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the following general formula (3-1).
R ⁹ CO (OA) _n OR ¹⁰ (3-1)
In formula (3-1), R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
OA represents an alkylene oxide addition unit having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and ethylene oxide, propylene oxide, and the like are preferable. When n is 2 or more, two or more OA in the formula may be the same or different.
n shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is 5-20.
R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent.

These nonionic surfactants may be used alone or in combination of two or more. Among these, from the viewpoints of detergency and manufacturability, it is preferable to include at least one selected from (1) polyoxyalkylene alkyl (or alkenyl) ethers and (3) fatty acid alkyl ester alkoxylates. Among them, preferred are polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester ethoxylate in which ethylene oxide is added to fatty acid methyl ester. And fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester.
The melting point of the nonionic surfactant is preferably 50 ° C. or lower, and more preferably 40 ° C. or lower.
The melting point here is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.
Moreover, 7-16 are preferable and, as for HLB of nonionic surfactant, 8-14 are more preferable.
HLB is a value determined by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by "New Edition Surfactant Handbook", Kogyoshosho Co., Ltd., 1991, page 234).

[Cationic surfactant]
The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used.
As the cationic surfactant, for example, a mono, di, or trialkyl cation having 1 to 3 long chain (preferably 8 or more carbon atoms) hydrocarbon groups can be used. In particular, a cationic surfactant containing 1 to 2 ester groups and 1 to 2 long-chain hydrocarbon groups in the molecule is preferable.
Specific examples of the cationic surfactant include mono long-chain alkyltrimethylammonium chloride containing one long-chain alkyl group or alkenyl group having 8 to 22 carbon atoms, two long-chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms. Di-long-chain alkyldimethylammonium chloride containing three, tri-long-chain alkylmethylammonium chloride containing three long-chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms, 1 long-chain alkyl group or alkenyl group having 8 to 22 carbon atoms N-acyloxyethyl-N, N-dimethyl-N-hydroxyethylammonium chloride and N, N-diacyloxyethyl-N, N- containing two long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms Dimethylammonium chloride or the like can be used.

[Amphoteric surfactant]
The amphoteric surfactant is not particularly limited as long as it is conventionally used in detergents, and various amphoteric surfactants can be used.
As the amphoteric surfactant, for example, sulfobetaine having one or two long chain (preferably having 8 or more carbon atoms) hydrocarbon groups and carboxybetaine can be used.
The long chain hydrocarbon group may include an ester group, an amide group, or an ether group. Further, the long chain hydrocarbon group may be a single chain type or a two chain type. Further, the ratio of the saturated / unsaturated type in the long chain hydrocarbon group, the distribution of the carbon chain length, the ratio of the cis isomer / trans isomer of the unsaturated group, etc. are not particularly limited. Further, the long chain hydrocarbon group may be derived from a fatty acid or a fatty acid methyl ester which is a raw material for producing the above-mentioned cationic surfactant. Specific examples of amphoteric surfactants include betaines such as N, N-diacyloxyethyl-N-methylammonioethyl sulfate and N, N-diacyloxyethyl-N-methylammonioethylcarboxylate; N-acyloxy Ethyl-N-hydroxyethyl-N-methylammoniobetaines; N-acylamidopropyl-N, N-dimethylammoniobetaines; and N-acylamidopropyl-N, N′-dimethyl-N′-β- And hydroxypropylammoniobetaine.
The amphoteric surfactant may contain an aminobetaine such as a compound whose nitrogen atom is not quaternized, a raw material alkanolamine, a neutralized product thereof, or a quaternized product thereof.

As the component (F), any one type may be used alone, or two or more types may be used in combination.
Among these, since it is excellent in cleaning performance, it is preferable to contain a nonionic surfactant as the component (F).
The content of the component (F) in the detergent composition may be appropriately set in consideration of the content of the component (A) and the component (E). The total amount of the component (A), the component (E) and the component (F) is preferably 5% by mass to 45% by mass with respect to the total amount in the detergent composition, preferably 6% by mass to 43%. The amount of mass% or less is more preferable, and the amount of 7 mass% or more and 42 mass% or less is more preferable. When the ratio is 5% by mass or more, the detergency is improved, and when it exceeds 45% by mass, the rinsing property is deteriorated.
The blending ratio (mass ratio) of the component (F) with respect to the sum of the component (A) and the component (E) is the sum of the component (A) and the component (E) / (F) component = 10/0 to 4/1. It is more preferable that it is in the range of 50/1 to 4/1 from the viewpoint of foam performance.

<Other optional components>
The detergent composition of the present invention may contain components other than the above components (A) to (F) as long as the effects of the present invention are not impaired. The other components are not particularly limited, and can be appropriately selected as necessary from various additives conventionally blended in detergent compositions. Examples of such additives include detergency builders, fragrances, dyes, fluorescent brighteners, enzymes, enzyme stabilizers, other polymers, anti-caking agents, reducing agents, metal ion scavengers, pH adjusters, etc. Examples include bleaching agents, bleach activators, bleaching catalysts, UV absorbers, and clay minerals. Specific examples thereof are shown below.

[Detergency Builder]
Detergency builders are roughly classified into alkaline agents, other inorganic builders, and organic builders. Any one of these may be used alone, or two or more may be used in appropriate combination.
In the present specification and claims, the “alkali agent” means a component having an action of raising the pH of a detergent solution and a constant pH buffering action.
Examples of the alkali agent include alkali metal carbonates or bicarbonates, alkali metal silicates, and amines.
Specific examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium potassium carbonate, sodium sesquicarbonate, and sodium bicarbonate.
Specific examples of the alkali metal bicarbonate include sodium bicarbonate and potassium bicarbonate.
Specific examples of the alkali metal silicate include sodium silicate, layered sodium silicate, sodium metasilicate, and sodium orthosilicate.
Specific examples of the amine include monoethanolamine, diethanolamine, and triethanolamine.
An alkali agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
However, in the present invention, since alkali metal carbonates and silicates adversely affect foam performance, the smaller the amount of alkali agent selected from alkali metal carbonates and silicates, the more preferable, the alkali It is particularly preferable that no agent is contained.

The inorganic builder is not particularly limited as long as it is conventionally used in a detergent composition for clothing, for example, amorphous aluminosilicate; orthophosphate, pyrophosphate, tripolyphosphate And phosphates such as salts, metaphosphates, hexametaphosphates, phytates; and crystalline silicates and complexes of carbonates and amorphous alkali metal silicates.
The form of the salt is not particularly limited, and examples thereof include alkali metal salts, alkaline earth metal salts, protonated amine salts, and ammonium salts. Examples of the alkali metal, alkaline earth metal, and protonated amine are the same as those exemplified as M in the formula (a1). Of these, alkali metal salts are preferred.
These inorganic builders can be used alone or in combination of two or more.

Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyimino Hydroxyaminocarboxylates such as disuccinate, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, and gluconate; pyromellitic acid Cyclocarboxylates such as salts, benzopolycarboxylates, and cyclopentanetetracarboxylates; ethers such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, and tartaric acid mono- or disuccinate Carboxylate; polymers having a well weight-average molecular weight of 10,000 or less of the carboxy group. As said polymer, the thing similar to the said (A) component is mentioned except the weight average molecular weight being 10,000 or less.
These organic builders can be used alone or in combination of two or more.

As the detergency builder, the inorganic builder is particularly preferable. Among them, phosphate is preferable and tripolyphosphate is particularly preferable from the viewpoint of cleaning performance.
Detergent composition, the content of tripolyphosphate salt, the (C) the ratio of the component (mass ratio), the amount to be within the scope of component (C) / tripolyphosphate = 19 / 1-1 / 19 preferable. The ratio is preferably 3/1 to 1/9, and more preferably 13/7 to 3/17.
The content of the detergency builder in the detergent composition is preferably 5% by mass or more and 25% by mass or less, and more preferably 6% by mass or more and 20% by mass or less with respect to the total amount in the detergent composition. When the content of the detergency builder is not less than the lower limit of the above range, foam performance and the like are improved. Moreover, the solubility to the water of a detergent composition deteriorates that it is more than an upper limit.

[Fragrance]
The fragrance is not particularly limited, and for example, fragrance components and fragrance compositions described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
In addition, a fragrance | flavor composition is a mixture which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.
A fragrance | flavor can be used individually by 1 type or in combination of 2 or more types as appropriate.
When mix | blending a fragrance | flavor in a cleaning composition, 0.001-10 mass% is preferable with respect to the whole quantity of a cleaning composition, and, as for the compounding quantity, 0.01-5 mass% is more preferable.

[Dye]
Various dyes can be blended in order to improve the appearance of the detergent composition.
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, pigments are preferred, and compounds having oxidation resistance such as oxides are particularly preferred. Examples of such a compound include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.
As the dye, one kind can be used alone, or two or more kinds can be used in appropriate combination.

[Fluorescent brightener]
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Examples thereof include fluorescent whitening agents such as phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.
Examples of commercially available optical brighteners include Whiteex (registered trademark) SA, Whitetex (registered trademark) SKC (trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl (registered trademark) AMS-GX, and Chino Pearl (registered). Trademarks) DBS-X, Chino Pearl (registered trademark) CBS-X (trade name; manufactured by Ciba Specialty Chemicals), Lemonite CBUS-3B (trade name, manufactured by Khyati Chemicals), and the like. Among these, Tinopearl (registered trademark) CBS-X and Tinopearl (registered trademark) AMS-GX are preferable.
As the fluorescent brightening agent, one kind can be used alone, or two or more kinds can be used in appropriate combination.
The compounding amount of the optical brightener is preferably 0.001% by mass or more and 1% by mass or less with respect to the total amount of the cleaning composition.

[enzyme]
The enzymes are classified according to the reactivity of the enzymes, and include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.
Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, and aspergillopeptidase A or B. As commercial products of protease, sabinase (registered trademark), alcalase (registered trademark), cannase (registered trademark), everase (registered trademark), deozyme (registered trademark) (above, trade name: manufactured by Novozymes); API21 (product) Name: Showa Denko Co., Ltd.); Maxacal, Maxapem (above, trade name: Genencor Corporation); Protease K-14 or K-16 (Protease described in JP-A-5-25492) .
Examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Examples of the lipase include commercially available lipases such as Lipolase (registered trademark), Lipex (registered trademark) (trade name; manufactured by Novozymes), Liposome (trade name; manufactured by Showa Denko KK), and the like.
As cellulase, cellzyme (trade name; manufactured by 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, and alkaline cellulase E-III (and above) And cellulase described in JP-A-63-264699).
Examples of amylase include commercially available Steinzyme (registered trademark), Termamyl (registered trademark), Duramil (registered trademark) (trade name; manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).
In the detergent composition, the enzyme content is preferably 0.05% by mass or more and 5% by mass or less based on the total amount of the detergent composition.

[Enzyme stabilizer]
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound, etc. can be mix | blended, for example. Of these, sodium tetraborate and calcium chloride are preferred.
As an enzyme stabilizer, 1 type can be used individually or in combination of 2 or more types as appropriate.
The compounding amount of the enzyme stabilizer is preferably 0.05% by mass or more and 2% by mass or less with respect to the total amount of the detergent composition.

[Other polymers]
As a binder or a powder physical agent when densifying the surfactant-containing particles, polyethylene glycol, polyvinyl alcohol, or the like can be blended in order to impart a re-contamination preventing effect to hydrophobic fine particles.
Moreover, as a soil release agent, a copolymer or terpolymer of terephthalic acid and ethylene glycol and / or propylene glycol units can be blended.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above, polyethylene glycol is preferable. The average molecular weight is preferably 200 to 200,000, more preferably 1500 to 7000. Here, the average molecular weight of polyethylene glycol is a value measured by GPC.
The said polymers can be used individually by 1 type or in combination of 2 or more types as appropriate.
When the polymers are blended in the cleaning composition, the blending amount is preferably 0.05% by mass or more and 5% by mass or less with respect to the total amount of the cleaning composition.

[Anti-caking agent]
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, and magnesium oxide.
As a caking inhibitor, 1 type can be used individually or in combination of 2 or more types as appropriate.

[Reducing agent]
Examples of the reducing agent include sodium sulfite and potassium sulfite.

[Metal ion scavenger]
The metal ion scavenger captures trace metal ions and the like in tap water, and has an effect of suppressing adsorption of metal ions to fibers (objects to be cleaned).
Examples of metal ion scavengers that can be incorporated into the detergent composition include aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and glycolethylenediaminehexaacetic acid, as well as those included in the detergency builder; 1-hydroxy Ethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1, 2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylene Phosphonic acid) and diethylenetriaminepenta Methylene phosphonic acid) organic phosphonic acid derivative or a salt thereof and the like; diglycolic acid, tartaric acid, oxalic acid, and organic acids or salts thereof such as gluconic acid.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
It is necessary to consider the content of the metal ion scavenger in the detergent composition as long as the performance is not impaired.

[PH adjuster]
As will be described later, the detergent composition of the present invention has a pH at 25 ° C. of 5.5 to 9.4 when it is an aqueous solution or aqueous dispersion having a solid concentration of 1% by mass. In order to obtain the above value, a pH adjusting agent may be blended as necessary. However, in the case where the pH becomes a desired value with only the above-described components, the pH adjuster is not necessarily blended.
Examples of pH adjusters include alkaline agents (eg, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine) listed as the detergency builder, and other alkaline compounds such as sodium hydroxide and potassium hydroxide; An ion scavenger, an alkali metal dihydrogen phosphate such as potassium dihydrogen phosphate, an acidic compound such as lactic acid, succinic acid, malic acid, gluconic acid, sulfuric acid, hydrochloric acid, citric acid, and linear alkylbenzene sulfonic acid; It is done. Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing. These pH adjusters can be used singly or in appropriate combination of two or more.

<PH>
The detergent composition of the present invention has a 1% by weight aqueous solution or aqueous dispersion (1 g of the detergent composition dissolved or dispersed in 99 g of water) having a pH of 5.5 to 9.4 at 25 ° C. Yes, 6.0 to 9.2 is preferable, and 6.5 to 9.1 is more preferable. When the pH is 5.5 or more, the detergency is improved. Moreover, foam performance becomes favorable because it is 9.4 or less, and the washing | cleaning liquid at the time of hand-washing washing becomes a mild thing on a hand skin.

In the present invention, “a 1% by mass aqueous solution or aqueous dispersion (1 g of the detergent composition dissolved or dispersed in 99 g of water) having a pH at 25 ° C. of 5.5 to 9.4” is 25 It means that the pH of a 1% by mass aqueous solution or aqueous dispersion (1 g of the detergent composition dissolved or dispersed in 99 g of water) is within the above range when the temperature at 0 ° C. is used as a reference. That is, when the aqueous solution or aqueous dispersion is prepared at a temperature other than 25 ° C., the pH range is corrected according to the temperature. The aqueous solution or aqueous dispersion in the pH range thus corrected is also included in the scope of the present invention.
In other words, even if the pH at a certain temperature is not in the range of 5.5 to 9.4, the pH is corrected to the range of 5.5 to 9.4 when 25 ° C. is used as a reference. Aqueous solutions or dispersions are included within the scope of the present invention.

The form of the detergent composition of the present invention may be a solid such as granules (powder and granules), tablets, briquettes, sheets or bars, or may be a liquid. Preferably it is solid, More preferably, it is granular.
When the form of the detergent composition of the present invention is granular, the average particle size of the detergent composition is preferably 200 to 1500 μm, more preferably 300 to 800 μm, and even more preferably 400 to 700 μm. . When the average particle size is at least the lower limit value, powdering during use is suppressed, and when it is at most the upper limit value, the solubility in water is good.
Moreover, 0.3-1.5 g / cm < ³ > is preferable and the bulk density of the said detergent composition has more preferable 0.4-1.0 g / cm < ³ >. The bulk density is a value measured according to JIS 3362: 1998.
In the case of a granular detergent composition, the water content is preferably less than 10.0% by mass.

The manufacturing method of the detergent composition of this invention is not specifically limited, According to the form of the detergent composition to be manufactured, it can manufacture according to a conventional method.
For example, as a manufacturing method in the case where the detergent composition is granular, for example, a slurry containing a detergent raw material is prepared and spray-dried; Extrusion / pulverization), stirring granulation method, rolling granulation method, etc .; and powdered detergent raw material mechanically mixed (powder mixing); It is done. Any one of these methods may be used alone, or two or more thereof may be appropriately combined.
From the viewpoint of production efficiency, it is preferable that at least the component (A) among the components blended in the detergent composition is powdered alone and then mixed with other powdery detergent raw materials.
As an example of a preferable manufacturing method, for example,
(A) A part or all of the detergent raw material other than the component is uniformly mixed with water to prepare a slurry, spray-dried particles obtained by spray-drying the slurry, and the powdery component (A) , A method of powder-mixing the remaining detergent raw materials (in powder form);
(A) Part or all of the components other than the component are mixed and granulated by stirring granulation method, crushing granulation method (kneading / extrusion / pulverization), rolling granulation method, etc. A method of powder-mixing the granule, the powdery component (A), and the remaining raw material (powder-like material); how to;
Etc.
In each method, after mixing the powder, a step of coating the surface of the particles with the component (C), a nonionic surfactant, a fragrance, a pigment, or the like may be performed.
When the detergent composition is a tablet, the granular detergent composition obtained as described above can be produced by tableting using a tableting machine.
When the detergent composition is a liquid, it can be prepared by mixing the above-described components together with water as necessary.

The detergent composition of the present invention exhibits excellent detergency and foam performance even when washing with high-hardness water. Therefore, it is useful for washing with high hardness water (for example, 10 ° DH). Further, since it has high foam performance, it is useful for hand-washing laundry. In addition, since the pH of the 1% aqueous solution or the aqueous dispersion is within the above range, the washing liquid when performing hand-washing is mild to the hand skin, which is also useful for hand-washing.
By combining the (A) component and the (B) component, the reason why the high cleaning performance and foam performance are exhibited especially under high hardness is that the (A) component does not easily precipitate even under high hardness and acts as an activator. Therefore, it is conceivable to have high cleaning performance, to stabilize the foam film in which the component (B) is produced, and to improve the foam sustainability.
Furthermore, it is thought that (C) component improves foam persistence by the foam stabilization effect by reducing the drainage rate of the liquid which exists in a foam film.
Moreover, it is thought that (D) component improves foaming power by stabilization of a foam film.
Moreover, by using together with (E) component, such as LAS and AS, the favorable foaming at the time of hand-washing and cloth slipperiness are expressed.

The object to be washed with the detergent composition of the present invention may be the same as that generally used as the object to be washed with the detergent composition (to be washed), such as clothes, cloths, sheets, and curtains. Examples include textile products.
The washing method using the detergent composition of the present invention is not particularly limited, and may be the same as a known washing method. As a specific example, there is a method in which a detergent composition is poured into water and the laundry is washed in the water (laundry liquid). The input amount at this time varies depending on the blending amount of the component (A) and other surfactants. Usually, the concentration of the detergent composition in the washing liquid is 0.1 to 10% by mass in the case of hand-washing laundry. (More preferably 0.2 to 1% by mass), and in the case of using a washing machine, 0.01 to 2% by mass (more preferably 0.02 to 1% by mass) is preferable. The laundry to be washed may be washing by hand or by a washing machine (such as a two-tank washing machine, a fully automatic washing machine, and a drum washing machine). In view of this, for example, hand-washing in which water is poured into a bag and the detergent composition is dissolved to wash clothes is preferable.

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
In this example, “%” is “% by mass” unless otherwise specified.
The measurement methods and raw materials used in the following examples are shown below.

[Measuring method]
[PH]
pH measurement measured pH of various detergent composition 1% solutions (25 degreeC) using the pH meter (HM-30S) by Toa DKK Corporation based on JISZ8802-1984.
(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 using polyethylene glycol as a standard substance.

[Measurement method of average particle diameter]
First, the measurement object (sample) was classified using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and a 100 g sample is put on the top 1680 μm sieve, and a lid is put on a low-tap sieve shaker (Iida Co., Ltd.). (Manufactured by Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes under atmospheric conditions of a temperature of 25 ° C. and a relative humidity of 40%, and then the samples remaining on the respective sieves and trays Was collected for each sieve mesh.
By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) , 350-500 μm (350 μm.on), 250-350 μm (250 μm.on), 149-250 μm (149 μm.on), and saucer-149 μm (149 μm.pass). %) Was calculated.
Next, the opening of the first sieve with a calculated mass frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the integration of the mass frequency from the tray to the sieve of a μm is c %, And the mass frequency on an a μm sieve was defined as d%, and the average particle diameter (mass 50% diameter) was determined by the following formula.

[Method for measuring moisture content]
The water content was measured using Kett (MOISTURE PETERMINATION BALANCE FD-600). The sample amount was 5 g, and the change in weight after heating at 140 ° C. for 20 minutes was taken as the amount of water.

[material]
(Raw material of α-sulfo fatty acid methyl ester (salt) (hereinafter sometimes referred to as MES))
-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 moisture 500 ppm or less, manufactured by Sumitomo Chemical Co., Ltd.
-35% hydrogen peroxide: 35% industrial hydrogen peroxide, manufactured by Mitsubishi Gas Chemical Co., Ltd.
-Sodium hydroxide: Caustic soda, industrial grade, manufactured by Daiso Corporation.

(Anionic surfactant (excluding component (A)))
-Sodium lauryl sulfate ester (hereinafter sometimes referred to as AS-Na): Trade name "SLS", manufactured by PEPMACO MANUFACTURING CORPORATION.
Sodium linear alkylbenzene sulfonate (hereinafter also referred to as LAS-Na): Linear alkyl (carbon number 10 to 14) benzene sulfonic acid (hereinafter also referred to as LAS-H) (trade name “Laipon”) LH-200 "(manufactured by Lion Corporation, pure content 96%) neutralized with NaOH at the time of slurry preparation for spray drying or granulation. The compounding quantity in Tables 1-3 shows the mass% as LAS-Na.

(Nonionic surfactant)
Polyoxyethylene alkyl ether (hereinafter also referred to as AE): an average of 9 moles of ethylene oxide adduct of an alcohol having 12 to 16 carbon atoms (trade name “CO-1214”, manufactured by P & G Chemicals) ( 90% pure, manufactured by Lion Corporation).

(Zeolite and other detergency builders)
Zeolite: Type A zeolite, trade name “Zeolite Na-4A”, manufactured by THAI SILICATE CHEMICALS.
-Sodium tripolyphosphate (hereinafter sometimes referred to as STPP): manufactured by Central Glass Co., Ltd.
・ Sodium carbonate: granular ash, manufactured by Asahi Glass Co., Ltd.
A mixture of sodium silicate: sodium silicate No. 1 / sodium silicate No. 2 in a mass ratio of 46:54, manufactured by Nippon Chemical Industry Co., Ltd.
-Sodium sulfate: neutral anhydrous sodium sulfate, manufactured by Nippon Chemical Industry Co., Ltd.

(Polymer compound having a carboxy group)
High molecular polymer 1: Powdered acrylic acid / maleic acid copolymer sodium salt, trade name “Socaran (registered trademark) CP-7 Granules NL”, weight average molecular weight 50000, manufactured by BASF Japan Ltd.
High polymer 2: Sodium salt of acrylic acid / maleic acid copolymer, trade name “AQUALIC (registered trademark) TL-500”, weight average molecular weight 15000, manufactured by Nippon Shokubai Co., Ltd.
High molecular polymer 3: sodium polyacrylate, trade name “Socaran (registered trademark) PA40”, weight average molecular weight 15000, manufactured by BASF Japan Ltd.
High polymer 4: Sodium polyacrylate, trade name “Socaran (registered trademark) PA25”, weight average molecular weight 4000, manufactured by BASF Japan Ltd.
High molecular polymer 5: sodium carboxymethyl cellulose, trade name “CMC Daicel”, product number: 1105, weight average molecular weight 60000, etherification degree 0.6 to 0.8, manufactured by Daicel Chemical Industries, Ltd.

(Other ingredients)
Higher alcohol: Alcohol mixture having an alkyl group having 12 to 16 carbon atoms, trade name “CO-1214”, manufactured by P & G Chemicals).
CBS: fluorescent brightener, trade name “Tinopearl (registered trademark) CBS-X”, manufactured by Ciba Specialty Chemicals.
AMS: fluorescent whitening agent, trade name “Tinopearl (registered trademark) AMS-GX”, manufactured by Ciba Specialty Chemicals.
Enzyme: Protease (Sabinase (registered trademark) 12T) / Amylase (Stainzyme (registered trademark) 12T) / Lipase (LIPEX (registered trademark) 100T) / Cellulase (Cell Clean 4500T) / Glucosidase (Manaway 4.0T) (or more) , All manufactured by Novozymes Japan Ltd.) = 6/2/2/1/4 (mass ratio).
Fragrance: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
-Dye: Ultramarine Blue, ultramarine, manufactured by ultramarine, Dainichi Seika Kogyo Co., Ltd.

<Production Example 1: Production of MES detergent particles>
[1. Production of paste-like MES]
A 1 kL reactor equipped with a stirrer was mixed with a fatty acid methyl ester mixture (methyl palmitate (trade name “Pastel M-16”, manufactured by Lion Corporation), methyl stearate (trade name “Pastel M-180”, Lion Corporation) (Mixed in advance) was added in an amount of 9: 1, and 330 kg of the mixture was added, and while stirring, 5% by mass of anhydrous sodium sulfate as a coloring inhibitor was added to the fatty acid methyl ester mixture. Then, while continuing stirring, 110 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas at a reaction temperature of 80 ° C. (1.2 times mol with respect to the fatty acid methyl ester mixture) was bubbled. Then, it was blown at a constant speed over 3 hours, and then aging was performed for 30 minutes while maintaining at 80 ° C.
Thereafter, 14 kg of methanol was supplied as a lower alcohol to carry out esterification. The esterification temperature was 80 ° C. and the aging time was 30 minutes.
Subsequently, the esterified product extracted from the reaction apparatus was continuously neutralized by adding an equivalent amount of aqueous sodium hydroxide solution using a line mixer.
Next, this neutralized product was injected into the bleaching agent mixing line, and 35% hydrogen peroxide solution was converted into a pure component, and an anionic surfactant concentration (α-sulfo fatty acid methyl ester sodium salt (MES-Na) and α-sulfo was added). 1% is supplied to and mixed with disodium fatty acid disodium salt (di-Na salt), and bleaching is performed while maintaining at 80 ° C. to obtain a pasty MES.

[2. Concentration of MES paste]
A vacuum thin film evaporator (heat transfer surface: 0.5 m ² , inner diameter of cylindrical processing section: 205 mm) rotating the MES paste obtained above at a rotation speed of 1,060 rpm and a blade tip speed of about 11 m / s. , The clearance between the heat transfer surface and the blade tip as scraping means: 3 mm, introduced to the trade name “Exeva (registered trademark)” manufactured by Shinko Pantech Co., Ltd. at 35 kg / h, and the inner wall heating temperature (heat transfer surface) The temperature was 135 ° C. and the degree of vacuum (pressure in the processing section) was 0.007 to 0.014 MPa.
The resulting concentrate had a temperature of 115 ° C. and a moisture content of 2.5%.

[3. Production of MES solids]
The MES paste obtained by concentration was continuously supplied at 222 kg / h to a double belt type belt cooler (NR3-Lo. Cooler) manufactured by Nippon Belting Co., Ltd., in which the clearance between input pulleys was adjusted to 2 mm, and cooled. At this time, the belt moving speed is 6 m / s, and the flow rate of the cooling water is 1500 L / h on the upper belt side (cooled by flowing down on the back side of the belt in a countercurrent manner), and 1800 L / h on the lower belt side (on the back side of the belt). The cooling water supply temperature was 20 ° C. The surfactant-containing material sheet discharged from the cooling belt was crushed at a rotation speed of 200 rpm with an attached pulverizer installed near the discharge pulley to obtain a flaky MES solid at 25 ° C. .

[4. Production of MES detergent particles]
The obtained flake-like MES solid (temperature is 25 ° C.) from a raw material inlet of a screw extrusion granulator (manufactured by Hosokawa Micron Corporation, Extrude Ohmic EM-6, spindle rotation speed 70 rpm), It was continuously fed at a rate of 100 kg / h. Then, by rotating the screw shaft and rotating the first and second paddles at 100 rpm, the MES solid was kneaded and extruded from the hole of the third orifice plate to obtain a noodle-like MES solid.
After cooling this noodle to 30 ° C. at room temperature, it is added together with zeolite (in the examples and comparative examples described later, in the case of MES detergent particles used in a composition containing no zeolite) and a pulverizer (Okada Seiko Co., Ltd.) Made into a speed mill ND-10, blade rotation speed 840 rpm, screen φ4 mm at a rate of 1 kg / min and crushed to obtain MES detergent particles having an average particle diameter of 500 μm.
The obtained MES detergent particles had the following properties.
When zeolite is blended: MES pure content 86.6%, zeolite 4%, moisture 3.4%, sodium sulfate 2.2%, methyl sulfate 3.8%.
When no zeolite was blended: MES pure 91.1%, moisture 2.5%, sodium sulfate 2.4%, methyl sulfate 4.0%.

<Examples 1 to 14, 16 and Comparative Examples 1 to 4>
A granular detergent composition having the composition (%) shown in Tables 1 and 2 was produced by the following production method A. In Tables 1 and 2, “Bal” of sodium sulfate indicates a balance amount (amount in which the total amount of the granular detergent composition is 100%). Example 8 is a reference example.
[Production method A of granular detergent composition: spray drying]
First, water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C.
Sodium sulfate and fluorescent brightening agent (CBS, AMS) were added thereto and stirred for 10 minutes. Subsequently, anionic surfactants (LAS-Na (LAS-H neutralized with NaOH), AS-Na), detergency builders (STPP, sodium carbonate, and sodium silicate), higher alcohols, and polymers After adding the polymers 1-5, it stirred for 10 minutes and added a part of powder A type zeolite. The slurry was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the obtained slurry for spray drying was 50 ° C. This spray drying slurry was spray dried with a countercurrent spray drying apparatus equipped with a pressure spray nozzle to obtain spray dried particles.
After mixing the obtained spray-dried particles, a part of the powder A-type zeolite, and enzymes (protease, amylase, lipase, cellulase, and glucosidase) with a V blender, and further adding MES detergent particles, While spraying nonionic surfactant (AE) and transferring at a speed of 0.5 m / s on a belt conveyor to color a part of the spray-dried particles (the height of the spray-dried particle layer on the belt conveyor is 30 mm, (Layer width 300 mm) A 20% by mass aqueous dispersion of the dye was sprayed on the surface to obtain a granular detergent composition having a water content of 6%.
A 1% aqueous solution of the obtained granular detergent composition was prepared and its pH was measured. The results are shown in Tables 1-2.

<Example 15, Comparative Example 5>
A granular detergent composition having the composition (%) shown in Table 2 was produced by the following production method B. In Table 2, “Bal” of sodium sulfate indicates a balance amount (amount in which the total amount of the granular detergent composition is 100%).
[Production method B of granular detergent composition: powder blend]
A detergent was produced according to the following procedure according to the composition shown in Table 2 using a Fukae FS-1200 high-speed mixer / granulator.
STPP, sodium sulfate, optical brightener (CBS, and AMS), and a portion of the zeolite were dry blended for 60 seconds with a mixer at a stirrer speed of 100 rpm and a shearer speed of 2000 rpm. Water (corresponding to 0.375% by weight) was added and the mixer was operated for 90 seconds at the same stirrer and shear speed. The temperature was maintained at 50 ° C. or lower with a cooling jacket through which water passed.
Water (equivalent to 1.4% by mass) as a binder, nonionic surfactant (AE), and polymer 1 were added to a mixer and granulated for 180 seconds at a stirrer speed of 100 rpm and a shearing machine speed of 2000 rpm. The temperature was maintained at 50 ° C. or lower by a cooling jacket through which water passed. The product obtained in this step was a granular solid. Stop the mixer shearer, stir the stirrer at 90 rpm for 120 seconds, add the enzyme and MES detergent particles, and then add zeolite (equivalent to 2% by mass) to surface-modify the flavor. Were sprayed to obtain surfactant-containing particles. In order to color a part of the obtained surfactant-containing particles, a granular detergent composition having a water content adjusted to 4% by spraying a 20% by mass aqueous dispersion of the dye in the same manner as in Production Method A Obtained.
A 1% aqueous solution of the obtained granular detergent composition was prepared and its pH was measured. The results are shown in Table 2.
In Example 13 and Comparative Example 4 only, the pH of a 1% aqueous solution of the granular detergent composition is shown in the table by adjusting the amount of sodium hydroxide used as a neutralizing agent when producing the detergent composition. The pH was adjusted.

The following evaluation was performed about the obtained granular detergent composition of Examples 1-16 and Comparative Examples 1-5. The results are also shown in Tables 1-2.
[Evaluation method]
[Evaluation of foaming power during hand washing]
Washing iron (inner diameter 30 cmφ, depth 10 cm) was prepared, and 3 L of water whose hardness and temperature had been adjusted were put therein. The hardness of water is as follows. First, 262.5 g of calcium chloride dihydrate is dissolved in 10 L of ion exchange water to prepare 1000 ° DH hard water, and then diluted with ion exchange water to have the hardness shown in Tables 1 and 2. Adjusted (1 ° DH = 10 mg (calcium oxide) / L (water)). The temperature of the water was 30 ° C.
A predetermined amount of the granular detergent composition (the amount in which the concentration of the granular detergent composition is the amount of detergent used (g / L) shown in Tables 1 and 2) shown in Tables 1 and 2 was added to the water, and stirred manually for 30 seconds. Next, a test cloth impregnated with 0.1% by weight of a fouling oil with the following composition at 0.1% by weight (about 150 g) was placed, and the test cloth was held in both hands and rubbed back and forth 20 times. And hand-washed for 1 minute.
Thereafter, the hand-washed test cloth was squeezed, and the height of foam on the surface of the wash water was measured with a test tube with a marked line. The measurement was performed at three locations, and the average value was defined as the bubble height. The foam height (mm) after washing the first test cloth was taken as the foaming force value, and the foam height of 35 mm or more was judged acceptable.
Moreover, about the measured bubble height, the ratio (The bubble height in any one of Examples 1-16 and Comparative Examples 1-5 / bubble height x 100 of Comparative Example 1) with respect to the bubble height of Comparative Example 1 was calculated. The results are also shown in Tables 1 and 2 as the rate of foam increase (%).

[Evaluation of foam durability during hand-washing]
In the evaluation of the foaming power at the time of washing by hand, the process of washing the test cloth by hand is repeated every time by replacing the test cloth with a new one, and the end point is the time when the foam height after washing is 3 mm. The number of test cloths that could be washed was evaluated as foam persistence. In addition, the foam persistence which can wash 8 or more test cloths was set as the pass.
(Composition of dirt oil)
・ Oleic acid: 45%
・ Triolein: 25%
・ Cholesterol oleate: 19.5%
-Liquid paraffin: 4%
・ Squalene: 4%
・ Cholesterol: 2.5%

[Evaluation of cleaning performance]
Artificial dirt cloth (manufactured by Laundry Science Association) produced by impregnating artificial dirt with oily co-fabricated cloth (unstained cloth) was cut into 5 × 5 cm to make a contaminated cloth. A Terg-O-meter (manufactured by UNITED STATES TESTING) was used as a cleaning tester.
900 mL of washing liquid (temperature 30 degreeC) which is the usage-amount (g / L) and hardness (degree DH) of the detergent which the density | concentration of a granular detergent composition and the hardness of water respectively show in Tables 1-2 is prepared.
The washing liquid, the above-mentioned 10 contaminated cloths, and the washing knitted cloth were placed in a washing tester, and washed at 120 rpm and 30 ° C. for 10 minutes according to the bath ratio of 30 times. Thereafter, it was transferred to a two-tub washing machine (Mitsubishi Electric Corp., product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. .
The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd., and the washing rate (%) was calculated using the following formula.
Washing rate (%) = (K / S of contaminated cloth before washing−K / S of contaminated cloth after washing) / (K / S of contaminated cloth before washing−K / S of unstained cloth) × 100
[Wherein, K / S = (1−R / 100) ² / (2R / 100), and R is the reflectance (%). ]
The washing rate (%) was calculated for 10 soiled cloths, and a detergent composition with an average value exceeding 75% was regarded as acceptable.

As shown in Tables 1-2, the granular detergent composition of Examples 1-16 is a pass line (foaming power (foam height) of 35 mm or more, in all evaluations of foaming power, foam durability, and cleaning performance, The bubble persistence was 8 sheets or more and the washing rate was 75% or more). In particular, Example 1 in which zeolite was blended had higher foaming power, foam sustainability and cleaning performance than Example 3 having the same composition except that no zeolite was blended. Similar results were confirmed in the comparison between Examples 4 and 5. Moreover, Example 10 which mix | blended the higher alcohol improved foaming power compared with Example 1 of the same composition except it.
On the other hand, Comparative Examples 1 and 2 in which the pH of the 1% aqueous solution was 11.1 and 10.9, Comparative Example 3 in which the polymer polymer 4 having a weight average molecular weight of 4000 was blended, and the blending amount of the polymer polymer 1 was 5 masses, respectively. % Comparative Example 5 had good cleaning performance but failed foaming ability and foam persistence. In Comparative Example 4 in which the pH of the 1% aqueous solution was 4.8, all evaluations of foaming power, foam persistence, and cleaning performance were unacceptable.

<Examples 17 to 23, Comparative Examples 6 to 8>
A granular detergent composition having the composition (%) shown in Table 3 was produced by the following production method C. In Table 3, “Bal” of sodium sulfate indicates a balance amount (amount in which the total amount of the granular detergent composition is 100%).
[Production method C of granular detergent composition: stirring granulation]
LAS-Na, STPP, sodium sulfate, fluorescent whitening agent, sodium silicate, higher alcohol, polymer polymers 1 to 3 and 5 and a slurry having a water content of 38% by mass in which a part of zeolite is dissolved or dispersed in water. After the preparation, spray-dried particles were obtained by spray-drying using a countercurrent spray-drying tower at a hot air temperature of 300 ° C.
The obtained spray-dried particles were put into a Ladige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume), and the main shaft 200 rpm The stirring of the chopper at 200 rpm was started. Nonionic surfactant (AE) was added to the mixture over 2 minutes, and after stirring for 5 minutes, a part of powder A-type zeolite (amount corresponding to 1% by mass) was added and stirred for 2 minutes. Activator-containing particles were obtained.
The obtained surfactant-containing particles, a part of the powder A-type zeolite (amount corresponding to 2% by mass), the enzyme, and the MES detergent particles are mixed with a V blender, and a fragrance is sprayed. In order to color part of the activator-containing particles, a 20% by mass aqueous dispersion of the dye was sprayed in the same manner as in Production Method A to obtain a granular detergent composition having a moisture content set to 7%.
A 1% aqueous solution of the obtained granular detergent composition was prepared and its pH was measured. The results are shown in Table 3.
The obtained granular detergent composition was evaluated in the same manner as in Example 1 (foaming power, foam sustainability, and cleaning performance). However, for the foam increase rate (%) in the foaming power evaluation, the ratio of the comparative example 6 to the foam height was obtained instead of the comparative example 1. The results are also shown in Table 3.

As shown in Table 3, in the granular detergent compositions of Examples 17 to 23, the pass line (foaming power (foam height) of 35 mm or more, foam persistence) in all evaluations of foaming power, foam sustainability, and cleaning performance. 8 sheets or more and a cleaning rate of 75% or more). Especially in Example 17 in which zeolite was blended, the foaming power, foam sustainability and cleaning performance were higher than those of Example 18 having the same composition. Moreover, Example 23 which mix | blended the higher alcohol improved foaming power compared with Example 16 of the same composition except it.
On the other hand, Comparative Example 6 in which the pH of the 1% aqueous solution was 10.5 was satisfactory in cleaning performance but failed in both foaming ability and foam persistence. Moreover, the comparative example 7 which did not mix | blend a high molecular polymer failed all evaluation of foaming power, foam persistence, and washing | cleaning performance. Further, Comparative Example 8 in which MES was not blended and LAS-Na was blended instead had good foaming power and foam persistence, but the cleaning performance was unacceptable and high hardness water was used. It was not suitable for washing.

  Since the detergent composition of the present invention exhibits excellent detergency and foam performance even when laundering is performed using high-hardness water, it can be used as a laundry detergent for hand washing.

Claims (8)

A detergent composition comprising:
(A) 2.5 mass% or more and less than 40 mass% of at least one compound selected from α-sulfo fatty acid alkyl ester and a salt thereof, and (B) polyacrylic acid, polymethacrylic acid, polymaleic acid, polyhydroxyacrylic Weight average molecular weight of 12,000 to 100,000, which is at least one selected from acid, polyfumaric acid, acrylic acid-maleic acid copolymer, acrylic acid-acrylic acid amide copolymer, and acrylic acid-allyl alcohol copolymer Containing 0.1% by mass or more and 4% by mass or less of at least one compound selected from the following polymer compounds having a carboxy group and salts thereof;
A detergent composition for hand-washing laundry, wherein the pH at 25 ° C. of a 1% by mass aqueous solution or aqueous dispersion of the detergent composition is from 5.5 to 9.4.   The detergent composition for hand-washing laundry according to claim 1, further comprising (C) 0.5% by mass or more and 30% by mass or less of zeolite.   The detergent composition for hand-washing laundry according to claim 1 or 2, further comprising a tripolyphosphate. Further contains tripolyphosphate,
Wherein (C) mass ratio of the zeolite and the tripolyphosphate ((C) Zeolite / tripolyphosphate) is 19 / 1-1 / 19, the detergent composition for hand-washing of claim 2.   The detergent composition for hand-washing laundry as described in any one of Claims 1-4 which does not contain an alkali metal carbonate and a silicate. The at least one compound selected from the (A) α-sulfo fatty acid alkyl ester and a salt thereof is a compound represented by the following general formula (a1), according to any one of claims 1 to 5. Detergent composition for hand washing laundry.
R ¹ —CH (SO ₃ M) —CO—O—R ² (a1)
[Wherein, R ¹ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, and M is a hydrogen atom or a counter ion. ] The detergent composition for hand-washing laundry according to any one of claims 1 to 6 , which is granular. A laundry method in which the detergent composition for hand-washing and washing according to any one of claims 1 to 7 is poured into water, and the laundry is washed by hand.