WO2011129432A1 - Granulated detergent composition - Google Patents

Abstract

A granulated detergent composition which comprises (A) an a-sulfofatty acid alkyl ester salt represented by general formula (I): R1-CH(SO3M)-COOR2 ·· (I) [wherein R1 is an alkyl or alkenyl group having 8 to 18 carbon atoms; R2 is alkyl; and M is a counter ion], (B) a C10-16 higher alcohol in an amount of 0.1 to less than 2% by mass relative to the total mass of the granulated detergent composition, (C) a phosphorus-based builder, and (D) an alkaline builder, characterized in that the content of granules which have diameters exceeding 710µm and up to 1400µm is 10 to 50% by mass. Even in washing using high-hardness water, the granulated detergent composition exhibits excellent detergency, foam retentivity, and good rinsing properties, and can give good real feelings of detergence.

Description

Granular detergent composition

The present invention relates to a granular detergent composition useful for washing textile products such as clothing, particularly for hand washing.
This application claims priority based on Japanese Patent Application No. 2010-095383 for which it applied to Japan on April 16, 2010, and uses the content here.

The granular detergent composition used for washing clothes and the like is usually mixed with an anionic surfactant as a cleaning component, and a cleaning builder is added for the purpose of improving cleaning power and providing various other performances. Yes. As detergency builders, alkali builders such as sodium carbonate and potassium carbonate, and phosphorus builders such as sodium tripolyphosphate (STPP) are widely used.

Conventionally, linear alkylbenzene sulfonate (LAS) has been widely used as an anionic surfactant used in granular detergent compositions. Recently, α-sulfo fatty acid alkyl ester salts have been used. The α-sulfo fatty acid alkyl ester salt has excellent detergency, and particularly has an advantage of exhibiting high detergency even when hard water is used and having good biodegradability.

The α-sulfo fatty acid alkyl ester salt is generally granulated alone or together with other surfactants to form a surfactant powder, and then blended with other detergent components to form a granular detergent composition. Yes.
For example, Patent Document 1 discloses a detergent composition containing an α-sulfo fatty acid alkyl ester salt, a higher alcohol, and a detergency builder.
Patent Document 2 discloses a granular detergent composition containing an α-sulfo fatty acid alkyl ester salt, a higher alcohol having 6 or more carbon atoms, and an alkali builder.
Patent Document 3 discloses a granular detergent composition containing an α-sulfo fatty acid alkyl ester salt, a higher alcohol, and a detergency builder.

JP 10-500166 gazette JP 2005-239865 A International Publication No. 04/094313 Pamphlet

α-Sulfo fatty acid alkyl ester salts exhibit the above-mentioned advantages, in particular, high detergency even when hard water is used (high water resistance). The use of is expected to expand.
However, the detergent composition containing the α-sulfo fatty acid alkyl ester salt tends to lose the foam, and the foam tends to disappear as compared with other anionic surfactants such as LAS (foam persistence). Low). This foam persistence tends to decrease as the water hardness increases.
The low foam persistence works favorably when washing is performed using a fully automatic washing machine or drum washing machine, but disadvantageously works when washing is done by hand washing. In other words, in the case of hand-washing, especially when washing repeatedly using the same washing liquid, the user tends to judge the detergency based on good foaming and foam persistence. The power may be considered low. For this reason, improvement of foam sustainability is required in such applications.
On the other hand, if the foam persistence of the granular detergent composition is simply improved, there is a problem that many foams remain at the time of rinsing and a lot of time and rinsing water are required for rinsing.
Since the granular detergent compositions of Patent Documents 1 to 3 described above are assumed to be used in a washing machine, they cannot satisfy the foam sustainability required during hand-washing. In addition, the granular detergent composition for hand-washing is required to improve the washing feeling during washing.

Therefore, the present invention has been made in view of the above circumstances, and even when washing is performed using water with high hardness, it exhibits excellent detergency and foam persistence, has good rinsing properties, and It aims at the granular detergent composition from which a favorable washing | cleaning feeling is obtained.

As a result of intensive studies, the inventors have improved the foam persistence of the α-sulfo fatty acid alkyl ester salt by combining a specific higher alcohol, a phosphorus builder and an alkali builder, and have good detergency and rinsing. I found out that it can be compatible with sex. As a result of further studies based on this knowledge, it was found that a good cleaning feeling can be obtained by controlling the particle size of the granular detergent composition, and the present invention has been completed.

That is, the granular detergent composition of the present invention is a granular detergent composition containing the following components (A) to (D), wherein particles having a particle diameter of more than 710 μm and not more than 1400 μm are 10 to 50% by mass. And
Component (A): α-sulfo fatty acid alkyl ester salt represented by the following formula (I):
R ¹ —CH (SO ₃ M) —COOR ² (I)
(In the formula (I), R ¹ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ² is an alkyl group, and M represents a counter ion.)
Component (B): a higher alcohol having 10 to 16 carbon atoms contained in an amount of 0.1% by mass or more and less than 2% by mass with respect to the total mass of the granular detergent composition.
(C) Component: Phosphorus builder.
(D) Component: Alkali builder.
The mass ratio represented by the content of the component (A) / the content of the component (B) is preferably 20 to 100, preferably contains the following component (E), and is for hand-washing laundry. Is more preferable.
Component (E): at least one anionic surfactant selected from linear alkylbenzene sulfonates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, alkyl ether sulfates and alkenyl ether sulfates.

According to the granular detergent composition of the present invention, even when washing is performed using water with high hardness, excellent detergency and foam persistence are exhibited, rinsing properties are good, and a good washing feeling can be obtained. .

(Granular detergent composition)
The granular detergent composition of the present invention contains the components (A) to (D).
Although the particle diameter of a granular detergent composition is not specifically limited, It is preferable that the particle diameter of all the particles shall be the range of more than 45 micrometers and 1400 micrometers or less.

The granular detergent composition contains 10 to 50% by mass of particles having a particle size of more than 710 μm and 1400 μm or less, preferably 25 to 50% by mass of particles having a particle size of more than 710 μm and 1400 μm or less. By including particles having a particle diameter of more than 710 μm and not more than 1400 μm, it is possible to give the user a feeling of cleaning due to the abrasive feel of such particles, the so-called scrubbing feeling. When the particle size in the granular detergent composition is 710 μm or less, it is difficult to feel scrubbing, and when the particle size exceeds 1400 μm, the solubility of the granular detergent composition in water deteriorates, and the granular detergent composition is applied to the laundry. May remain. In addition, when the particle diameter of the granular detergent composition is more than 710 μm and less than 1400 μm, the user hardly feels cleaning, and if it is more than 50% by mass, the granular detergent composition is poured into water. There is a possibility that the solubility becomes poor and the granular detergent composition remains on the laundry.

In the present invention, the particle ratio of the granular detergent composition having a particle diameter of more than 710 μm and 1400 μm or less is, for example, sieve A (opening: 1400 μm), sieve B (opening: 710 μm), sieve C (opening: 45 μm) and tray D can be measured according to JIS K3362.
Specifically, the sieve C, the sieve B, and the sieve A are stacked in this order on the tray D, the sample is placed on the sieve A, and the sieve A is covered with an upper lid to form a sieve set. Crush the granular detergent composition with your hands. Then, the particles on the sieve A and the tray D are removed, and the masses of the particles remaining on the sieve B (particle diameters greater than 710 μm and 1400 μm or less) and the particles remaining on the sieve C (particle diameters greater than 45 μm and less than 710 μm) Can be calculated by the following equation (1).

Particle ratio (mass%) of particles having a particle diameter of more than 710 μm and not more than 1400 μm = {[mass of particles having a particle diameter of more than 710 μm and not more than 1400 μm (g)] ÷ [mass of particles having a particle diameter of more than 710 μm and not more than 1400 μm (g) + particle diameter of more than 45 μm Mass of particles of 710 μm or less (g)]} × 100 (1)

The bulk density of granular detergent compositions, is preferably 0.3 kg / dm ³ or more, more preferably 0.4 ~ 1.2kg / dm ^3, more preferably at 0.5 ~ 1.1kg / dm ³ is there. When the bulk density is 0.3 kg / dm ³ or more, the space (storage location) required for storing the granular detergent composition can be reduced. On the other hand, if it is 1.2 kg / dm ³ or less, the solubility in water will be good.
The bulk density is a value measured according to JIS K3362-1998.

The amount of water in the granular detergent composition is not particularly limited, but is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and still more preferably 6 to 8% by mass from the viewpoint of solubility and storage stability. The moisture content can be determined by measuring the sample with an infrared moisture meter (manufactured by Kett Scientific Laboratory) at a sample surface of 5 g and a sample surface temperature of 130 ° C. for 20 minutes.

The granular detergent composition preferably has a pH (25 ° C.) of 5 to 12 and more preferably 7 to 11.5 when it is made into a 1% by mass aqueous solution or aqueous dispersion. If it is in this pH range, even if it is used for hand-washing washing, rough hand can be suppressed.

<(A) component: α-sulfo fatty acid alkyl ester salt>
Component (A) is an α-sulfo fatty acid alkyl ester salt represented by the following formula (I).

R ¹ —CH (SO ₃ M) —COOR ² (I)
(In the formula (I), R ¹ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ² is an alkyl group, and M represents a counter ion.)

The alkyl group or alkenyl group of R ¹ may be linear or branched, and is preferably linear. R ¹ has 8 to 18 carbon atoms, preferably 14 to 16 carbon atoms. If the carbon number of R ¹ is less than 8 or more than 18, good detergency may not be obtained.
The alkyl group for R ² may be linear or branched, and is preferably linear. R ² preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1. When the number of carbon atoms of R ² is a 6 exceeds, in some cases satisfactory detergency can not be obtained.
Examples of R ² include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable.

The counter ion represented by M may be any one that forms a pair with the anion R ¹ CH (COOR ² ) SO ₃ ^— and electrically neutralizes it to form a water-soluble salt with the anion. For example, cations formed from alkali metals or alkaline earth metals, protonated amines, ammonium ions and the like can be 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 one of primary to tertiary, and preferably has a total carbon number of 1 to 6. 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, triethanolamine and the like.
As M, a cation formed from an alkali metal is preferable. Among them, the alkali metal is more preferably sodium or potassium, and even more preferably sodium.
As the component (A), α-sulfo fatty acid methyl ester sodium salt (MES) in which R ^{2 in the} above formula (I) is a methyl group and M is a sodium cation is preferable.

As the component (A), to the number of carbon atoms of R ¹ may be used the same ones alone, may be used in combination of the carbon number of R ¹ are different suitably 2 or more. Among them, the component (A) has a ratio of [(A) component having 14 carbon atoms of R ¹ ]: [(A) component having 16 carbon atoms of R ¹ ] (mass ratio) of 45:55 to 95: 5. And more preferably 60:40 to 90:10.

The content of the component (A) in the granular detergent composition is preferably 5 to 40% by mass when not used together with the component (E) described later, that is, when the total amount of the anionic surfactant is the component (A). 10 to 20% by mass is more preferable. If it is less than 5% by mass, good detergency may not be obtained, and if it exceeds 40% by mass, the solubility may be insufficient.
When used in combination with the component (E) described later, the content of the component (A) in the granular detergent composition is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. If it is less than 3% by mass, good detergency may not be obtained, and if it exceeds 30% by mass, the rinsing properties may be deteriorated.

As the component (A), a commercially available product may be used, or a component produced by a known production method described in International Publication No. 2004-111166 pamphlet, International Publication No. 2009-054406 pamphlet, or the like 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 to further accelerate 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, 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 before or after the neutralization step. 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 and pulverization as necessary. The pulverization can be carried out by a known granulation method such as a kneading / extrusion granulation method (kneading / extrusion / pulverization), an agitation granulation method, or a rolling granulation method.

In the α-sulfo fatty acid alkyl ester salt obtained by the production method as described above, in addition to the α-sulfo fatty acid alkyl ester salt itself, an α-sulfo fatty acid dialkali salt (R ² in the formula (I) is usually added. Those substituted with a counter ion of M. Hereinafter, sometimes 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 active ingredient (AI) content as the surfactant is the sum of the α-sulfo fatty acid alkyl ester salt (pure component) and the di-salt. Calculated as content.
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.

<(B) component: higher alcohol having 10 to 16 carbon atoms>
Component (B) is a higher alcohol having 10 to 16 carbon atoms. The component (B) is more preferably a higher alcohol having 12 to 14 carbon atoms. The component (B) is determined in consideration of the type of the component (A), particularly the carbon number of R ^{1 in} the formula (I).
Examples of the type of component (B) include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and the like. These can be used alone or in combination of two or more. Among them, it is preferable to set [higher alcohol having 12 carbon atoms] / [higher alcohol having 14 carbon atoms] = 1 to 9 (mass ratio).

In the component (B), the hydrocarbon chain may be linear or branched, and is preferably linear. If the hydrocarbon chain is a straight chain, the foam durability can be further improved.

The content of the component (B) in the granular detergent composition is, for example, preferably 0.1% by mass or more and less than 2% by mass, more preferably 0.1 to 1.5% by mass, and 0.3 to 0.7% by mass. % Is more preferable. When it is less than 0.1% by mass, the foam persistence is insufficient, and when it is 2% by mass or more, the rinsing property is inferior.
In addition, the mass ratio of the component (A) to the component (B) in the granular detergent composition is preferably (A) component content / (B) component content = 13 to 200, more preferably 20 to 100. preferable. When it is less than 13, the rinsing property tends to be inferior, and when it exceeds 200, the foam persistence tends to be lowered. Furthermore, if it is 20-100, it is excellent in both the effect of rinse property and foam persistence.

<(C) component: phosphorus builder>
Component (C) is a phosphorus builder. As the component (C), a conventionally known phosphorus builder can be used. For example, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate can be used. Among them, pyrophosphate and tripolyphosphate are preferable. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, among which alkali metal salts are preferable. Sodium salt is more preferable. That is, as the component (C), STPP and sodium pyrophosphate (TSPP) are preferable.
(C) As a component, the said component can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the component (C) in the granular detergent composition is preferably 3 to 30% by mass, and more preferably 10 to 20% by mass. If it is less than 3% by mass, it is difficult to obtain the cleaning effect of the component (C), and if it exceeds 30% by mass, the particles may remain undissolved.

<(D) component: alkali builder>
(D) A component is an alkali builder. As the component (D), conventionally known alkali builders can be used. Examples thereof include alkali metal carbonates or bicarbonates, alkali metal silicates, and amines.
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium potassium carbonate, and sodium sesquicarbonate.
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, sodium orthosilicate, and the like. As the silicate, Na ₂ O / SiO ₂ (molar ratio) is preferably 1.0 to 4.5, more preferably 1.6 to 4.0, and 2.0 to 3.5. Are more preferred.
Specific examples of the amine include monoethanolamine, diethanolamine, and triethanolamine.
Of these, alkali metal carbonates and alkali metal silicates are preferable, and sodium carbonate and sodium silicate are more preferable from the viewpoint of improving detergency.
(D) As a component, the said component can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the component (D) in the granular detergent composition is preferably 5 to 40% by mass, more preferably 10 to 20% by mass. If it is less than 5% by mass, it is difficult to obtain the cleaning effect of component (D), and if it exceeds 40% by mass, the particles may remain undissolved.

<(E) component: at least one anionic surfactant selected from linear alkylbenzene sulfonate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, alkyl ether sulfate and alkenyl ether sulfate>
Component (E) includes component (E): linear alkylbenzene sulfonate (LAS), alkyl sulfate, alkenyl sulfate (hereinafter, alkyl sulfate and alkenyl sulfate may be collectively referred to as AS), α- It is at least one anionic surfactant selected from olefin sulfonate (AOS), alkyl ether sulfate and alkenyl ether sulfate (hereinafter, alkyl ether sulfate and alkenyl ether sulfate are collectively AES). A granular detergent composition can aim at the further improvement of foam persistence by containing (E) component.

LAS preferably has 8 to 18 carbon atoms in its alkyl group, and more preferably 10 to 14 carbon atoms from the viewpoint of detergency. The alkyl group of LAS may be linear or branched. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, etc. Sodium salt is more preferable.

The alkyl sulfate preferably has 10 to 20 carbon atoms in the alkyl group, and more preferably has 10 to 14 carbon atoms from the viewpoint of detergency. The alkyl group of the alkyl sulfate may be linear or branched. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, etc. Sodium salt is more preferable.
The alkenyl sulfate preferably has 10 to 20 carbon atoms in the alkenyl group, and more preferably has 10 to 14 carbon atoms from the viewpoint of detergency. The alkenyl group of the alkenyl sulfate may be linear or branched. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, etc. Sodium salt is more preferable.

AOS preferably has 10 to 20 carbon atoms. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, etc. Sodium salt is more preferable.

The alkyl ether sulfate is not particularly limited, and is any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) having an average of 0.5 to 10 moles and having a linear or branched alkyl group having 10 to 20 carbon atoms is preferable.
The alkenyl ether sulfate is not particularly limited, but is any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9. 9 to 9.9 / 0.1) having an average of 0.5 to 10 moles and having a linear or branched alkenyl group having 10 to 20 carbon atoms is preferable.

As the component (E), among the above-mentioned components, linear alkylbenzene sulfonate sodium having 10 to 14 carbon atoms or sodium alkyl sulfate having 10 to 14 carbon atoms is preferable.
(E) As a component, the said component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the component (E) in the granular detergent composition can be determined in consideration of the content of the component (A) and the like. For example, the content is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass.

<Optional component>
In the granular detergent composition, a surfactant other than the component (A) and the component (E) (hereinafter referred to as an optional surfactant), the component (C) and the component (D) as long as the effects of the present invention are not impaired. ) Detergency builders (optional detergency builders) other than ingredients, perfumes, dyes, fluorescent brighteners, enzymes, enzyme stabilizers, polymers, anti-caking agents, reducing agents, metal ion scavengers, pH adjusters, bleaching agents , Bleach activators, bleach catalysts, UV absorbers, clay minerals, and the like.

≪Optional surfactant≫
The optional surfactant is not particularly limited, and is an anionic surfactant (optional anionic surfactant) other than the components (A) and (E), a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Is mentioned.
[Arbitrary anionic surfactant]
(1) 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), an average of 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.
(2) 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), an average of 0.5 Alkyl (or alkenyl) ether carboxylic acids and salts thereof having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with ˜10 mol.
(3) Alkyl polyhydric alcohol ether sulfuric acid such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms and salts thereof.
(4) Long chain monoalkyl, dialkyl or sesquialkyl phosphoric acid and salts thereof.
(5) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphoric acid and salts thereof.
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, ammonium salts and the like. Examples of the alkali metal, alkaline earth metal, and protonated amine are the same as those exemplified as M in the formula (I). Of these, alkali metal salts are preferred.
These optional anionic surfactants may be used singly or in appropriate combination of two or more.

[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 is 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 long-chain fatty acid polyoxyalkylene alkyl ester in which an alkylene oxide is added between ester bonds of the 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.
These nonionic surfactants may be used singly or in appropriate combination of two or more.

[Cationic surfactant]
As a cationic surfactant, if it is conventionally used in a detergent, it will not specifically limit, 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 having 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. 1 di-long chain alkyldimethylammonium chloride, 3 long-chain alkylmethylammonium chlorides having 3 to 8 carbon atoms or 3 alkenyl groups, 1 long-chain alkyl group or alkenyl group having 8 to 22 carbons N-acyloxyethyl-N, N-dimethyl-N-hydroxyethylammonium chloride, N, N-diacyloxyethyl-N, N-dimethyl containing two long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms Ammonium chloride and the like can be used.
These cationic surfactants may be used alone or in combination of two or more.

[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 or 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, 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, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxy And propylammoniobetaine.
The amphoteric surfactant may contain an aminobetaine such as a compound in which the nitrogen atom is not quaternized, a raw material alkanolamine, a neutralized product thereof, or a quaternized product thereof.
These amphoteric surfactants may be used singly or in appropriate combination of two or more.

Any one surfactant may be used alone, or two or more surfactants may be used in combination.
The content of the optional surfactant in the granular detergent composition can be appropriately set in consideration of the contents of the component (A) and the component (E). The total amount of the component (A), the component (E) and the optional surfactant is preferably 5 to 40% by mass, more preferably 10 to 30% by mass with respect to the total amount in the granular detergent composition. An amount of 10 to 25% by mass is more preferable. If the content is less than 5% by mass, the detergency may be insufficient, and if it exceeds 40% by mass, the rinsing property may be deteriorated.

≪Optional cleaning builder≫
Examples of the optional detergency builder include inorganic builder and organic builder other than the components (C) and (D).
Examples of such inorganic builders include zeolites such as A-type zeolite, P-type zeolite, and X-type zeolite, and amorphous aluminosilicates.
Examples of organic builders include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate, and the like; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; weight Organic builders, such as a polymer having a average molecular weight of 10,000 or less of the carboxy group.
These optional detergency builders can be used alone or in combination of two or more.

≪Perfume≫
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.
The fragrance composition is a mixture comprising a fragrance component, a solvent, a fragrance stabilizer, and the like.
A fragrance | flavor can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the fragrance in the granular detergent composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

≪Dye≫
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. Such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like.
As the dye, one kind can be used alone, or two or more kinds can be used in appropriate combination.

≪Fluorescent whitening agent≫
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- ( Examples thereof include fluorescent whitening agents such as styrylphenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.
Examples of commercially available optical brighteners include Whiteex SA, Whitetex SKC (trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba Specialty Chemicals), Lemonite CBUS-3B (trade name; manufactured by Khyati Chemicals), and the like. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are preferred.
As the fluorescent brightening agent, one kind can be used alone, or two or more kinds can be used in appropriate combination.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001% by mass or more and 1% by mass or less.

≪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, aspergillopeptidase A or B, and the like. As commercial products of protease, sabinase, alcalase, cannase, everase, deozyme (above, trade name: manufactured by Novozymes); API21 (trade name: manufactured by Showa Denko KK); Maxacar, Maxapem (above, trade name: Genencor) Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.
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, Lipex (trade name; manufactured by Novozymes), and liposome (trade name; manufactured by Showa Denko KK).
Cellulases include cellzymes (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 (or above) And cellulases described in JP-A-63-264699).
Examples of the amylase include commercially available stainzymes, termamyls, duramils (above, trade names: 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).
The enzyme content in the granular detergent composition is preferably 0.05 to 5% by mass.

≪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 content of the enzyme stabilizer in the granular detergent composition is preferably 0.05 to 2% by mass or less.

≪Polymers≫
In the present invention, the average molecular weight is used as a binder or a powder property modifier used when densifying the particles of the granular detergent composition, or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). A polyethylene glycol having a molecular weight of 200 to 200,000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, a cellulose derivative such as polyvinyl alcohol, hydroxypropylmethylcellulose (HPMC), and the like can be blended.
Moreover, a copolymer or terpolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above polymers, HPMC is preferable and HPMC having a weight average molecular weight of 20,000 or more is more preferable from the viewpoint of imparting flexibility to the laundry and preventing recontamination. Such polymers can be used singly or in appropriate combination of two or more.
The content of the above polymers in the granular detergent composition is preferably 0.05 to 5% by mass.

≪Anti-caking agent≫
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like.
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 the adsorption of metal ions to the laundry.
In addition to those included in the optional detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; Hydroxyethane-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 ( Methylenephosphonic acid), diethylenetriaminepenta Methylene phosphonic acid) organic phosphonic acid derivative or a salt thereof and the like; diglycolic acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
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 granular detergent composition as long as the performance is not impaired.

≪pH adjuster≫
Examples of the pH adjuster include the alkaline agents mentioned as the detergency builder, other alkaline compounds such as sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, and triethanolamine, the metal ion scavenger, and dihydrogen phosphate. Examples include alkali metal dihydrogen phosphates such as potassium, acidic compounds such as lactic acid, succinic acid, malic acid, gluconic acid, sulfuric acid, hydrochloric acid, and citric acid. 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.

(Production method)
The manufacturing method of the granular detergent composition of this invention can be manufactured with a well-known manufacturing method. For example, the components (A) to (D), and if necessary, the component (E) and optional components can be dispersed and dissolved in water and then spray-dried to obtain a powdery granular detergent composition. In addition, for example, the components (A) to (D) and, if necessary, the component (E) and optional components are subjected to kneading / extrusion, stirring granulation, rolling granulation, etc. Then, a granular detergent composition in a desired form can be obtained by compression molding or the like, and further by pulverization as necessary.

(Washing method)
The washing method using the granular detergent composition of the present invention is not particularly limited and may be the same as a known washing method. A specific example is a method in which a granular detergent composition is poured into water and the laundry is washed in the water (laundry liquid). The laundry to be washed may be washing by hand or by a washing machine (two-tank washing machine, fully automatic washing machine, drum washing machine, etc.). Therefore, for example, hand washing in which water is poured into a bag to dissolve the granular detergent composition and the clothes are washed is preferable. The amount of the granular detergent composition in water varies depending on the blending amount of the component (A) and other surfactants, but the concentration of the granular detergent composition in the washing liquid is 0.1 mass for washing by hand. % To less than 10% by mass, and 0.01% to less than 1% by mass for a washing machine.
The washing object by the granular detergent composition of the present invention may be the same as that generally used as a washing object (to be washed) by the granular detergent composition. For example, clothes, cloths, sheets, curtains, etc. Textile products.

According to the present invention, since it contains the components (A) to (D), it exhibits excellent detergency and foam persistence even when washing is performed using water with high hardness (for example, 10 ° DH or more). And rinsing properties are good. In addition, since the granular detergent composition contains 10 to 50% by mass of the specific particles, the user can obtain a good cleaning feeling due to the scrub feeling due to the specific particles.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
In this example, “%” is “% by mass” unless otherwise specified, and “parts” is “parts by mass”.
The blending amount of each component in Tables 1 to 8 is a blending amount converted as a pure component.
The blending amount of “Zeolite *” in the table indicates the total amount of zeolite in the MES detergent particles and separately added zeolite.

(Raw materials used)
<(A) component>
Α-sulfo fatty acid methyl ester salt (MES): produced according to the following production example (in the above formula (I), [component (A) having 14 carbon atoms of R ¹ ): [16 carbon atoms of R ¹ ] (A) component] = 90: 10, R ² carbon number 1, M is a sodium cation, AI of MES = 86.6%, zeolite 4.0%, moisture 3.4%, sodium sulfate 2.2%, Methyl sulfate 3.8%.)

Production example of MES << 1. Production of paste-like MES >>
In a 1 kL reactor equipped with a stirrer, 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 by mass, and 330 kg of the mixture was poured, and while stirring, 5% of anhydrous sodium sulfate was added as a coloring inhibitor 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 (industrial grade moisture of 500 ppm or less, manufactured by Sumitomo Chemical Co., Ltd.) was supplied as a lower alcohol for 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 aqueous solution of sodium hydroxide (industrial grade, manufactured by Daiso Corporation) using a line mixer.
Next, this neutralized product was poured into a bleaching agent mixing line, and 35% hydrogen peroxide (35% hydrogen peroxide for industrial use, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as a pure component to determine the AI concentration (α-sulfo fatty acid). 1% to the total concentration of methyl ester sodium salt (MES-Na) and α-sulfo fatty acid disodium salt (di-Na salt), mixed, bleached at 80 ° C, and pasted into MES Got.

≪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”, manufactured by Shinko Pantech Co., Ltd. at 35 kg / hr, and the inner wall heating temperature (heat transfer surface temperature) 135 Concentration was carried out at a temperature of 0 ° C. and a degree of vacuum (pressure in the processing section) of 0.007 to 0.014 MPa.
The resulting concentrate had a temperature of 115 ° C. and a moisture content of 2.5%.
The moisture content is a value obtained by measuring about 0.05 g of a sample with a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd., model: MKC-210, Method: 2, stirring speed 4).

≪3. Manufacture of MES solids >>
The MES paste obtained by the 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 cooling water flow rate is 1500 L / h on the upper belt side (cooled by flowing down on the back surface of the belt in a countercurrent manner), and 1800 L / h on the lower belt side (on the back surface 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. Manufacture of MES detergent particles >>
The obtained flaky MES solid (temperature: 25 ° C.) was fed 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, 95 parts of noodle-like MES together with 5 parts of powder A-type zeolite was pulverized (Okada Seiko Co., Ltd., speed mill ND-10 type, blade rotation speed 840 rpm, screen φ4 mm 1 kg / Min, and pulverized to obtain MES detergent particles having an average particle size of 500 μm.

<(A ′) component: Comparative product of component (A)>
C12 soap: sodium laurate, manufactured by Kanto Chemical Co., Inc.

<(B) component>
・ Linear C8 higher alcohol: Octyl alcohol, Conol 10WS (trade name), manufactured by Shin Nippon Chemical Co., Ltd. ・ Linear C10 higher alcohol: Decyl alcohol, Conol 1098 (trade name), manufactured by Shin Nippon Rika Co., Ltd./Linear C12 Higher alcohol: Lauryl alcohol, Conol 20P (trade name), manufactured by Shin Nippon Chemical Co., Ltd., C13 Higher alcohol: Contains a branched carbon chain (2-methyl), 49% linear, diamond Dole 13 (trade name), manufactured by Mitsubishi Chemical Corporation, straight chain C12 / 14 higher alcohol: 68-74% by mass having 12 carbon atoms, 24-30% by mass having 14 carbon atoms, CO-1270 (product) Name), manufactured by P & G Chemicals, linear C14 higher alcohol: myristyl alcohol, Conol 1495 (trade name), Shin Nippon Rika Made by Co., Ltd. ・ Linear C16 higher alcohol: Setanol, Conol 1695 (trade name), manufactured by Shin Nippon Rika Co., Ltd. ・ Linear higher alcohol: Stearyl alcohol, Conol 30SS (trade name), manufactured by Shin Nippon Rika Co., Ltd.

<(C) component>
-Sodium tripolyphosphate (STPP): manufactured by Central Glass Co., Ltd.-Sodium pyrophosphate (TSPP): manufactured by Nippon Chemical Industry Co., Ltd.

<(D) component>
・ Sodium carbonate: granular ash, Asahi Glass Co., Ltd. ・ Sodium silicate: No. 2 sodium silicate, powdered sodium silicate No. 2 (trade name), manufactured by Nippon Chemical Industry Co., Ltd.

<(E) component>
-Sodium lauryl sulfate ester (AS-Na): SLS (trade name), manufactured by PEPMACO MANUFACTURING CORPORATION-Linear alkylbenzene sodium sulfonate (LAS-Na): linear alkylbenzene having 10 to 14 carbon atoms in the linear alkyl group A sulfonic acid (Lypon LH-200 (manufactured by Lion Corporation) LAS-H (96% pure)) neutralized at the time of slurry preparation for spray drying or granulation. The blending amount in the table indicates mass% as LAS-Na.

<Others>
Polyoxyethylene alkyl ether (AE): A compound obtained by adding an average of 9 moles of ethylene oxide to an alcohol having 12 to 16 carbon atoms (CO-1214 (trade name), manufactured by P & G Chemicals). 90%, manufactured by Lion Corporation)
Polyoxyethylene polyoxypropylene alkyl ether (compound obtained by adding EO and PO to alcohol): Higher alcohol having 12 to 13 carbon atoms (Neodol 23 (trade name), manufactured by Shell Chemicals Japan Co., Ltd.) with ethylene oxide Compound with an average of 15 moles and an average of 3 moles of propylene oxide, manufactured by Lion Corporation, sodium sulfate: neutral anhydrous sodium sulfate, manufactured by Nippon Chemical Industry Co., Ltd., zeolite: A-type zeolite, zeolite Na-4A (trade name) 80% pure, manufactured by THAI SILICATE CHEMICALS, Inc., fluorescent whitening agent CBS: Chino Pearl CBS-X (trade name), manufactured by Ciba Japan Co., Ltd., fluorescent whitening agent AMS: Chino Pearl AMS-GX (trade name), Ciba・ Japan Co., Ltd. ・ Enzyme: Protease (SA (Nase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX 100T) / Cellulase (Cell Clean 4500T) / Glucosidase (Manaway 4.0T) (all from Novozymes Japan Ltd.) = 6/2/2/1 / 4 (mass ratio) mixture and fragrance: fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
-Dye: Ultramarine (Ultramarine Blue, manufactured by Dainichi Seika Kogyo Co., Ltd.)

(Examples 1-27, Comparative Examples 1, 3-11)
The granular detergent compositions having the compositions shown in Tables 1 to 4 and 7 to 8 were produced by the following production method A. In the table, “Balance” of sodium sulfate indicates an amount at which the total amount of the granular detergent composition is 100%.

<The manufacturing method A of a granular detergent composition>
For production of the granular detergent composition, an FS-1200 high-speed mixer / granulator (manufactured by Fukae Kogyo Co., Ltd.) was used. (C) component, (D) component, sodium sulfate, part of powder A-type zeolite (amount excluding powder A-type zeolite (1.6% equivalent amount) for surface modification described later) is stirred by a mixer. Dry blending was performed for 60 seconds at a speed of 100 rpm and a shearing machine speed of 2000 rpm. Water (equivalent to 0.375%) was added and the mixer was run 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 (1.4% equivalent amount) as a binder and nonionic surfactant (AE and alcohol EO / PO adduct) were added to the 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's shearing machine, stir the stirrer at 90 rpm for 120 seconds, add the enzyme and MES detergent particles, and then add the powder A-type zeolite (equivalent to 1.6% in terms of pure content) The surface was modified, and the fragrance and component (B) were sprayed to obtain surfactant-containing particles. The obtained surfactant-containing particles were transferred on a belt conveyor (speed: 0.5 m / s) in order to color a part of the particles (the surfactant-containing particle layer on the belt conveyor had a height of 30 mm, a layer A granular detergent composition having a water content of 4% was obtained by spraying a 20% aqueous dispersion of a pigment having a width of 300 mm).

(Examples 28 to 30)
A granular detergent composition having the composition shown in Table 4 was produced by the following production method B. In the table, “Balance” of sodium sulfate indicates an amount at which the total amount of the granular detergent composition is 100%.

<The manufacturing method B of a granular detergent composition>
LAS-Na or AS-Na, (C) component, (D) component, sodium sulfate, fluorescent brightener (CBS, AMS), (B) component, part of powder A-type zeolite (Ladyge described later) A slurry with a water content of 38% was prepared by dissolving or dispersing the total amount (excluding the amount equivalent to 2.4%) of the amount added to the mixer and the amount added to the V blender in water, and this slurry was put into a countercurrent spray drying tower. Then, spray-dried particles were obtained by spray-drying under conditions of 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 excavator and a clearance between the shovel and the wall surface of 5 mm (filling rate: 50% by volume), and the main shaft was 200 rpm. The chopper was stirred at 200 rpm. Nonionic surfactant (AE and alcohol EO / PO adduct) was added to it over 2 minutes and stirred for 5 minutes, and then a part of powder A-type zeolite (equivalent to 0.8% in terms of pure content) was added. The mixture was stirred and stirred for 2 minutes to obtain surfactant-containing particles.
The obtained surfactant-containing particles, a part of the powder A-type zeolite (equivalent to 1.6% in terms of pure content), the enzyme and MES detergent particles were mixed in a V blender, and a fragrance was sprayed. Further, in order to color a part of the surfactant-containing particles, a 20% aqueous dispersion of the dye was sprayed in the same manner as in Production Method A to obtain a granular detergent composition having a water content of 7%.

(Examples 31 to 47, Comparative Example 2)
The granular detergent compositions having the compositions shown in Tables 4 to 7 were produced by the following production method C. In the table, “Balance” of sodium sulfate indicates an amount at which the total amount of the granular detergent composition is 100%.

<The manufacturing method C of a granular detergent composition>
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. Sodium sulfate and fluorescent brightener (CBS, AMS) were added thereto and stirred for 10 minutes. Subsequently, an anionic surfactant (LAS-Na (LAS-H neutralized with NaOH), AS-Na or soap), component (C) and component (D) were added, and the mixture was stirred for 10 minutes and powdered A part of the A-type zeolite (amount excluding V blender input (1.6% equivalent amount) described later) was added. 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 slurry was spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles.
The obtained spray-dried particles, a part of the powder A-type zeolite (equivalent to 1.6% in terms of pure content), and enzymes (protease, amylase, lipase, cellulase, glucosidase) were mixed in a V blender. Furthermore, after adding the particle | grains for MES detergent, the fragrance | flavor, nonionic surfactant (AE and alcohol EO / PO adduct), and (B) component were sprayed, and surfactant-containing particle | grains were obtained. In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a pigment was sprayed in the same manner as in Production Method A to obtain a granular detergent composition having a water content of 6%.

(Adjustment of particle size)
About the obtained granular detergent composition, the particle diameter was adjusted with the following operation.
A sieve A having an inner diameter of 20 cm (aperture: 1400 μm), a sieve B (aperture: 710 μm), a sieve C (aperture: 45 μm), and a tray D (all manufactured by Tokyo Screen Co., Ltd.) were prepared. On the saucer D, sieves were set in the order of sieve C, sieve B, and sieve A. 100 g of granular detergent composition was placed on sieve A in a single sieving operation. The top cover was put on and sieved according to JIS K3362. In the sieving operation, the sieve was tilted and held with one hand so that the granular detergent composition spread evenly on the surface of the net, and the other hand was hit 150 times with the edge of the sieve. The sieve was rotated about 1/6 for every 25 hits.
Only the granular detergent composition (particles having a particle diameter of more than 710 μm and 1400 μm or less) remaining on the sieve B and the granular detergent composition (particles having a particle diameter of more than 45 μm and 710 μm or less) remaining on the sieve C are more than 710 μm and 1400 μm in the table. It mixed so that it might become the following particle | grain ratio and the particle | grain ratio of particle diameter over 45 micrometers 710 micrometers, and it was set as the granular detergent composition of each example.

(Evaluation methods)
<Scrub feeling evaluation>
A washbasin (inner diameter: 30 cmφ, depth: 10 cm) was charged with 1 L of water having a hardness adjusted and a water temperature of 25 ° C. The hardness of water is adjusted by dissolving 262.5 g of calcium chloride dihydrate in 10 L of ion exchange water to prepare 1000 ° DH hard water, and then diluting with ion exchange water to become 15 ° DH hard water. (1 ° DH = 10 mg (calcium oxide) / L (water)). Put one piece (about 150g) of impregnated soil oil of the following composition into cotton shirt at 0.2% by mass, then sprinkle 1g of granular detergent composition of each example on cotton shirt and hand wash for 1 minute Then, scrub feeling was evaluated. The scrub feeling was evaluated by 10 panelists based on the following criteria, and the average score was classified into the following criteria and evaluated.

≪Composition of dirt oil≫
Oleic acid: 45%
Trio Rain: 25%
Cholesterol oleate: 19.5%
Liquid paraffin: 4%
Squalene: 4%
Cholesterol: 2.5%

<< Criteria >>
3 points: scrub feeling 2 points: slightly scrub feeling 1 point: no scrub feeling

≪Evaluation criteria≫
◎ (Pass): Average point is 2.5 points or more ○ (Pass): Average point is 2.0 or more and less than 2.5 points × (Fail): Average point is less than 2.0 points

<Evaluation of undissolved particles>
A two-tank washing machine (CW-C30A1-1, manufactured by Mitsubishi Electric Corporation) was filled with 30 L of water having a water temperature of 20 ° C. and a hardness of 15 ° DH, and 50 g of the granular detergent composition of each example was placed therein and standard for 30 seconds. Stir with a stream of water. Next, 7 sheets (about 1 kg) of a black shirt impregnated with soil oil as a test cloth at 0.2% by mass were added and washed with a soft water flow for 5 minutes. After washing, it was dehydrated and rinsed with 30 L of water having a water temperature of 20 ° C. and a hardness of 15 ° DH for 3 minutes. The rinsing operation was performed twice in total. After the second rinse, the total value of the particles adhering to the dehydrated black shirt was determined and evaluated according to the following evaluation criteria.

≪Evaluation criteria≫
(Pass): Particles are not attached to the cotton skin shirt.
○ (Pass): 1 to 5 particles are attached to the cotton skin shirt.
Δ (pass): 5 or more and less than 15 particles are adhered to the cotton shirt.
X (failed): 15 or more particles adhered to the cotton skin shirt.

<Detergency evaluation>
The cleaning power was evaluated based on the cleaning rate determined by the following method.
As the contaminated fabric, a commercially available contaminated fabric (WFK-10D, manufactured by Washerei Forschungs Institute) was cut into 5 × 5 cm. A Terg-O-meter (manufactured by UNITED STATES TESTING) was used as the cleaning tester.
Place 900 mL of water having a water temperature of 25 ° C. and a hardness of 15 ° DH and 2.7 g of the granular detergent composition of each example into a cleaning tester, and put 10 of the above-mentioned contaminated cloths and cleaning knitted cloths, and a bath ratio of 30 times. And washed at 120 rpm and 25 ° C. for 10 minutes. Thereafter, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1, manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L at a water temperature of 25 ° C. and a hardness of 15 ° 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 by the following equation (2) for the unwashed and washed cloths. .
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 (2)
[Wherein, K / S = (1−R / 100) ² / (2R / 100), and R is reflectance (%)]
The cleaning rate (%) was calculated for 10 contaminated cloths, and the average value of the cleaning rates of 10 contaminated cloths was obtained. A detergent composition having an average value of 65% or more was regarded as acceptable.

<Foam durability evaluation>
A solution was prepared by dissolving 3 g of each granular detergent composition in 1 L of water having a water temperature of 25 ° C. and a hardness of 15 ° DH. Into a glass cylindrical tube having an inner diameter of 3 cm and a height of 25 cm, 20 mL of the prepared solution and 5 μL of soil oil were charged. Next, while keeping the temperature constant at 25 ° C., it was shaken for 1 minute using a shaker, and the height (mm) of the foam after 5 minutes from the shaking stop was measured.
A detergent composition having a foam height of 20 mm or more after 5 minutes from the shaking stop was regarded as acceptable.

<Rinseability evaluation>
A two-tub washing machine (CW-C30A1-1, manufactured by Mitsubishi Electric Corporation) was filled with 30 L of water having a water temperature of 25 ° C. and a hardness of 15 ° DH. Stir with a stream of water. Next, 7 pieces (about 1 kg) of soil oil impregnated at 0.2% by mass with respect to a cotton skin shirt as a test cloth were placed and washed with a standard water flow for 10 minutes. After washing, it was dehydrated and rinsed with 30 L of water having a water temperature of 25 ° C. and a hardness of 15 ° DH for 3 minutes. The rinsing operation was performed twice in total. The state of the rinsing liquid after completion of the second rinsing was evaluated according to the following evaluation criteria.

≪Evaluation criteria≫
A (Pass): The size of the foam is 1 mm or less, and the foam is less than 10% of the liquid level.
○ (Pass): The size of the bubbles is 1 mm or less, and the bubbles occupy 10% or more and less than 50% of the liquid level.
Δ (pass): The size of the foam is 1 mm or less, and the foam occupies 50% or more of the liquid surface.
X (failed): Bubbles account for 50% or more of the liquid surface, and there are bubbles of about 2 to 3 mm.

About the granular detergent composition of each example, scrub feeling evaluation, particle undissolved evaluation, washing rate measurement, foam persistence evaluation, and rinse evaluation are performed, and the results are shown in the table.

As shown in Tables 1 to 6, the granular detergent compositions of Examples 1 to 47 to which the present invention was applied were all evaluated for scrub feeling evaluation, particle undissolved evaluation, washing rate measurement, foam sustainability evaluation, and rinse evaluation. Everything was good. Particularly, Examples 28 to 47 containing the component (E) had a foam persistence of 45 or more, and were excellent in the foam persistence.
On the other hand, Comparative Examples 1 and 2 containing no component (A) had a cleaning rate of 60% or less, and were inferior in cleaning power to Examples 1 to 47. Comparative Example 3 containing no component (B), Comparative Example 4 in which the content of the component (B) is 0.04% by mass, and Comparative Examples 6 to 7 in which the carbon number of the higher alcohol is outside the scope of the present invention are: The foam persistence was low. In Comparative Example 5 in which the content of the component (B) is 2.5% by mass, the rinsing property is “x” and the alcohol odor is conspicuous.
In Comparative Examples 8 to 9 containing no component (C) or component (D), the cleaning rate was less than 65%. In Comparative Example 10 in which the specific particle ratio is less than 10% by mass, the scrub feeling evaluation is “x”, and in Comparative Example 11 in which the specific particle ratio is more than 50% by mass, the undissolved evaluation and the rinsing property evaluation are both “ X ".
From the above results, the granular detergent composition to which the present invention is applied exhibits excellent detergency and foam sustainability even when washing is performed using water with high hardness, has good rinsing properties, and is good. A feeling of washing was obtained, and it was found that the washing was particularly suitable for hand washing.

According to the granular detergent composition of the present invention, even when washing is performed using water with high hardness, excellent detergency and foam persistence are exhibited, rinsing properties are good, and a good washing feeling can be obtained. .

Claims (4)

1. A granular detergent composition containing the following components (A) to (D),
   A granular detergent composition comprising 10 to 50% by mass of particles having a particle diameter of more than 710 μm and 1400 μm or less.
   Component (A): α-sulfo fatty acid alkyl ester salt represented by the following formula (I):
   R ¹ —CH (SO ₃ M) —COOR ² (I)
   (In the formula (I), R ¹ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ² is an alkyl group, and M represents a counter ion.)
   Component (B): a higher alcohol having 10 to 16 carbon atoms contained in an amount of 0.1% by mass or more and less than 2% by mass with respect to the total mass of the granular detergent composition.
   (C) Component: Phosphorus builder.
   (D) Component: Alkali builder.
2. The granular detergent composition according to claim 1, wherein the mass ratio represented by the content of the component (A) / the content of the component (B) is 20 to 100.
3. The granular detergent composition according to claim 1 or 2, comprising the following component (E).
   Component (E): at least one anionic surfactant selected from linear alkylbenzene sulfonates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, alkyl air sulfates and alkenyl ether sulfates.
4. The granular detergent composition according to any one of claims 1 to 3, which is for hand-washing laundry.