JP2016047871A - Powder detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition for clothing generating a moderate slimy feeling during washing and excellent in resoiling prevention effect.SOLUTION: There is provided a powder detergent composition for clothing containing a polymer compound which contains (a) an anionic surfactant of 8 mass% to 40 mass% inclusive, (b) an alkali agent of 10 mass% to 60 mass% inclusive, (c) a monomer constituent unit having an anionic group and a monomer constituent unit having a cationic group and has a weight average molecular weight of 300,000 or less, where a mass ratio of (a)/(c) is 2 to 200 inclusive, and a pH of 0.5 mass% solution at 25°C is 10.2 to 12.0 inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a powder detergent composition for clothing and a washing method.

  Washing machines are spreading in Asian regions such as Greater China and ASEAN, but hand-washing still exists. In hand-washing laundry, the detergent concentration is used at a relatively high concentration of 0.2 to 1.5%, and many users dissolve the detergent in water and then immerse the laundry for a certain period of time before washing. It is known.

  On the other hand, in addition to the cleaning effect, another function is imparted to the laundry detergent. For example, a function of imparting flexibility to clothing and a function of imparting a soil release effect to clothing are known.

  Patent Document 1 discloses a detergent composition that includes a surfactant containing a nonionic surfactant, an alkali agent, and a quaternary nitrogen-containing polymer in a predetermined range and can impart a high cleaning effect and good flexibility to a textile product. Things are listed.

  Patent Document 2 discloses sebum stains on cotton cloth containing amphoteric polymers (excluding graft copolymers) obtained by copolymerizing an anionic monomer and a cationic monomer and polyethylene glycol in a predetermined range. A cleaning composition capable of imparting a soil release effect such as is described.

JP 2002-060789 A JP 2001-131590 A

The present inventors have examined a new function in addition to the cleaning effect, and it has been found that a person performing hand-washing may expect a cleaning power due to the presence of a null in the washing liquid. Therefore, it may be desired that the washing liquid has an appropriate null. Moreover, in order to improve the detergency in hand-washing, it is desirable to have an excellent anti-recontamination effect so that dirt once detached does not reattach to clothing.
The present invention provides a powder detergent for clothing that is moderately nullified during washing and has an excellent anti-contamination effect.

The present invention comprises (a) an anionic surfactant (hereinafter referred to as component (a)) of 8% by mass or more and 40% by mass or less, (b) an alkali agent (hereinafter referred to as component (b)) of 10% by mass or more, 60 A polymer compound having a weight average molecular weight of 300,000 or less (hereinafter referred to as component (c)), including a monomer constituent unit having (c) a cationic group and a monomer constituent unit having an anionic group. Containing
The mass ratio of (a) / (c) is 2 or more and 200 or less,
The pH of a 0.5 mass% aqueous solution at 25 ° C is 10.2 or more and 12.0 or less,
The present invention relates to a powder detergent composition for clothing.

  Moreover, this invention relates to the washing | cleaning method which has the process of wash | cleaning the clothing which contacted the washing | cleaning liquid containing the powder detergent composition for clothing of the said invention and the said water, and the process of rinsing the wash | cleaned clothing with water.

  According to the present invention, there is provided a powder detergent composition for clothing that is moderately nullified during washing and has an excellent recontamination preventing effect.

<(A) component>
As the anionic surfactant, one or more anions selected from alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate salt, α-sulfo fatty acid ester salt, and fatty acid salt Surfactant is mentioned. Among these, one or more anionic surfactants selected from alkyl benzene sulfonates, alkyl sulfate esters, and polyoxyalkylene alkyl ether sulfates are preferable, and alkyl benzene sulfonates are more preferable. Here, the carbon number of the alkyl group in the anionic surfactant is preferably 8 or more, more preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, more preferably. Is 14 or less. The oxyalkylene group is preferably an ethyleneoxy group. The average number of added moles is preferably 0.5 or more, more preferably 1 or more, and is preferably 10 or less, more preferably 5 or less. The salt of the anionic surfactant is preferably an alkali metal salt such as sodium salt or potassium salt. The use of the component (a) is particularly preferable from the viewpoint that the washing liquid has a null.

<(B) component>
The component (b) is preferably one or more alkali agents selected from alkali metal carbonates, amorphous alkali metal silicates, crystalline alkali metal silicates, and alkanolamines. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium sesquicarbonate, and sodium hydrogen carbonate. Alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. The alkali agent is preferably one or more alkali agents selected from sodium carbonate and potassium carbonate, and more preferably sodium carbonate. The use of the component (b) is particularly preferable from the viewpoint that the washing liquid has a null.

<(C) component>
The component (c) is a polymer compound including a monomer constituent unit having a cationic group and a monomer constituent unit having an anionic group and having a weight average molecular weight of 300,000 or less.

  Examples of the monomer structural unit having a cationic group [hereinafter referred to as monomer unit (c1)] include a monomer unit having at least one group selected from an amino group and a quaternary ammonium group.

  The monomer unit (c1) is preferably, for example, a monomer unit derived from one or more monomers selected from a compound of the following general formula (c1-1) and a compound of the general formula (c1-2).

[Where:
R ^1c , R ^2c , R ^3c , R ^7c , R ^8c , and R ^9c are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom or 1 or more carbon atoms 3 or less alkyl groups are preferred.
X and Y are each independently a group selected from an alkylene group having 1 to 12 carbon atoms, —COOR ^12c —, —CONHR ^12c —, —OCOR ^12c —, and —R ^13c —OCO—R ^12c —. And an alkylene group having 1 to 3 carbon atoms or —COOR ^12c — is preferable. Here, R ^12c and R ^13c are each independently an alkylene group having 1 to 5 carbon atoms.
R ^4c is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or (R ^1c ) (R ^2c ) C═C (R ^3c ) —X—, and (R ^1c ) (R ^2c ) ^C═ C (R ^3c ) —X— is preferred.
R ^5c and R ^6c are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, preferably an alkyl group having 1 to 3 carbon atoms.
R ^10c is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or (R ^7c ) (R ^8c ) C═C (R ^9c ) —Y—, and having 1 to 3 carbon atoms. Are preferred.
R ^11c is a hydrogen atom, or an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
Z ^- is an anion such as halogen ion, sulfate ion, 1 or more carbon atoms, 3 an alkyl sulfate ion, 1 or more carbon atoms, 3 an alkyl which may be aromatic sulfonate ion substituted by a group And hydroxy ions. ]

  Examples of the compound of the general formula (c1-1) include acryloyl (or methacryloyl) aminoalkyl (C1 or more and 5 or less) -N, N, N-trialkyl (C1 or more and 3 or less) quaternary ammonium salt. , Acryloyl (or methacryloyl) oxyalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, N- (ω-alkenyl (2 carbon atoms) 10 or less))-N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N , N-dialkyl (C1 or more, 3 or less) quaternary ammonium salt. Among them, N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt is preferable, for example, N, N-diallyl -N, N-dimethylammonium salt and the like. N, N-diallyl-N, N-dimethylammonium chloride is more preferred.

  Examples of the compound represented by the general formula (c1-2) include acryloyl (or methacryloyl) aminoalkyl (1 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) amine, acryloyl (or methacryloyl). Oxyalkyl (1 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) amine, N- (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (C1 or more and 3 or less) amine, N, N-di (ω-alkenyl (C2 or more and 10 or less))-N-alkyl (C1 or more and 3 or less) amine, allylamine, diallylmethylamine Diallylamine. Preferred are compounds selected from allylamine, diallylmethylamine, diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, and acryloyl (or methacryloyl) oxyethyl-N, N-dimethylamine.

  The monomer structural unit having an anionic group [hereinafter referred to as monomer unit (c2)] is a structural unit derived from a monomer having an anionic group. The monomer unit (c2) is acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate , Vinyl sulfonate, methallyl sulfonate, sulfopropyl methacrylate, and monomer units derived from one or more monomers selected from mono-ω-methacryloyloxyalkyl phosphate (1 to 12 carbon atoms). It is done. The monomer unit (c2) is a monomer unit derived from one or more monomers selected from acrylic acid or its sodium salt or potassium salt, methacrylic acid or its sodium salt or potassium salt, and maleic acid or its sodium salt or potassium salt Is preferred.

  Component (c) has a monomer unit (c1) to monomer unit (c2) molar ratio [monomer unit (c1)] / [monomer unit (c2)] of preferably 30/70 or more, more preferably 35/65. More preferably, 40/60 or more, still more preferably 45/55 or more, and preferably 90/10 or less, more preferably 85/15 or less, more preferably 80/20 or less, still more preferably 75/25 or less. It is.

The component (c) can include a monomer unit represented by —SO ₂ — (hereinafter referred to as monomer unit (c3)). As a method for introducing such a monomer unit into the polymer, a predetermined amount of SO ₂ gas is blown into a solution containing the monomer derived from the monomer units (c1) and (c2), and benzoyl peroxide, t- Butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2′-azobis (2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, It can be obtained by polymerization using a polymerization initiator selected from methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfate, and hydrogen peroxide. A solvent can be used at the time of polymerization. Specifically, alcohols selected from water, methanol, ethanol and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazo Lydinone, acetonitrile, propionitrile, toluene, xylene and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, and preferably 200 ° C. or lower, more preferably 100 ° C. or lower. In the present invention, polymerization can also be performed by light or radiation. For example, the polymerization can be efficiently performed by irradiating light having a wavelength of 300 nm or more and 450 nm or less.

  The proportion of the monomer unit (c3) is preferably 0 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 20 mol in the total monomer units of the component (c). % Or less, more preferably 15 mol% or less, still more preferably 10 mol% or less. Moreover, (c) component may have another monomer structural unit in the range which does not impair the effect of this invention.

  Component (c) is a total ratio of monomer units (c1) and monomer units (c2), or a total ratio of monomer units (c1), monomer units (c2) and monomer units (c3). Among these, preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.

  The component (c) is a polymer compound having a weight average molecular weight of 300,000 or less. This weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent. The weight average molecular weight of the component (c) is preferably 1000 or more, more preferably 2000 or more, further preferably 5000 or more, and preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. .

  Component (c) may be randomly polymerized, block polymerized, or graft polymerized. In the case of graft polymerization, the monomer unit (c1), the monomer unit (c2), and preferably the monomer unit (c3) may be present in either the main chain or the side chain in the polymer. The component (c) of the present invention is composed of a polymer composed only of the monomer unit (c1) and the monomer unit (c2), or composed only of the monomer unit (c1), the monomer unit (c2) and the monomer unit (c3). The polymer is mentioned.

As the component (c),
N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl) to be the monomer unit (c1) ) Oxyalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt and acryloyl (or methacryloyl) oxyalkyl (1 to 5 carbon atoms) Or less) —N, N-dialkyl (1 to 3 carbon atoms) amine, preferably N, N-diallyl-N, N-dimethylammonium salt, more preferably N, N-diallyl -N, N-dimethylammonium chloride;
A monomer selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, and maleic anhydride to be a monomer unit (c2);
These copolymers are preferred.

In addition, as the component (c),
N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl) to be the monomer unit (c1) ) Oxyalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt and acryloyl (or methacryloyl) oxyalkyl (1 to 5 carbon atoms) Or less) —N, N-dialkyl (1 to 3 carbon atoms) amine, preferably N, N-diallyl-N, N-dimethylammonium salt, more preferably N, N-diallyl -N, N-dimethylammonium chloride;
A monomer selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, and maleic anhydride to be a monomer unit (c2);
Sulfur dioxide to be the monomer unit (c3);
These copolymers are preferred.
The use of the component (c) is particularly preferable from the viewpoint of detergency.

<Composition of powder detergent composition for clothing>
In the powder detergent composition for clothing of the present invention, the component (a) is 8% by mass or more, preferably 10% by mass or more, more preferably 12% by mass or more, and 40% by mass or less, preferably 35% by mass or less. More preferably, it contains 30 mass% or less. This range is preferable from the viewpoint of the presence of the washing liquid and the cleaning power.

  In the powder detergent composition for clothing of the present invention, the component (b) is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and 60% by mass or less, preferably 50% by mass or less. More preferably, it contains 45 mass% or less. This range is preferable from the viewpoint of the presence of the washing liquid and the cleaning power.

  In the powder detergent composition for clothing of the present invention, the component (c) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 15%. It is contained by mass% or less, preferably 12 mass% or less, more preferably 10 mass% or less. This range is preferable from the viewpoint of nullification of the washing liquid.

  In the powder detergent composition for clothing of the present invention, the mass ratio of the component (a) to the component (c) is (a) / (c) and is 2 or more and 200 or less. The mass ratio of (a) / (c) is preferably 4 or more, more preferably 5 or more, more preferably 10 or more, and preferably 150 or less, preferably 120 or less, more preferably 100 or less, more preferably 50 or less, more preferably 30 or less. This range is preferable from the viewpoint of generating appropriate nulling during washing.

  The detergent composition of the present invention can contain a sequestering agent as the component (d). Examples of the component (d) include one or more sequestering agents selected from zeolite and tripolyphosphate. In the powder detergent composition for clothing of the present invention, the component (d) is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less. This range is preferable from the viewpoint of the fluidity of the detergent composition when the component (c) is blended.

  The powder detergent composition for clothing of the present invention comprises a water-soluble neutral inorganic salt as component (e), a water-soluble polymer as component (f) (hereinafter, excluding component (c)), a powder surface coating agent, an enzyme , Anti-staining agents, reducing agents (sulfites, etc.), antifoaming agents (silicones, etc.), bleaching agents, bleach activators, fluorescent dyes, color granules, fragrances, coloring agents (pigments and dyes) etc. be able to. Moreover, if it is in the range which does not impair the effect of this invention, nonionic surfactants, such as polyoxyethylene alkyl ether, can also be mix | blended.

  (E) As a component, sodium sulfate, potassium sulfate, sodium chloride, or potassium chloride is mentioned, for example. Among these, sodium sulfate or potassium sulfate is preferable, and sodium sulfate is more preferable.

  The content of the component (e) is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more in the detergent composition of the present invention from the viewpoint of economy, and preferably Is 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 25% by mass or less.

  Examples of the component (f) include organic polymers having a solubility in 100 g of water at 25 ° C. of 0.5 g or more and a weight average molecular weight of 1,000 or more. For example, polyalkylene glycol, salt of acrylic acid-maleic acid copolymer, polyacrylate, carboxymethylcellulose, soluble starch, saccharides and the like can be mentioned. Among them, carboxylic acid polymers having a weight average molecular weight of 2,000 or more and 100,000 or less and weight average molecular weights of 2,000 or more and 100,000 or less in terms of sequestering ability, dispersibility of solid or particle dirt and ability to prevent recontamination. Polyethylene glycol is preferred. Component (f) is a salt of an acrylic acid-maleic acid copolymer having a weight average molecular weight of 2,000 or more and 100,000 or less, a polyacrylate having a weight average molecular weight of 2,000 or more and 100,000 or less, and a weight average molecular weight of 2,000. A water-soluble polymer selected from polyethylene glycol of 100,000 or less is preferable. Here, examples of the salt include sodium salt, potassium salt, and ammonium salt.

  The weight average molecular weight of the component (f) is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent.

  The content of the component (f) in the detergent composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. In addition, the content of the component (f) is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass or less in the detergent composition.

  As the nonionic surfactant, the carbon number of the alkyl group is preferably 8 or more, more preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, more preferably 14 And the average number of added moles of ethyleneoxy group is preferably 1 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. Etc. The content of the nonionic surfactant in the detergent composition is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less.

  The detergent composition of the present invention is in powder form, and the water content in the composition (according to the heat loss method described in JIS K 3362: 2008) is preferably 0.5% by mass or more from the viewpoint of solubility and productivity. , More preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 6% by mass or less.

In the powder detergent composition for clothing of the present invention, the pH of a 0.5 mass% aqueous solution at 25 ° C is 10.2 or more and 12.0 or less. This pH is preferably 10.3 or more, more preferably 10.4 or more, and preferably 11.5 or less, more preferably 11.2 or less. This range is preferable from the viewpoint of generating appropriate nulling during washing.
Here, the measurement of pH can be performed as follows. A pH electrode (model 6367) is pre-calibrated with a phthalate buffer solution (pH 4.01), a phosphate standard solution (pH 6.84), and a borate standard solution (pH 9.18) on a pH meter D-52 manufactured by HORIBA, Ltd. Rinse thoroughly with ion-exchanged water. Next, a pH electrode is placed in the aqueous solution, and measurement is performed using the AUTO HOLD mode of the pH meter until the measured value becomes constant.

  The detergent composition of the present invention has an apparent density (apparent density measured by a method defined by JIS K 3362: 2008) of preferably 1600 g / L or less, more preferably 1300 g / L or less, more preferably 1000 g / L. It is as follows. In terms of convenience and waste reduction, the apparent density is preferably 300 g / L or more, more preferably 350 g / L or more, more preferably 400 g / L or more, and more preferably 500 g / L or more.

  The detergent composition of the present invention can be produced by applying a known method. For example, spray drying method, dry neutralization method described in Japanese Patent No. 3313372, dry granulation method, dry blending method, fluidized bed drying method, thin film drying method, extrusion granulation method, rolling granulation method, stirring granulation It can be produced by applying a method, a compaction granulation method, a surfactant-carrying method, or a combination thereof.

<How to wash>
The present invention provides a method for washing clothes using a cleaning liquid prepared by mixing the powder detergent composition for clothes of the present invention and water.

The German hardness of the water mixed with the detergent composition may be 1 ° dH or higher, further 2 ° dH or higher, and further 5 ° dH or higher, preferably 30 ° dH or lower, more preferably 25 ° dH or lower. .
Here, the German hardness (° dH) in this specification means the concentration of calcium and magnesium in water in terms of CaCO ₃ as 1 mg / L (ppm) = about 0.056 ° dH (1 ° dH = 17. 8 ppm).

  In general, water used for washing contains calcium ions and magnesium ions as hardness components. In the present invention, the water mixed with the detergent composition is one containing calcium ions and magnesium ions as hardness components. In the present invention, the molar ratio of calcium ions to magnesium ions in water mixed with the detergent composition may be 5/5 or more, or 6/4 or more in terms of calcium ions / magnesium ions, and 9/1. Or may be 8/2 or less.

  In the washing method of the present invention, the concentration of the component (c) in the cleaning liquid is preferably 2 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm or more, and preferably 1000 ppm or less, more preferably 500 ppm or less. More preferably, the powder detergent composition for clothing can be used in an amount of 100 ppm or less.

  The washing method of the present invention is also effective in a method of washing clothes by hand. That is, the present invention is also effective in a method of washing clothes by hand using a cleaning liquid prepared by mixing the detergent composition of the present invention and water. Since the cleaning liquid prepared from the detergent composition of the present invention has an appropriate null, it can give the user a desirable feel during hand-washing.

  Examples of the hand-washing washing method using the detergent composition of the present invention include a method of washing clothes by bringing the garment into contact with a cleaning liquid prepared from the detergent composition of the present invention. The cleaning effect is high when the contact time is long. Preferably, a better effect is obtained when the garment is brought into contact with the cleaning liquid for 10 minutes or more. A higher effect can be obtained by applying the cleaning solution directly to the soiled portion. In the present invention, it is preferable that the time from the first contact of the clothing with the cleaning liquid to the end of the cleaning is 10 minutes or more. When rinsing is performed, the end of cleaning is defined as the start of rinsing.

  In the washing method of the present invention and the hand washing laundry method of the present invention, it is preferable to wash the clothes after immersing the clothes in the washing liquid. The time for immersing the clothing in the cleaning solution is preferably 10 minutes or more, more preferably 15 minutes or more, more preferably 25 minutes or more, and preferably 720 minutes or less, more preferably 300 minutes or less, more preferably 180 minutes. Min or less, more preferably 120 min or less.

  In the washing method of the present invention and the hand washing method of the present invention, the mass of the washing liquid with respect to the mass of the garment is preferably 2 times or more, more preferably 3 times or more, more preferably 5 times or more, and preferably It is 100 times or less, more preferably 50 times or less, more preferably 25 times or less.

  Furthermore, by thoroughly rubbing or brushing the clothes in contact with the cleaning liquid according to the present invention by hand, not only a good detergency is obtained, but also rich foaming is visually preferable.

After rubbing or the like, the clothes are taken out from the cleaning solution, squeezed to drain the water, or drained using a dehydrator, and immersed again in fresh water (hereinafter referred to as rinse water). The rinsing water may be either water stored in a basin or running water. The mass of rinsing water for clothing is preferably 2 times or more, more preferably 5 times or more, more preferably 10 times or more, and preferably 1,000 times or less, more preferably, based on the total amount of rinsing water. 500 times or less, more preferably 100 times or less. If this operation is repeated several times, the bubbling disappears and the rinsing can be terminated at this point.
In addition, as rinse water, the water used for preparation by mixing as the said washing | cleaning liquid can be used.

  The washing method of the present invention, and further the hand washing method of the present invention comprises a step of washing clothing, preferably a step of washing by hand, and the washed clothing, wherein the washing liquid comprising the powder detergent composition for clothing of the present invention and water is contacted It is preferred to have a process of rinsing with water.

The powder detergent composition for clothes shown in Table 1 was prepared, and the following items were evaluated.
<Evaluation with null>
In a 100 mL glass beaker, 0.5 g of the above composition was dissolved in 100 g of water at 25 ° C. and 10 ° dH (Ca ion / Mg ion molar ratio: 7/3). Next, the condition of the nulls when the fingertips were immersed in the obtained cleaning liquid and rubbed together was evaluated in the following four stages using Comparative Example 1 as a reference (evaluation point 0).
+: Larger with null than standard 0: Same as standard with null-: Smaller with null than standard ---: No null

<Recontamination prevention evaluation>
5 g of the composition was dissolved in 1000 g of water at 25 ° C. and 10 ° dH (Ca ion / Mg ion molar ratio: 7/3), and then carbon black selected by the Japan Oil Chemists' Society (Asahi Carbon Co., Ltd.) 0.25 g is added and carbon black is uniformly dispersed by irradiating with ultrasonic waves of 26 ± 1.5 KHz for 5 minutes. Next, this was transferred to a sample cup of a stirring type detergency tester (Targ-O-Tometer) at 25 ° C., and a 6 cm × 6 cm cotton white cloth (standard product selected by Japan Oil Chemists' Society, Laundry Science) Put 5 sheets of # 2023 cloth sold by the association) and stir for 10 minutes at a rotation speed of 100 ± 5 times / min. Next, the white cotton cloth is taken out and lightly squeezed by hand so that the water content is 200% by mass or less, and then 1000 mL of water at 25 ° C. and 10 ° dH (Ca ion / Mg ion molar ratio is 7/3). And rinsing for 3 minutes using a stirring type detergency tester (rotation speed 100 ± 5 times / min), and this rinsing operation is performed twice in total. Next, after air drying, ironing was performed and the reflectance at 550 nm was determined. The recontamination prevention rate was determined from the reflectance by [(reflectance of cotton after test) / (reflectance of cotton before test)] × 100, and evaluated according to the following criteria.
Evaluation criteria ○: Recontamination prevention rate is 75% or more ×: Recontamination prevention rate is less than 75%

(Note) The components in the table are as follows.
1) Linear alkyl (C10-C13) sodium benzenesulfonate.
2) Linear alkyl (carbon number 12-14) sodium sulfate 3) Linear alkyl (carbon number 12) ether sodium sulfate (ethylene oxide average addition mole number 2)
4) Polyoxyethylene alkyl ether (the alkyl group is a linear alkyl group having 12 carbon atoms, the average number of moles of ethylene oxide added is 6)
5) Light ash, manufactured by Central Glass Co., Ltd. 6) Polymerized at a molar ratio of N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6. Copolymer (weight average molecular weight 20,000)
7) Copolymer polymerized at a molar ratio of N, N-diallyl-N, N-dimethylammonium chloride / acrylic acid = 69.5 / 30.5 (weight average molecular weight 450,000)

* Comparative Example 2 showed a pH adjusted value with 1 mol / L HCl. A detergent aqueous solution adjusted to this pH was used for evaluation of nullification and anti-recontamination property.
** Comparative Example 4 and Comparative Example 5 showed pH adjusted values with 1 mol / L NaOH. A detergent aqueous solution adjusted to this pH was used for evaluation of nullification and anti-recontamination property.

Claims (7)

(A) Anionic surfactant 8 mass% or more and 40 mass% or less, (b) Alkali agent 10 mass% or more and 60 mass% or less, (c) Monomer structural unit and anionic group having a cationic group A high molecular compound having a monomer constituent unit and having a weight average molecular weight of 300,000 or less,
The mass ratio of (a) / (c) is 2 or more and 200 or less,
The pH of a 0.5 mass% aqueous solution at 25 ° C is 10.2 or more and 12.0 or less,
Powder detergent composition for clothing.   One or more kinds of anionic surface activity in which (a) is selected from alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate, α-sulfo fatty acid ester salt, and fatty acid salt The powder detergent composition for clothes according to claim 1, which is an agent.   The powder for clothing according to claim 1 or 2, wherein (b) is one or more alkali agents selected from alkali metal carbonates, amorphous alkali metal silicates, crystalline alkali metal silicates, and alkanolamines. Detergent composition. The monomer structural unit having a cationic group of (c) is a monomer unit derived from one or more monomers selected from a compound of the following general formula (c1-1) and a compound of the general formula (c1-2). The powder detergent composition for clothes according to any one of claims 1 to 3.

[Where:
R ^1c , R ^2c , R ^3c , R ^7c , R ^8c and R ^9c are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
X and Y are each independently a group selected from an alkylene group having 1 to 12 carbon atoms, —COOR ^12c —, —CONHR ^12c —, —OCOR ^12c —, and —R ^13c —OCO—R ^12c —. It is. Here, R ^12c and R ^13c are each independently an alkylene group having 1 to 5 carbon atoms.
R ^4c is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or (R ^1c ) (R ^2c ) C═C (R ^3c ) —X—.
R ^5c and R ^6c are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group.
R ^10c is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or (R ^7c ) (R ^8c ) C═C (R ^9c ) —Y—.
R ^11c is a hydrogen atom, or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms.
Z ⁻ is an anion. ]   (C) The monomer structural unit having an anionic group is acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, a styrene sulfonate, or 2-acrylamido-2-methylpropane. One or more selected from sulfonate, allyl sulfonate, vinyl sulfonate, methallyl sulfonate, sulfopropyl methacrylate, and mono-ω-methacryloyloxyalkyl phosphate (1 to 12 carbon atoms) The powder detergent composition for clothing according to any one of claims 1 to 4, which is a monomer unit derived from a monomer.   The molar ratio of the monomer structural unit having a cationic group and the monomer structural unit having an anionic group (c) [monomer structural unit having a cationic group] / [monomer structural unit having an anionic group] The powder detergent composition for clothing according to any one of claims 1 to 5, wherein is 30/70 or more and 90/10 or less.   The washing | cleaning method which has the process of wash | cleaning the clothing which contacted the washing | cleaning liquid containing the powder detergent composition for clothing of any one of Claims 1-6, and water, and the process of rinsing the washed clothing with water.