WO2009084479A1 - Detergent composition for clothing - Google Patents

Abstract

Disclosed is (1) a detergent composition for clothing, which contains an anionic surfactant (a) represented by general formula (I) and a clay mineral (b). Also disclosed is (2) a detergent composition for clothing, which contains the anionic surfactant (a), the clay mineral (b) and a nonionic surfactant (d) represented by general formula (IV). Those detergent compositions for clothing exhibit excellent cleaning performance, anti-soil-redeposition performance and softening performance. R1-O-(A1O)m-(EO)n-SO3M (I) [In the formula (I), R1 represents a hydrocarbon group having 6-22 carbon atoms; A1O represents an oxyalkanediyl group having 3 and/or 4 carbon atoms; EO represents an oxyethylene group; m represents a number of 1-10; and n represents a number of 0-20.] R3-O-(C3H6O2)y-H (IV) [In the formula (IV), R3 represents a hydrocarbon group having 6-22 carbon atoms; and y represents the condensation degree of glycerin, which is a number of 1-7.]

Description

Detergent composition for clothing

The present invention relates to a detergent composition for clothing.

In recent years, consumer expectation regarding laundry detergents is high cleaning performance against dirt, prevention of re-contamination of dirt (coloring components such as wrinkles and mud released from the clothes during the washing process are concentrated in the wash water, and clothes in the wash water In addition to prevention of the phenomenon of redeposition of the garment and darkening of the clothing), flexibility after washing and the like can be mentioned.
When clothes are washed, the softness is lost due to dropping off of the fiber treatment agent or adhesion of salts, resulting in a stiff feel, but in order to prevent this and add flexibility to the texture of the clothes, the softness of clay minerals Is being considered.
For example, a detergent composition containing a smectite-type clay mineral (Japanese Patent Laid-Open No. 49-85102), a fabric softening product using a combination of bentonite and a pentaerythritol compound (Japanese Patent Laid-Open No. 5-140869), bentonite and a soluble potassium salt A detergent composition for softening using a combination of the above (No. 8-506843), a detergent composition containing a fabric softening component using a combination of a clay mineral and a flocculant (No. 2002-541342), and the like are known. Yes.

Further, as a part of enhancing the detergency against oil stains and the like, a nonionic surfactant has been added as a main surfactant. For example, a combination of a nonionic surfactant and a specific ratio of cationic surfactant / anionic surfactant has a high cleaning performance against sebum soil and is also considered to have an excellent softening effect. A cleaning composition (JP-A-11-217585) has been proposed.
A soft detergent composition (International Publication No. 2007/114484) containing glyceryl monoether and clay mineral is also known.
However, a detergent for clothing that satisfies both the cleaning performance, the performance of preventing recontamination of dirt, and the softening performance has not been obtained.

The present invention relates to the following laundry detergent compositions [1] and [2] [1] containing an anionic surfactant (a) represented by the general formula (I) and a clay mineral (b) A detergent composition for clothing.
R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
(Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O represents an oxyalkanediyl group having 3 and / or 4 carbon atoms, EO represents an oxyethylene group, and m and n are The number of moles added is shown, m is 1 to 10, and n is 0 to 20.)
[2] For clothing containing an anionic surfactant (a) represented by the general formula (I), a clay mineral (b), and a nonionic surfactant (d) represented by the general formula (IV) Detergent composition.
R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
(In the formula, R ¹ , A ¹ O, EO, m and n are the same as described above.)
R ³ —O— (C ₃ H ₆ O ₂ ) yH (IV)
(In the formula, R ³ represents a hydrocarbon group of 6 to 22, and y represents a degree of glycerol condensation and is a number of 1 to 7.)

The present invention relates to a detergent composition for clothing excellent in cleaning performance, recontamination prevention performance, and softening performance.
The present inventors have found that the above-mentioned problems can be solved by combining a specific surfactant and clay mineral, focusing on the interaction between the clay mineral and the anionic surfactant with respect to the flexibility-imparting effect. It was.
That is, the 1st clothing detergent composition (1st invention) of this invention contains the anionic surfactant (a) represented by general formula (I), and a clay mineral (b), It is characterized by the above-mentioned. And
R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
(Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O represents an oxyalkanediyl group having 3 and / or 4 carbon atoms, EO represents an oxyethylene group, and m and n are The number of moles added is shown, m is 1 to 10, and n is 0 to 20.)
The second garment detergent composition of the present invention (second invention) comprises an anionic surfactant (a), a clay mineral (b), and a general formula (IV) represented by the general formula (I). It contains the nonionic surfactant (d) represented by these.
R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
(In the formula, R ¹ , A ¹ O, EO, m and n are the same as described above.)
R ³ —O— (C ₃ H ₆ O ₂ ) yH (IV)
(In the formula, R ³ represents a hydrocarbon group of 6 to 22, and y represents a degree of glycerol condensation and is a number of 1 to 7.)
Hereinafter, each component of the detergent composition for clothing of the first invention and the second invention will be described.

<Anionic surfactant (a) represented by general formula (I)>
The anionic surfactant (a) used in the present invention is an alkyl ether sulfate ester salt represented by the following general formula (I).
R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
(Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O represents an oxyalkanediyl group having 3 and / or 4 carbon atoms, EO represents an oxyethylene group, and m and n are The number of moles added is shown, m is 1 to 10, and n is 0 to 20.)

The hydrocarbon group represented by R ¹ in the general formula (I) is preferably an alkyl group having 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms. Furthermore, it is preferable that it is a linear alkyl group derived from fats and oils raw materials from performance aspects, such as foaming power and emulsification power, and environmental aspects called carbon neutral.
As the oxyalkanediyl group represented by (A ¹ O) in the general formula (I), an oxytrimethylene group, an oxypropane-1,2-diyl group, an oxybutane-1,2-diyl group, an oxybutane-1,3 -Diyl group, oxybutane-2,3-diyl group, oxytetramethylene group, and combinations of two or more thereof. Of these, oxypropane-1,2-diyl group and oxybutane-1,2-diyl group are more preferable.
M in the general formula (I) is the number of added moles of (A ¹ O), and is a number of 1 to 10, preferably 1 to 5 from the viewpoint of improving the reactivity at the time of production and the softening performance. And more preferably 1 to 3.
N in the general formula (I) is the number of added moles of (EO), and is a number from 0 to 20, preferably from 0 to 10 and more preferably from 0 to 10 from the viewpoint of improving the softening performance. 5.

M in the general formula (I) is a cation group that forms a salt, and examples thereof include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions.
Examples of the alkali metal include sodium, potassium, and lithium, examples of the alkaline earth metal include calcium, and examples of the alkanol ammonium ion include triethanolammonium ion. Among these, alkali metals such as sodium and potassium are preferable, and sodium is particularly preferable.
The anionic surfactant (a) is preferably in the form of a powder from the viewpoint of handleability, but may be in the form of a hydrous paste or the like.

The method for producing the anionic surfactant (a) represented by the general formula (I) is not particularly limited. For example, it can be produced by a method including the following steps (I) to (III).
Step (I): Step of adding 1 to 10 mol of an alkanediyl oxide having 3 and / or 4 carbon atoms to 1 mol of an alcohol having a hydrocarbon group having 6 to 22 carbon atoms. Step (II): In the above step (I) Step (III) of adding ethylene oxide to the resulting alkanediyl oxide adduct (III): Step of sulfating and then neutralizing the alkoxylate obtained in the above step (II)

The anionic surfactant (a) obtained by the above method is a mixture of alkyl ether sulfates represented by the following general formulas (i) to (iv), and those satisfying the general formula (I): It is a compound of (ii) and (iv).
R ¹ —O—SO ₃ M (i)
R ¹ —O— (A ¹ O) x—SO ₃ M (ii)
R ¹ —O— (EO) y—SO ₃ M (iii)
R ¹ —O— (A ¹ O) z- (EO) z′—SO ₃ M (iv)
In the general formulas (ii) to (iv), x, y, z and z ′ are each an integer of 1 or more, and R ¹ and M are the same as R ¹ and M in the general formula (I). is there.
The content of the anionic surfactant (a) in the garment detergent composition of the present invention may be an effective amount that can achieve the object and effect of the present invention, and in the garment detergent composition of the present invention. Are not anionic surfactants (a) represented by the general formula (I), that is, alkyl ether sulfates not [m = 1 to 10] and / or [n = 0 to 20], For example, the above compounds (i) and (iii) may be included. From this viewpoint, the content of the anionic surfactant (a) in the total alkyl ether sulfate ester salt is preferably 10% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more. .

The hydrocarbon group of the alcohol in the step (I) is preferably an alkyl group having 8 to 16 carbon atoms, more preferably an alkyl group having 10 to 14 carbon atoms, and more preferably 12 to 14 carbon atoms from the viewpoints of versatility and handleability. Are particularly preferred. Furthermore, it is preferable that it is a linear alkyl group from a viewpoint of foaming power and emulsifying power performance.
The amount of the alkanediyl oxide having 3 and / or 4 carbon atoms used is such that the number of moles of alkanediyl oxide added to 1 mole of the alcohol is 1-10.
The amount of ethylene oxide used in step (II) is such that the number of moles of ethylene oxide added per mole of the alkanediyl oxide adduct obtained in step (I) is 0-20.
The implementation of the steps (I) and (II) can be performed by a conventionally known method. That is, a reaction vessel is charged with alcohol and 0.5 to 1 mol% of KOH or the like as a catalyst, heated and dehydrated, and at a temperature of 130 to 160 ° C., predetermined amounts of alkanediyl oxide and ethylene oxide, respectively. It can be produced by a block addition reaction.

Examples of the sulfation method in step (III) include a method using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid, etc., and particularly, waste sulfuric acid and waste hydrochloric acid, etc. From the viewpoint of preventing generation of sulfur, a method of continuously supplying sulfur trioxide in a gaseous or liquid state simultaneously with the alkoxylate is preferable.
There is no limitation on the neutralization method of the obtained sulfate, batch type that neutralizes while adding and stirring the sulfate in a predetermined amount of neutralizer, and supply the sulfate and neutralizer continuously into the pipe In addition, a continuous type that is neutralized with a stirring mixer can be employed. Examples of the neutralizing agent that can be used include an aqueous alkali metal solution, aqueous ammonia, and triethanolamine. An aqueous alkali metal solution is preferable, and sodium hydroxide is more preferable.

<Clay mineral (b)>
There is no restriction | limiting in particular in the clay mineral (b) used by this invention, A natural product or a synthetic product may be sufficient and the form may be either a powder form and a granular form. When the clay mineral (b) is made into a clay granulated product, it means one containing a flocculant, an additive and the like used during granulation.
Examples of the clay mineral (b) include talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, etc.) , Muscovite, paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penanthite, sudowite, dombasite, etc.), brittle mica (clinentite, margarite, etc.), sulite, serpentine (anti Examples include golite, lizardite, chrysotile, amesite, cronsteadite, burcherin, greenerite, garnierite, and kaolin (kaolinite, dickite, nacrite, halloysite, etc.).
Among these, talc, smectite, swellable mica, vermiculite, chrysotile and kaolin are preferable, and smectite is more preferable.
These may be used alone or in appropriate combination of two or more.

As the clay mineral (b), from the viewpoint of softening performance, a clay mineral or a clay granule mainly composed of a smectite-type layered clay mineral represented by the general formula (II) is more preferable, montmorillonite, hectorite, Among them, a clay mineral or a granulated granule containing montmorillonite as a main component is particularly preferable.
_{[Si 8 (Mg a Al b} ) O 20 (OH) 4] X- · X / n [Me] n + (II)
(Wherein a, b and x are 0 <a ≦ 6 and 0 ≦ b ≦ 4, 0.2 ≦ x = 12-2a-3b ≦ 1.2, and Me is Li, Na, Ka, (At least one of Ca, Mg and NH ₄ is shown, and n is the valence of Me.)
The smectite-type layered clay mineral is considered to exhibit a softening performance when the layer structure expands in a liquid medium and is dispersed and adsorbed on clothing. Here, “main component” means that the clay mineral represented by the general formula (II) is 90% by mass or more, preferably 92% by mass or more, more preferably 95% by mass or more in the total clay mineral. Means that.
When the clay mineral (b) is used as a powder, the average particle size is preferably 0.1 to 40 μm, more preferably 0.5 to 35 μm, still more preferably 1 to 30 μm, and particularly preferably 1 to 25 μm.
Here, the average particle diameter of the clay mineral (b) can be measured using, for example, a laser diffraction / scattering particle diameter distribution measuring apparatus having a dry measurement unit.

Further, from the viewpoint of solubility and recontamination prevention of dirt such as carbon, the content of Na in the clay mineral represented by the general formula (II) is preferably 1.0% by mass or more in the clay mineral. More preferably 5% by mass or more. Moreover, when it is a clay granulated material, 1.0 or more are preferable, as for the mass ratio (Na / Ca) of Na and Ca, 1.5 or more are more preferable, and 2.0 or more are still more preferable.
In order to obtain a clay mineral having a high (Na / Ca) mass ratio, it is only necessary to select a production area if it is a natural product. When producing a clay granulated product, for example, a clay ore slurry or a clay mineral pulverized product is used. It can be prepared by adding Na salt such as sodium carbonate, and it can be prepared by a known method if it is a synthetic product.
The mass ratio of (Na / Ca) in the clay granulated product was determined by pulverizing the clay granulated product in a mortar and passing 0.1 g of the sample that passed through a sieve having an opening of 125 μm using a microwave wet ashing device (automatic). -After hydrogen peroxide decomposition, the volume can be made up to 50 mL in a volumetric flask and measured with an inductively coupled plasma (ICP) emission spectrometer to quantify and calculate the amount of Na and Ca.

The bulk density of the clay granulated material is preferably 500 to 1200 g / L, more preferably 600 to 1100 g / L, and particularly preferably 700 to 1050 g / L from the viewpoint of non-classification. Here, the bulk density is measured according to JIS K3362.
The average particle diameter of the clay granulated material is preferably 100 to 2000 μm, more preferably 200 to 900 μm, and particularly preferably 300 to 800 μm from the viewpoint of low dust generation and non-classification. Here, the average particle diameter can be determined from the weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve of JIS Z8801.
The water content of the clay granulated material is preferably 18% by mass or less, more preferably 16% by mass or less, and particularly preferably 14% by mass or less from the viewpoint of particle strength.

Examples of commercially available products containing the clay mineral (b) represented by the general formula (II) as a main component include trade names “Zood Rozil DGA212”, “Round Rozil PR414”, “Round Rozil DG214”, “ "Round rosyl DGA powder", "Hulasoft-1 powder", Raviossa brand names: "Detasoft GIS", "Detasoft GIB", "Detasoft GISW", Hojun Corporation brand names: "Bengel Bright 11", "Bengel" Bright 23 ”, trade names manufactured by CSM:“ Quest Soft ”,“ Pure Bentonite ”,“ Standard Bentonite ”,“ Premium Bentonite ”,“ Odosolv K-400 ”manufactured by Kurosaki Shirato Kogyo Co., Ltd., and the like.
Among the commercially available products, there are granulated granule types obtained by adding a binder component, but the binder component may be added as long as the effects of the present invention are not impaired.

<Nonionic surfactant (c) represented by formula (III)>
The detergent composition for clothing of the present invention preferably contains a nonionic surfactant (c) represented by the following general formula (III) from the viewpoint of further improving the cleaning performance.
R ² —O— (A ² O) x—H (III)
(In the formula, R ² represents a hydrocarbon group having 6 to 22 carbon atoms, A ² O represents an oxyalkanediyl group having 2 to 4 carbon atoms, and x represents the number of added moles and is 1 to 20).
Here, the hydrocarbon group which is R ² in the general formula (III) is preferably an alkyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and particularly preferably 12 to 14 carbon atoms. Furthermore, it is preferable that it is a linear alkyl group derived from fats and oils raw materials from performance aspects, such as foaming power and emulsification power, and environmental aspects called carbon neutral.

Examples of the oxyalkanediyl group represented by (A ² O) in the general formula (III) include oxyethylene group, oxytrimethylene group, oxypropane-1,2-diyl group, oxybutane-1,2-diyl group, oxybutane -1,3-diyl group, oxybutane-2,3-diyl group, oxytetramethylene group, and combinations of two or more thereof. Of these, oxyethylene groups and oxypropane-1,2-diyl groups are more preferred.
X in the general formula (III) is the number of added moles of (A ² O), and is a number from 1 to 20, and preferably from 2 to 14 from the viewpoint of improving production efficiency and softening performance during production. More preferably, it is 3-12.
Preferred examples of the nonionic surfactant (c) represented by the general formula (III) include ethers of an oxyethylene group or oxypropane-1,2-diyl group and an alkyl group having 10 to 14 carbon atoms. The content of the nonionic surfactant (c) to be mentioned may be an effective amount that can achieve the object and effect of the present invention. In the garment detergent composition of the present invention, the general formula (III) The nonionic surfactant (c) represented by the formula (1) may be included, that is, x is not 1 to 20. From this viewpoint, the content of the nonionic surfactant (c) in the total nonionic surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. .

<Nonionic surfactant (d) represented by general formula (IV)>
The detergent composition for clothing of the present invention contains a nonionic surfactant (d) represented by the following general formula (IV) from the viewpoint of further enhancing the softening performance.
R ³ —O— (C ₃ H ₆ O ₂ ) yH (IV)
(In the formula, R ³ represents a hydrocarbon group of 6 to 22, and y represents a degree of glycerol condensation and is a number of 1 to 7.)
Here, the hydrocarbon group represented by R ³ in the general formula (IV) is preferably an alkyl group having 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms.
In general formula (IV), y is the degree of glycerin condensation and is a number of 1 to 7, preferably 2 to 6, more preferably 3 to 3, from the viewpoint of reactivity during production. 5.
The ratio is preferably 1.2 to 5, more preferably 1.5 to 3.
Further, in the nonionic surfactant (d) represented by the general formula (IV), [R ³ —O— (C ₃ H ₆ O ₂ ) ₃ to ₅ —H from the viewpoint of softening performance and cleaning performance. / R ³ —O— (C ₃ H ₆ O ₂ ) ₁ to ₇ —H] is preferably 0.3 or more, more preferably 0.35 or more, and particularly preferably 0.4. That's it.

The nonionic surfactant (d) includes a plurality of compounds having different degrees of condensation y of glycerin in the general formula (III) from the viewpoints of washing performance at low temperature and softness performance. It is preferable to contain at least 3 species, particularly at least 3 species. Among the nonionic surfactants (d), those having a glycerin condensation degree y of 3 to 5 exhibit the highest cleaning performance. However, even within this range, when the condensation degree y of glycerin consists of only one, it is easy to crystallize, so the solubility in water is particularly poor at low temperatures, and as a result, the detergency tends to decrease. . On the other hand, when the nonionic surfactant (d) contains a plurality of compounds having different glycerin condensation degrees y, crystallization is suppressed, so that high solubility is exhibited even at a low temperature, resulting in good cleaning performance. . Therefore, it is more preferable that the nonionic surfactant (d) contains 2 or more, and all 3 (y = 3, 4, 5) among those having a glycerin condensation degree y of 3 to 5. .

From the viewpoint of detergency, the condensation degree y of glycerin, which is a raw material of the nonionic surfactant (d), is most preferably 4. In a glyceryl ether having a glycerin condensation degree of 1 to 7, the condensation degree y is 4 The glyceryl monoether content is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
Further, from the viewpoint of detergency and re-contamination prevention, the content of glyceryl monoether having a glycerin condensation degree y of 2 in the nonionic surfactant (d) is preferably less than 50% by mass, more preferably 35% by mass or less. Further, in the nonionic surfactant (d), the content of glyceryl monoether having a glycerin condensation degree y of 1 is preferably less than 30% by mass, more preferably 20% by mass or less.

Specific examples of the nonionic surfactant (d) are ethers of polyglycerol and an alkyl group having 8 to 22 carbon atoms, such as polyglycerol octyl ether, polyglycerol decyl ether, polyglycerol lauryl ether, Examples thereof include polyglycerol alkyl ethers such as glycerol myristyl ether, polyglycerol palmityl ether, polyglycerol isostearyl ether, polyglycerol stearyl ether, polyglycerol oleyl ether, and polyglycerol behenyl ether. Among these, monoethers of polyglycerin having a condensation degree of 3 to 5 and a linear alkyl group having 10 to 14 carbon atoms are more preferable.

(Detergent composition for clothing)
Each of the anionic surfactant (a), the clay mineral (b), and the contained nonionic surfactant (c) which may be contained as necessary in the detergent composition for clothing of the first invention The amount is not particularly limited, but is as follows from the viewpoints of cleaning performance, recontamination prevention performance, and softening performance.
The content of the anionic surfactant (a) is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, still more preferably 4 to 60% by mass, and particularly preferably 6 to 50% by mass.
The content of the clay mineral (b) is preferably 1 to 80% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 40% by mass, and particularly preferably 3 to 30% by mass. When the clay mineral (b) is a natural product, it contains impurities such as quartz, cristobalite, calcite, feldspar, etc., but the content of the clay mineral (b) means one containing these impurities.
The content of the nonionic surfactant (c) is preferably 0 to 80% by mass, more preferably 0.5 to 70% by mass, still more preferably 1 to 50% by mass, and particularly preferably 3 to 25% by mass. %.
When the nonionic surfactant (c) is used, the mass ratio of the anionic surfactant (a) to the nonionic surfactant (c) [anionic surfactant (a) / nonionic surfactant (c) )] Is preferably 0.3 or more, more preferably 0.5 or more, more preferably 0.9 or more as the lower limit, and preferably 10 or less, more preferably 5 or less, more preferably 2 as the upper limit. .5 or less.

The contents of the anionic surfactant (a), the clay mineral (b), and the nonionic surfactant (d) in the detergent composition for clothing of the second invention are not particularly limited, From the viewpoint of recontamination prevention performance and softening performance, it is as follows.
The content of the anionic surfactant (a) is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, still more preferably 4 to 60% by mass, and particularly preferably 6 to 50% by mass.
The content of the clay mineral (b) is preferably 1 to 80% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 40% by mass, and particularly preferably 3 to 30% by mass. When the clay mineral (b) is a natural product, it contains impurities such as quartz, cristobalite, calcite, feldspar, etc., but the content of the clay mineral (b) means one containing these impurities.
The content of the nonionic surfactant (d) is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass, still more preferably 1 to 50% by mass, particularly preferably 3 to 25% by mass.
The mass ratio of the anionic surfactant (a) to the nonionic surfactant (d) [anionic surfactant (a) / nonionic surfactant (d)] is preferably 0.3 or more as a lower limit. The upper limit value is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.

The detergent composition for clothing of the first and second inventions can be obtained by mixing the above components and drying appropriately, but other surfactants usually used in the art as long as the effects of the present invention are not impaired. , Alkaline agent, inorganic salt, zeolite, bleach (percarbonate, perborate, bleach activator, etc.), bleach activator, viscosity modifier, reducing agent (sulfite, etc.), fluorescent brightener, Foaming agents, antifoaming agents, preservatives, enzymes such as cellulase and protease, dyes, fragrances and the like can be blended.
Examples of the alkali agent include water-soluble inorganic salts such as carbonates, hydrogen carbonates, and silicates, and poorly water-soluble inorganic substances such as crystalline silicates.
Examples of the inorganic salt include alkali metal salts such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid, and sodium chloride and sodium sulfate are particularly preferable.
Other cleaning components include water-soluble organic acid salts such as citrate and fumarate, poorly water-soluble inorganic substances such as crystalline or amorphous aluminosilicates, carboxylic acid polymers, carboxymethylcellulose, soluble starch, saccharides, etc. And water-soluble polymers.

[1] Manufacture example 1 of manufacture of each component of detergent composition <Manufacture of anionic surfactant (a-1)>
A straight chain alcohol having 12 carbon atoms (trade name: Calcoal 2098 manufactured by Kao Corporation) and 3.5 g of KOH were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device at 110 ° C. and 1.3 kPa. Dehydration was performed for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and 1460 g of propane-1,2-diyl oxide (hereinafter referred to as “PO”) was charged. After addition reaction and aging at 120 ° C., cooling to 80 ° C., removing unreacted PO at 4.0 kPa, adding 3.8 g of acetic acid into the autoclave, and stirring at 80 ° C. for 30 minutes The alkoxylate having an average added mole number of PO of 2.0 was obtained.
As a result of gas chromatographic analysis and NMR analysis of the obtained alkoxylate, the alcohol or alkoxylate having 0 mol of PO addition was 2% by mass, the alkoxylate having 1 mol of PO addition was 22% by mass, and the alkoxy having 2 mols of PO addition. The rate was 29% by mass, and the alkoxylate having a PO addition mole number of 3 was 22% by mass.
The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas. The resulting sulfate was neutralized with an aqueous NaOH solution to obtain a composition containing polyoxypropane-1,2-diylalkyl ether sulfate.
As a result of gas chromatographic analysis and NMR analysis, the obtained composition contained 98% by mass of the anionic surfactant (a) represented by the formula (I).

Production Example 2 <Production of Anionic Surfactant (a-2)>
In the same manner as in Production Example 1, linear alcohol having 12 carbon atoms [trade name: Calcoal 2098] was dehydrated. After dehydration, nitrogen substitution was performed, and after raising the temperature to 120 ° C., 511 g of PO was charged. After an addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 1107 g of ethylene oxide (hereinafter referred to as “EO”) was charged. After addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C., and unreacted EO was removed at 4.0 kPa. After removing unreacted EO, 3.8 g of acetic acid was added to the autoclave, and after stirring at 80 ° C. for 30 minutes, extraction was performed and the average PO addition mole number was 0.7 and the average EO addition mole number was 2.0. An alkoxylate was obtained.
As a result of gas chromatographic analysis and NMR analysis of the resulting alkoxylate, the alcohol or alkoxylate having 0 mol of PO addition was 39% by mass, the alkoxylate having 1 mol of PO addition was 45% by mass, and the alkoxy having 2 mols of PO addition. The rate was 13% by mass, and the alkoxylate having a PO addition mole number of 3 was 2% by mass.
The resulting alkoxylate was sulfated in the same manner as in Production Example 1, and then neutralized to obtain an alkyl ether sulfate ester salt composition.
As a result of gas chromatographic analysis and NMR analysis, the obtained composition contained 60 mass of an anionic surfactant (a) represented by the general formula (I) (corresponding to m = 1 in the general formula (I)). % Was included.

<Other anionic surfactants>
LAS: sodium dodecylbenzenesulfonate (soft type), manufactured by Kao Corporation, trade name: Neoperex G-15
AS: Sodium tetradecyl sulfate prepared using a straight-chain alcohol having 14 carbon atoms [manufactured by Kao Corporation, trade name: Calcoal 4098] as a raw material. Mass ratio of alkyl chain length: C12 / C14 = 2/98 (corresponding to m = 0 in general formula (I))
AES: polyoxyethylene tetradecyl ether sulfate prepared from a straight-chain alcohol having 14 carbon atoms (trade name: Calcoal 4098, manufactured by Kao Corporation) as a raw material. Mass ratio of alkyl chain length: C12 / C14 = 2/98, EO average added mole number = 1.0

<Clay mineral (b)>
-Clay mineral 1: Made by Zude Chemi, trade name: Round rosyl DGA212 (bentonite granules, Na / Ca mass ratio: 2.545)
-Clay mineral 2: manufactured by Sud Kemi, trade name: Round rosyl PR414 (bentonite granule, mass ratio of Na / Ca: 0.833)
Clay mineral 3: manufactured by Hojun Co., Ltd., trade name: Bengel Bright 23 (bentonite powder, Na / Ca mass ratio: 2.27)
-Clay mineral 4: manufactured by Hojun Co., Ltd., trade name: Bengel Bright 11 (bentonite powder, Na / Ca mass ratio: 0.025)

<Ethoxylate nonion>
Polyoxyethylene alkyl ether manufactured by Kao Corporation was used. Alkyl chain length: C12 / C14 = 72/28, EO average added mole number = 6
<Other ingredients>
・ Crystalline silicate: Pre-feed granule (manufactured by Tokuyama Siltech Co., Ltd.)
・ Soap: Fatty acid salt having 12 to 20 carbon atoms ・ PEG: Polyethylene glycol (weight average molecular weight 10,000)
Zeolite: “Zeo Builder” (Zeo Builder, median diameter: 3.0 μm)
-Polymer: Polyacrylic acid (average molecular weight 15,000 by GPC; converted to polyethylene glycol)
Enzyme: “Cellulase K” (inoculated with Bacillus sp. KSM-635 strain, see JP-A-63-264699), “Cannase 24TK” (manufactured by Novozyme), “Sabinase 6.0T” (Novozyme) Used at a mass ratio of 3: 1: 2.

<Nonionic surfactant (d-1)>
Lauryl alcohol 93.2 g (0.50 mol) and lanthanum triflate 2.94 g (0.0050 mol) were placed in a 300 mL four-necked flask and heated to 90 ° C. with stirring under a nitrogen stream. Next, while maintaining the temperature, 148.16 g (2.0 mol) of glycidol was added dropwise over 24 hours, and the stirring was continued for 2 hours to obtain 243.5 g of a reaction product. As a result of gas chromatographic analysis of the obtained reaction product, the conversion rate of glycidol was 99.9% or more, the content of lauryl alcohol was 6.0% by mass, and the content of polyglycerol was 2.2% by mass.
Furthermore, after separating the components of this synthetic product having a glycerin condensation degree of 1 and 2 by column separation, and using these as preparations, a compound having a glycerin condensation degree y of 1 in the lauryl polyglyceryl ether obtained by gas chromatography and As a result of quantifying the compound having a glycerin condensation degree y of 2, the compound having a glycerin condensation degree y of 1 was 12.2% by mass, and the compound having a glycerin condensation degree y of 2 was 11.4% by mass.
Further, in the obtained lauryl polyglyceryl ether, the proportion of those having a glycerin condensation degree y of 3 to 5 was 43.3% by mass relative to the total of those having a y of 1 to 7. Therefore, it was confirmed that the product (d-1) contains a plurality of compounds having different glycerin condensation degrees y.

[2] Evaluation method of detergency, recontamination preventing property and flexibility Examples 1 to 10 and Comparative Examples 1 to 5
The above ingredients were blended in the proportions shown in Table 1 to prepare a powder laundry detergent composition, and the following methods were used to evaluate the cleaning power, recontamination preventing property, and flexibility. The results are shown in Table 1.

(1) Evaluation of detergency (preparation of collar red cloth)
A collar fabric was prepared according to JIS K3362 (1998).
(Cleaning conditions and evaluation method)
The detergency of each composition was compared based on Comparative Example 1 according to the method for evaluating the detergency of a synthetic detergent for clothing described in JIS K3362 (1998). The use concentration of the detergent composition for clothing in Table 1 was 1.0 g / L.
(Evaluation criteria)
○: Superior to Comparative Example 1 Δ: Equivalent to Comparative Example 1 ×: Inferior to Comparative Example 1

(2) Evaluation of carbon recontamination prevention property 1.0 g of the detergent composition was dissolved in 1 L of tap water at 20 ° C. Next, 0.25 g of carbon black selected by Japan Oil Chemical Association (Asahi Carbon Co., Ltd., suitable for cleaning Asahi cleaning) is added to this and irradiated with 26 ± 1.5 kHz ultrasonic wave for 5 minutes. Was uniformly dispersed.
The carbon black dispersion (20 ° C) is transferred to a sample cup of a stirring type detergency tester (trade name: Terg-O-Tometer, manufactured by Ueshima Seisakusho Co., Ltd.), and a 6 cm x 6 cm cotton white cloth (Japanese oil) A standard product selected by the Chemical Society, # 2023 cloth sold by the Laundry Science Association) was added and stirred at a rotational speed of 80 rpm for 10 minutes.
Next, the white cotton cloth was taken out, rinsed thoroughly and then dried, and the recontamination prevention rate was calculated by the following formula.
Recontamination prevention rate (%) = [(reflectance of white cotton cloth after test) / (reflectance of white cotton cloth before test)] × 100
The reflectance was measured by using a 550 nm filter under the trade name: NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd.
The recontamination prevention rate of each detergent composition was compared based on Comparative Example 1.
(Evaluation criteria)
A: Higher anti-recontamination property than Comparative Example 1 (10% or more of the anti-recontamination rate of Comparative Example 1)
○: Recontamination prevention property is relatively higher than Comparative Example 1 (5% or more and less than 10% of the recontamination prevention rate of Comparative Example 1)
Δ: Equivalent to Comparative Example 1 ×: Less recontamination prevention than Comparative Example 1 (5% or less of the recontamination prevention rate of Comparative Example 1)

(3) Evaluation of flexibility (preparation of evaluation towel)
A commercially available cotton towel (100% cotton) was used in a mini washing machine (“N-BK2” manufactured by Matsushita Electric Industrial Co., Ltd.), and a nonionic surfactant (alkyl chain length C12, C14 primary alcohol with an average of 6 moles of ethylene oxide added), crystalline silicate (pre-feed granule), sodium carbonate mixed at 1: 1: 3 (mass ratio) at 0.5 g / L used. After washing at a water temperature of 20 ° C. for 7 minutes, centrifugal dehydration, rinsing for 3 minutes, dehydration, rinsing for 3 minutes, and dehydration were repeated 5 times in total to remove the treatment agent.
(Flexible processing)
To 5 L of water at 20 ° C., 5.0 g of the detergent composition shown in Table 1 and 0.3 kg of cotton towel (4 sheets of 70 cm × 30 cm) were added and washed for 7 minutes. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes, dehydrated and air-dried.
(Evaluation methods)
A pair of the towel washed with the detergent composition and the pretreated towel was used, and five judges judged the sensory evaluation of the softness of the touch. When there is no difference and when it becomes hard, 0 points, when it becomes slightly softer, 1 point, when it becomes slightly softer, 2 points, when it becomes clear softly 3 points, the total points of 5 people are shown as follows It was. At this time, a grade of ○ or higher was regarded as an acceptable level.
(Evaluation criteria)
◎: Total of 10 points or more ○: Total of 6 points or more and less than 10 points △: Total of 3 points or more and less than 6 points ×: Total of less than 3 points

From Table 1, the garment detergent compositions of Examples 1 to 10 are remarkably superior in washing performance, recontamination prevention performance, and softening performance as compared to the garment detergent compositions of Comparative Examples 1 to 5. I understand that. Regarding the carbon recontamination prevention property, the detergent compositions of Examples 2, 6 and 9 were particularly excellent.

Examples 11 to 19 and Comparative Examples 6 to 11
The above ingredients were blended in the proportions shown in Table 2 to prepare a powdered laundry detergent composition, and the detergency, recontamination preventing property and flexibility were evaluated by the above methods. The results are shown in Table 2.

From Table 2, the garment detergent compositions of Examples 11 to 19 are remarkably superior in cleaning performance, recontamination prevention performance, and softening performance as compared with the garment detergent compositions of Comparative Examples 6 to 11. I understand that. Regarding the carbon recontamination preventing property, the detergent compositions of Examples 11, 12, 13 and 16 were particularly excellent.

ADVANTAGE OF THE INVENTION According to this invention, the detergent composition for clothing excellent in the washing | cleaning performance, the recontamination prevention performance, and the softening performance can be provided.
The detergent composition of the present invention is excellent in cleaning performance, recontamination prevention performance and softening performance, and can be widely used as a detergent composition for clothing, but is particularly useful for cotton clothing.

Claims (13)

1. A detergent composition for clothing containing an anionic surfactant (a) represented by the general formula (I) and a clay mineral (b).
   R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
   (Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O represents an oxyalkanediyl group having 3 and / or 4 carbon atoms, EO represents an oxyethylene group, and m and n are The number of moles added is shown, m is 1 to 10, and n is 0 to 20.)
2. The laundry detergent composition according to claim 1, further comprising a nonionic surfactant (c) represented by the general formula (III).
   R ² —O— (A ² O) x—H (III)
   (In the formula, R ² represents a hydrocarbon group having 6 to 22 carbon atoms, A ² O represents an oxyalkanediyl group having 2 to 4 carbon atoms, and x represents the number of added moles and is 1 to 20).
3. A detergent composition for clothing containing an anionic surfactant (a) represented by the general formula (I), a clay mineral (b), and a nonionic surfactant (d) represented by the general formula (IV) .
   R ¹ —O— (A ¹ O) m- (EO) n—SO ₃ M (I)
   (In the formula, R ¹ , A ¹ O, EO, m and n are the same as described above.)
   R ³ —O— (C ₃ H ₆ O ₂ ) yH (IV)
   (In the formula, R ³ represents a hydrocarbon group of 6 to 22, and y represents a degree of glycerol condensation and is a number of 1 to 7.)
4. In the nonionic surfactant (d) represented by the general formula (IV), [R ³ —O— (C ₃ H ₆ O ₂ ) ₃ to ₅ —H / R ³ —O— (C ₃ H ₆ O The clothes detergent composition according to claim 3, wherein the mass ratio of ₂ ) ₁ to ₇ -H] is 0.3 or more.
5. The mass ratio of the anionic surfactant (a) to the nonionic surfactant (d) [anionic surfactant (a) / nonionic surfactant (d)] is 0.3 or more. Or the detergent composition for clothes of 4.
   
6. The laundry detergent composition according to any one of claims 1 to 5, wherein R ^{1 in the} general formula (I) is a linear alkyl group having 6 to 22 carbon atoms.
7. The detergent composition for clothing according to any one of claims 1 to 6, wherein m in the general formula (I) is 1 to 3.
8. The garment detergent composition according to any one of claims 1 to 7, wherein the content of the anionic surfactant (a) is 1 to 80% by mass.
9. The laundry detergent composition according to any one of claims 1 to 8, wherein the clay mineral (b) content is 1 to 80% by mass.
10. The garment detergent composition according to claim 2, wherein the content of the nonionic surfactant (c) is 0 to 80% by mass.
11. The garment detergent composition according to claim 3 or 4, wherein the content of the nonionic surfactant (d) is 0.1 to 80% by mass.
12. The laundry detergent composition according to any one of claims 1 to 11, wherein the clay mineral (b) is a smectite-type layered clay mineral.
13. Use of the composition according to any one of claims 1 to 12 in a laundry detergent.