WO2015098265A1 - Powder cleaning agent composition - Google Patents

Abstract

The present invention is a powder cleaning agent composition containing (a) an anionic surfactant, (b) a carboxylic acid whereof the primary acid dissociation constant is between 1 and 5 inclusive, the maximum acid dissociation constant is 7 or lower, and the molecular weight is between 46 and 5,000 inclusive, and (c) one or more species of compounds chosen from among inorganic sulfates and inorganic halogenated compounds, each in a predetermined range. The powder cleaning agent composition has a content of 10% or less by mass in inorganic carbonate whereof the solubility is 0.1 g or greater in 100 g of water at 20°C. The powder cleaning agent composition contains, in a specific mass ratio and serving as (a), a specific alkyl sulfate ester salt and one or more species chosen from among specific polyoxyethylene alkyl sulfate ester salts and specific alkyl benzene sulfonates. The (a)/(b) ratio by mass is between 1 and 40 inclusive. The powder cleaning agent composition has a total content of 4% by mass or less in predetermined protease granulated material and predetermined cellulase granulated material. When the powder cleaning agent composition is diluted 300-fold in water at 20°C, the pH is between 2.5 and 6.5 inclusive.

Description

Powder cleaning composition

The present invention relates to a powder detergent composition and a method for washing clothes by hand.

Background Art In a powder cleaning composition, an alkaline component is generally blended because it is considered that the cleaning power is enhanced by making the pH of the cleaning liquid alkaline.

Japanese Patent Application Laid-Open No. 2013-213184 discloses that a powder cleaning composition containing an alkali carbonate or an alkali hydrogen carbonate salt as an alkali component exhibits an excellent detergency against a stain on a collar sleeve in washing clothes or the like. It is disclosed.

In recent years, there has been a tendency for the spread of washing machines in the Asian region. However, hand-washing is still widely performed because of its detergency, economical viewpoint, cultural background, and washing awareness. Hand-washing is suitable for fine cleaning according to the situation, such as how soil is removed and the type of clothing, compared to washing with a washing machine.

However, hand washing is a work accompanied by physical and mental fatigue. In addition, when measuring or dissolving the cleaning agent, the powder cleaning agent is grasped by hand and stirred in water, so that irritation may be felt due to the influence of the components in the cleaning agent. In addition, during washing, the hands are put in the washing solution for a long time, so the hands feel wet and irritated by the influence of alkali components and cleaning ingredients. May cause discomfort and may need to be treated with hand cream. For this reason, there is a demand for products that appeal to the mildness of the cleaning ingredients for clothing cleaners.

In Japanese translations of PCT publication No. 2008-519148, laundry detergent, particularly heavy liquid laundry detergent capable of providing a pH of around 6 in washing water of a washing machine, decomposes deposits that cause darkening on the fabric surface. It has been disclosed that it may be useful for improved grease cleaning and cleaning of bleachable soils such as tea and wine.

US Patent Application Publication No. 2013/0184195 describes laundry detergents, particularly heavy liquid laundry detergents that can provide a pH of around 6 in the washing water of a washing machine, with excellent stain removal and detergent ingredients in clothing. It is disclosed that it does not remain.

Japanese Patent Application Publication No. 2002-509981 discloses that an acidic detergent composition containing an acidic protease is excellent in removing stain stains such as coffee and can prevent adhesion of scales formed by hardness components in water. .

Japanese Patent Application Laid-Open No. 2007-238861 discloses that a powder cleaning composition for a dishwasher, in which a polymer having an alkali component and a cationic group is blended, is excellent in food stain removal and water spot formation suppressing effect. It is disclosed.

SUMMARY OF THE INVENTION
(A) component: Anionic surfactant 0.1 mass% or more, 50 mass% or less,
Component (b): a carboxylic acid having a primary acid dissociation constant of 1 or more and 5 or less, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 or more and 5,000 or less 1% by mass or more and 15% by mass And (c) component: one or more compounds selected from inorganic sulfates and inorganic halogen compounds 30% by mass or more and 80% by mass or less of a powder detergent composition,
As component (a), the carbon number of the alkyl group is 10 or more and 16 or less, the polyoxyethylene alkylsulfuric acid ester salt having an ethylene oxide average addition mole number of 1 or more and 3 or less, and the carbon number of the alkyl group is 10 or more and 16 or less. 1 or more types chosen from alkylbenzene sulfonate, and the alkyl sulfate ester salt whose carbon number of an alkyl group is 10 or more and 16 or less,
A polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an ethylene oxide average addition mole number of 1 to 3 is represented as (a) _AES, and the alkyl group has 10 to 16 carbon atoms. the following alkylbenzene sulfonate indicated as (a) _LAS, the number of carbon atoms in the alkyl group is 10 or more, and the display 16 following the alkyl sulfate and (a) _aS, (a) _aS / [(a) _AES + (a) _LAS ] is a mass ratio of 0.05 or more and 0.9 or less,
The mass ratio of (a) component / (b) component is 1 or more and 40 or less,
The content of inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 10% by mass or less,
Protein content is 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less protease granulation product and protein content 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less The total content of cellulase granulate is 4% by mass or less,
When the powder detergent composition is diluted 300 times with water at 20 ° C., the pH is 2.5 or more and 6.5 or less.
The present invention relates to a powder cleaning composition.

The present invention also relates to a method for washing clothes by hand using the powder cleaning composition of the present invention.

Detailed description of the invention Japanese Patent Application Laid-Open No. 2013-213184 is excellent in detergency because it contains a large amount of an alkali component, but it causes serious damage to hands during washing in the Asian region, so there is room for improvement. was there. In addition, it has been found that, in hand-washing washing, even if it is a detergent containing a relatively large amount of alkali components, it is surprisingly not possible to exert sufficient cleaning power against food-derived oil stains.
The detergent compositions described in JP-T-2008-519148 and US Patent Application Publication No. 2013/0184195 are in a liquid state and are assumed to be used in a washing machine. However, handwashers in Asia have many users of powder detergents, so there is room for improvement in terms of use. In addition, hand damage is greatly influenced by pH at the time of washing and the concentration of the surfactant, but in Japanese translations of PCT publication No. 2008-519148 and US Patent Application Publication No. 2013/0184195, There is no indication regarding the effect, and in particular the disclosure about the relationship between surfactant concentration and hand irritation was insufficient. Furthermore, in Japanese translations of PCT publication No. 2008-519148 and US Patent Application Publication No. 2013/0184195, there is a room for improvement because of the low detergency of food-derived oil stains in the hand-washing scene, which is regarded as a major issue.

In JP 2002-509981 A, a large amount of the acidic protease compounded causes serious damage to the hands during hand washing, and the detergency against food-derived oil stains is insufficient. There was room for improvement.

Japanese Patent Application Laid-Open No. 2007-238861 exhibits excellent cleaning power against food-derived oil stains due to alkali components, but when used in a dishwasher or in a “speed course”, alkali components remain in the dishes after use. In some cases, slipping occurred. For this reason, there has been a demand for a further improvement in cleaning power that can suppress sliminess even in detergents for dishwashers.

The present invention provides a powder detergent composition that has excellent solubility in water, has a high detergency against food-derived oil stains, is gentle on the hand skin, and does not remain sticky on the object after washing. provide.

According to the present invention, the powder detergent composition has excellent solubility in water, has a high detergency against food-derived oil stains, is gentle on the hand skin, and does not easily remain wet on the object after washing. Things are provided.
The powder detergent composition of the present invention has a high detergency for food-derived oil stains by keeping the pH during washing in an acid state in washing clothes. Moreover, since the powder cleaning composition of this invention is excellent in the solubility to water, there is no residue. Moreover, the powder cleaning composition of this invention can reduce the damage to a hand skin. Moreover, the powder cleaning composition of this invention can reduce the sliminess of the tableware after washing | cleaning in the washing | cleaning of tableware or the washing | cleaning by a dishwasher.

In the powder cleaning composition of the present invention, in addition to the use of the component (a), the component (b) and the component (c), the condition of the cleaning pH after dilution with water described later is important.

<(A) component>
The component (a) is an anionic surfactant. In the powder detergent composition of the present invention, as component (a), polyoxyethylene alkylsulfuric acid having an alkyl group having 10 to 16 carbon atoms, preferably 14 or less, and an average number of moles of ethylene oxide added of 1 to 3 One or more selected from ester salts (hereinafter referred to as (a) _AES ) and alkylbenzene sulfonates having an alkyl group of 10 to 16 carbon atoms (hereinafter referred to as (a) _LAS ), and the carbon number of the alkyl group Containing 10 or more and 16 or less alkyl sulfate ester salt (hereinafter referred to as (a) _AS ).
The component (a) includes one or more anionic surfactants selected from (a) _AES and (a) _LAS , and (a) _AS, and optionally includes an anionic surfactant other than these.

From the viewpoint of detergency against oil stains at a washing pH of less than 7.0, especially 6.5 or less, the mass ratio of the (a) _AS content to the total of (a) _AES and (a) _LAS content is ( a) _AS / [(a) _AES + (a) _LAS ], which is 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less, more preferably 0.5 or less. From the viewpoint of rinsing properties, the mass ratio of (a) _AS / [(a) _AES + (a) _LAS ] is 0.05 or more, preferably 0.1 or more, more preferably 0.15 or more, more Preferably it is 0.2 or more. That is, in the present invention, a polyoxyethylene alkyl sulfate ester salt in which the alkyl group of the component (a) has 10 to 16 carbon atoms and the ethylene oxide average added mole number is 1 to 3 is represented as (a) _AES. An alkylbenzene sulfonate having an alkyl group having 10 to 16 carbon atoms is represented as (a) _LAS, and an alkyl sulfate salt having an alkyl group having 10 to 16 carbon atoms is represented as (a) _AS. Thus, the mass ratio of (a) _AS / [(a) _AES + (a) _LAS ] is in the above range.

The anionic surfactant other than (a) _AES , (a) _LAS, and (a) _AS is not particularly limited. For example, an alkenylbenzene having an alkenyl group having 10 to 18 carbon atoms. Sulfonate, polyoxyalkylene alkenyl ether sulfate ester salt having an alkenyl group having 10 to 18 carbon atoms and an alkyleneoxy group having an average addition mole number of 1 to 10, alkenyl having an alkenyl group having 10 to 18 carbon atoms Sulfuric acid ester salt, α-olefin sulfonate having an alkyl group or alkenyl group having 10 to 18 carbon atoms, α-sulfo fatty acid salt having 10 to 18 carbon atoms, fatty acid portion having 10 to 18 carbon atoms An α-sulfo fatty acid lower alkyl ester salt having an ester moiety having 1 to 5 carbon atoms, 2 or more, 16 or less of a higher fatty acid or its salt (soap), and the like.

As the salt of the anionic surfactant, an alkali metal salt is preferable, a sodium salt or potassium salt is more preferable, and a sodium salt is more preferable.

From the viewpoint of detergency and rinsability in hard water, the proportion of (a) _AES , (a) _LAS and (a) _{AS in} the component (a) is preferably 60% by mass or more, more preferably 70% by mass. Above, more preferably 80% by mass or more, and preferably 100% by mass or less, or 100% by mass.

The powder cleaning composition of the present invention preferably contains (a) _AES and (a) _AS as the component (a).

In the powder cleaning composition of the present invention, from the viewpoint of detergency against food-derived oil stains, the anionic surfactant (a) component is 0.1% by mass or more, preferably 1% by mass or more, more preferably Is 5% by weight or more, more preferably 10% by weight or more, more preferably 20% by weight or more, and 50% by weight or less, preferably 45% by weight or less, more preferably 40% by weight or less, more preferably 30% by weight. % Or less.

<(B) component>
The component (b) of the present invention is a carboxylic acid having a first acid dissociation constant of 1 or more and 5 or less, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 or more and 5,000 or less.

The component (b) has an effect of lowering the pH of water used during washing and keeping the pH during washing in an acidic region.
From the viewpoint of keeping the pH during washing in the acidic region, an organic compound having at least one carboxyl group in the molecule is used. For the purpose of efficiently lowering the pH and quickly dissolving the powder, the number of carboxyl groups in the molecule is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 8 or less, more Preferably it is 6 or less. The component (b) is preferably an acid type or a partially neutralized compound, and the degree of neutralization is 0% or more and 60% or less, preferably 40% or less.

The component (b) has a first acid dissociation constant (pKa1) of 1 to 5 and a maximum acid dissociation constant (pKa _max ) of 7 or less. The maximum acid dissociation constant (pKa _max ) of the component (b) in the present invention is the acid dissociation constant at 20 ° C. in water, in the carboxyl group not neutralized as a salt, Among them, the one showing the highest pKa is indicated. Tap water is usually water whose pH exceeds 7.0 due to the influence of alkalinity, and the pH is hardly lowered even when an acidic component is added for buffering ability. When a compound having a pKa _max of more than 7 is added to such water, the pH cannot be lowered effectively. For example, in the case of citric acid, pKa1 is 3.1, pKa2 is 4.8, and pKa3 is 6.4 at 20 ° C., so pKa _max is 6.4, and in the case of monosodium citrate, pKa1 at 20 ° C. is 4.8, pKa2 is 6.4, and the carboxyl group derived from pKa3 is a sodium salt and can be ignored. Therefore, pKa _max is 6.4 of pKa2. The component (b) has a pKa _max of 7 or less, preferably 6.8 or less, more preferably 6.6 or less, from the viewpoint of efficiently reducing the pH during washing. And it is preferably 1 or more, more preferably 2 or more.

Component (b) has a molecular weight of 5,000 or less, preferably 3,000 or less, more preferably 1,000 or less, more preferably 500 or less, more preferably from the viewpoint of powder solubility during washing. Is 250 or less. The component (b) has a molecular weight of 46 or more, preferably 80 or more, more preferably 100 or more, from the viewpoint of the safety and odor of the base.

Furthermore, from the viewpoint of powder production and storage stability, the component (b) has a solubility in 100 g of water at 20 ° C. of preferably 0.2 g or more, more preferably 1 g or more, more preferably 5 g or more, more preferably 10 g. More preferably, it is 30 g or more, more preferably 50 g or more, and preferably 500 g or less, more preferably 300 g or less.

(B) As the component, such as citric acid _{(pKa1: 3.1, pKa max:} 6.4, molecular weight: Solubility 73g in water 100g of 192.1,20 ℃), malonic acid (pKa1: 2.9, pKa _max : 5.7, molecular weight: 104.1, solubility in 100 g of water at 20 ° C., 139 g), maleic acid (pKa 1: 1.9, pKa _max : 6.6, molecular weight: 116.1, in 100 g of water at 20 ° C. Solubility 78 g), fumaric acid (pKa 1: 3.0, pKa _max : 4.5, molecular weight: 116.1, solubility in 100 g of water at 20 ° C., 0.6 g), formic acid (pKa 1: 3.8, pKa _max : 3) .8, molecular weight: 46.0), oxalic acid _{(pKa1: 1.3, pKa max:} 4.3, molecular weight: 90.0,20 solubility 10g for 100g water in ° C.), propionic acid (pKa1: 4 9, pKa _max: 4.9, molecular weight: 74.1), lactic acid _{(pKa1: 3.8, pKa max:} 3.8, molecular weight: Solubility 88g in water 100g of 90.1,20 ° C.), acetic acid (pKa1 : 4.6, pKa _max : 4.6, molecular weight: 60.1), malic acid (pKa 1: 3.4, pKa _max : 5.1, molecular weight: 134.1, solubility in 100 g of water at 20 ° C 56 g) , tartaric acid _{(pKa1: 3.2, pKa max:} 4.8, molecular weight: 150.1,20 solubility 21g for 100g water in ° C.), succinate _{(pKa1: 4.2, pKa max:} 5.6, molecular weight: 118.1, solubility in 100 g of water at 20 ° C. (5.8 g), glycolic acid (pKa 1: 3.8, pKa _max : 3.8, molecular weight: 76.1, solubility in 100 g of water at 20 ° C. 10 g), benzoic acid (PKa 1: 4.2, pKa _max : 4.2, molecular weight: 122.1, solubility in 100 g of water at 20 ° C. is 0.3 g), salicylic acid (pKa 1: 2.8, pKa _max : 2.8, molecular weight: 138. 1. Solubility of 0.2 g in 100 g of water at 20 ° C.), phthalic acid (pKa 1: 2.9, pKa _max : 5.1, molecular weight: 166.1, solubility in 100 g of water at 20 ° C., 0.7 g), 1, 2,3-benzenetricarboxylic acid _{(pKa1: 2.8, pKa max:} 5.9, molecular weight: 210.1,20 solubility 1.5g in water 100g of ° C.), 1,2,4,5 benzene tetracarboxylic acid (pyromellitic _{acid, pKa1: 1.9, pKa max:} 5.6, molecular weight: 254.2,20 solubility 1.5g in water 100g of ° C.), and include carboxylic acid selected from the salts thereof. Among them, citric acid, malonic acid, maleic acid, fumaric acid, formic acid, oxalic acid, propionic acid, lactic acid, acetic acid, malic acid, tartaric acid, succinic acid, glycolic acid, benzoic acid, salicylic acid, phthalic acid, 1,2,3 A carboxylic acid selected from benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and salts thereof, citric acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, malic acid, 1 , 2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and carboxylic acids selected from salts thereof are more preferable, citric acid, malonic acid, succinic acid, maleic acid, 1,2 More preferred are carboxylic acids selected from 1,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and salts thereof. The salt is preferably an alkali metal salt such as sodium salt or potassium salt. The component (b) may be a hydrate or an anhydride.

In the powder cleaning composition of the present invention, the component (b) is 1% by mass or more, preferably 2% by mass or more, more preferably from the viewpoint of lowering the pH of water used for cleaning and the base cost. 3 mass% or more and 15 mass% or less, Preferably it is 13 mass% or less, More preferably, it is 10 mass% or less, More preferably, it contains 8 mass% or less.

In addition, the powder detergent composition of the present invention has a mass ratio of (a) component / (b) component of 1 or more, preferably 2 or more, from the viewpoint of detergency against dietary oil and pH during washing. Is 3 or more, more preferably 3.5 or more, and 40 or less, preferably 20 or less, more preferably 10 or less, more preferably 7 or less, more preferably 5 or less. The mass ratio of component (a) / component (b) is the mass ratio of the content of component (a) to the content of component (b).

<(C) component>
The component (c) is one or more compounds selected from inorganic sulfates and inorganic halogen compounds. The component (c) of the present invention is not only used as a skeleton for forming a powder composition, but also has an effect of reducing irritation caused by a surfactant by protecting hands during hand washing. The component (c) is not particularly limited as long as it is an inorganic sulfate or an inorganic halogen compound. For example, from the viewpoint of protecting hands, a compound selected from sodium sulfate, magnesium sulfate, sodium chloride and magnesium chloride is used. preferable. The component (c) may be a hydrate or an anhydride.

The powder detergent composition of the present invention preferably contains one or more compounds selected from inorganic sulfates as the component (c). The proportion of the inorganic sulfate in the component (c) is 100% by mass or less than 100% by mass, preferably 97% by mass or less, and 60% by mass or more, more preferably 70% by mass or more. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
The powder cleaning composition of the present invention more preferably contains at least sodium sulfate as component (c). The proportion of sodium sulfate in the component (c) is 100% by mass or less than 100% by mass, preferably 97% by mass or less, and 60% by mass or more, more preferably 70% by mass or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.

The powder cleaning composition of the present invention preferably contains, as component (c), one or more compounds selected from inorganic sulfates and one or more compounds selected from inorganic halogen compounds. When the component (c) includes one or more compounds selected from inorganic sulfates and one or more compounds selected from inorganic halogen compounds, the mass ratio of inorganic sulfate / (inorganic sulfate + inorganic halogen compound) Is preferably 0.5 or more, more preferably 0.6 or more, preferably 0.7 or more, preferably 0.8 or more, preferably 0.9 or more, and preferably 0.99 or less, 0.97 The following is more preferable. The mass ratio of inorganic sulfate / (inorganic sulfate + inorganic halogen compound) is the mass ratio of the content of inorganic sulfate to the total content of inorganic sulfate and inorganic halogen compound.
Moreover, it is also preferable that the powder cleaning composition of this invention contains sodium sulfate and sodium chloride as (c) component. When sodium sulfate and sodium chloride are included as the component (c), the mass ratio of sodium sulfate / (sodium sulfate + sodium chloride) is preferably 0.5 or more, more preferably 0.6 or more, and 0.7 or more. Preferably, 0.8 or more is preferable, 0.9 or more is preferable, 0.99 or less is preferable, and 0.97 or less is more preferable. The mass ratio of sodium sulfate / (sodium sulfate + sodium chloride) is the mass ratio of the content of sodium sulfate to the total content of sodium sulfate and sodium chloride.

In the powder cleaning composition of the present invention, the component (c) is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, more preferably from the viewpoint of long-term storage stability and powder production suitability. Is 45% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, and 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 65% by mass. Contain less than mass%.

<(D) component>
The powder detergent composition of the present invention can optionally contain a nonionic surfactant as component (d). (D) A component can be mix | blended as a cleaning adjuvant. Although it does not specifically limit as a nonionic surfactant, A polyoxyalkylene alkyl ether type nonionic surfactant is preferable, and the compound of the following general formula (1) is mentioned specifically ,.
R ¹ —O [(EO) _a / (PO) _b ] —H (1)
[Wherein, R ¹ represents an alkyl group or an alkenyl group having 10 or more carbon atoms, preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less. EO is an ethyleneoxy group and PO is a propyleneoxy group. a is the number average addition mole number and is a number of 0 or more and 30 or less, b is the number average addition mole number and is a number of 0 or more and 10 or less, and the case where both a and b are 0 is excluded. ]

In the general formula (1), the number average added mole number of a is preferably 6 or more, more preferably 7 or more, more preferably 8 or more, and preferably 25 or less, more preferably 20 or less, more preferably 15 or less. The number average added mole number of b is 0 or more, and preferably 5 or less, more preferably 3 or less, more preferably 2 or less, more preferably 1 or less. In the general formula (1), EO and PO may be arranged in any form of a random copolymer or a block copolymer.

From the viewpoint of detergency against food-derived oil stains and powder production, the content of component (d) is 0% by mass or more and 30% by mass or less, preferably 25% by mass or less, more preferably in the composition. It is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. (D) The lower limit of content in the case of containing a component is in a composition, Preferably it is 1 mass% or more, More preferably, it is 3 mass% or more.

The mass ratio of component (d) / component (a) is preferably 0/100 or more, and preferably 70/30 or less, more preferably 60/40 or less, more preferably 50/50 or less, more preferably Is 40/60 or less, more preferably 30/70 or less. When the component (d) is contained, the lower limit value of the mass ratio of the component (d) / the component (a) is preferably 5/95 or more, more preferably 10/90 or more, more preferably 15/85 or more. . The mass ratio of component (d) / component (a) is the mass ratio of the content of component (d) to the content of component (a).

<Other components and methods of use>
The powder cleaning composition of the present invention can contain an amphoteric surfactant. The amphoteric surfactant is not particularly limited, and examples thereof include alkylamine oxides having 8 to 18 carbon atoms, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazolinium betaines. And phosphobetaine. From the viewpoint of foaming, one or more amphoteric surfactants selected from the group consisting of sulfobetaine, amide betaine and carbobetaine are preferred. The content of the amphoteric surfactant is preferably 0% by mass or more and 10% by mass or less, more preferably 8% by mass or less, more preferably 6% by mass or less in the composition from the viewpoint of rinsing properties. .

The powder detergent composition of the present invention can contain a cationic surfactant. The cationic surfactant is not particularly limited, but is preferably a quaternary ammonium type surfactant or a tertiary amine type surfactant, and further an ether bond, an oxyalkylene group, an ester group, or an amide. A quaternary ammonium type surfactant or a tertiary amine type surfactant having one hydrocarbon group having 6 to 22 carbon atoms which may be separated by a group is preferred. The content of the cationic surfactant is preferably 0% by mass or more and 10% by mass or less, more preferably 8% by mass or less, more preferably 6% by mass or less in the composition from the viewpoint of powder production. is there.

The powder cleaning composition of the present invention has a pH of 2.5 or higher, preferably 2.6 or higher, more preferably 2.6 or higher when diluted 300-fold with 20 ° C. water from the viewpoint of safety for hands during cleaning. Is 2.8 or more, more preferably 3.0 or more, more preferably 3.2 or more, more preferably 3.4 or more, more preferably 3.6 or more, more preferably 3.8 or more, more preferably 4 From the viewpoint of detergency against oil stains, it is 6.5 or less, preferably 6.0 or less, more preferably 5.5 or less, and more preferably 5.0 or less. At this pH, the water used for dilution has an alkalinity of 10 mg / L or more and 300 mg / L or less and a hardness of 1 ° DH in order to achieve a predetermined pH corresponding to the variety of water used for washing. The water is preferably 50 ° DH or less. Furthermore, the powder cleaning composition of the present invention preferably has a pH in the above range when diluted 300-fold with 20 ° C. water having an alkalinity of 100 mg / L and a hardness of 10 ° DH. The alkalinity in the present invention is a value obtained by converting the total amount of carbonic acid, carbonate ion, and hydrogen carbonate ion into the weight of calcium carbonate (calculated as CaCO ₃ ), and its unit is mg / L.

In the powder cleaning composition of the present invention, the content of the component (a) is 20% by mass or more, preferably 50% by mass or more, more preferably from the viewpoint of cleaning performance against oil stains. 70% by mass or more. Further, the content of the component (a) in the total amount of the surfactant is preferably 100% by mass or less. Moreover, 100 mass% may be sufficient as content of (a) component in the whole quantity of surfactant.

The powder cleaning composition of the present invention can be blended with known components as cleaning components within a range that does not significantly affect cleaning performance, hand damage, and pH during use. Specifically, bleach (perborate, bleach activator, etc.), anti-staining agent, softener (bentonite, etc.), reducing agent, fluorescent brightener, foam suppressor (silicone, etc.), fragrance , Enzymes (cellulase, protease, peptinase, lipase, dextranase, amylase, etc.), colorants, inorganic silicates, and the like.

In the powder cleaning composition of the present invention, an inorganic carbonate that exhibits alkalinity when dissolved in water can be blended within the range where the pH during washing is kept acidic, but the pH during washing is less than 7, Furthermore, from the viewpoint of maintaining 6.5 or less, the content of the inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 10% by mass or less. The content of the inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is preferably 8% by mass or less and more preferably 4% by mass or less in the composition. Content of the inorganic carbonate whose solubility with respect to 100 g of water of 20 degreeC is 0.1 g or more is 0 mass% or more in a composition, and may be 0 mass%. Furthermore, in the present invention, the mass ratio of the inorganic carbonate / (b) component having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is preferably 70/30 or less, more preferably 60/40 or less, more preferably Is 50/50 or less, and preferably 0/100 or more. The mass ratio of the inorganic carbonate / (b) component having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is an inorganic substance having a solubility in 100 g of water at 20 ° C. of the content of the component (b) of 0.1 g or more. It is a mass ratio of carbonate content.

The inorganic carbonate having a solubility in 100 g of water at 20 ° C. of less than 0.1 g does not lower the pH at the time of washing, and therefore can be arbitrarily blended in such an amount that does not impair the effects of the present invention. . The solubility of this inorganic carbonate is less than 0.1 g, preferably 0.05 g or less, and more preferably 0.02 g or less. The content of the inorganic carbonate having a solubility in 100 g of water at 20 ° C. of less than 0.1 g is preferably 5% by mass or more, more preferably 8% by mass or more, more preferably 10% by mass in the composition. % Or more. Although not particularly limited, examples of the inorganic carbonate having a solubility in 100 g of water at 20 ° C. of less than 0.1 g include calcium carbonate, magnesium carbonate, barium carbonate, zinc carbonate, and the like. Inorganic carbonates selected from are preferred.

In the present invention, the content of the protease granulated product and the cellulase granulated product is limited in consideration of the feeling during hand washing. This limits the content of proteases and cellulases.

That is, the powder cleaning composition of the present invention has a protein content of 1 mg / enzyme granulated product of 1 g or more and a protease granulated product of 300 mg / enzyme granulated product of 1 g or less and a protein content of 1 mg / enzyme granulated product. The total content of cellulase granulation of 1 g or more and 300 mg / enzyme granulation 1 g or less is 4% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. The total content of these granules is 0% by mass or more, and may be 0% by mass. In addition, the protein about an enzyme granulated material says the protein used as the enzyme of each granulated material.

The content of the protease is preferably 2% by mass or less, more preferably 1% by mass as a granulated product having a protein content of 1 mg / g enzyme granulated product or more and 300 mg / gase enzyme granulated product 1 g or less in the composition. Below, more preferably 0.8% by mass or less. The content of the protease granule is 0% by mass or more in the composition, and may be 0% by mass. In addition, the content of cellulase is preferably 3% by mass or less, more preferably 3% by mass or less, more preferably, as an enzyme granulated product having a protein content of 1 mg / g enzyme granulated product or more and 300 mg / enzyme granulated product 1 g or less. It is 2 mass% or less, More preferably, it is 1 mass% or less. The content of the cellulase granulated product is 0% by mass or more in the composition, and may be 0% by mass.

The protein content in the enzyme granulation can be measured using a protein quantification kit (standard protein: bovine serum albumin) manufactured by Bio-Rad, and the Foreign Lowry method (OH Lowry et al., J. Biol. Biol.Chem., 193, 265 (1951)). The content of protein contained in 1 g of the enzyme granulated product is 1 mg or more, preferably 3 mg or more, more preferably 5 mg, respectively, from the viewpoint of granulated product production and safety. The amount is 300 mg or less, preferably 200 mg or less, more preferably 150 mg or less.

Moreover, in the powder detergent composition of the present invention, the total content of protease and cellulase is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.1% by mass or less. It is more preferably 08% by mass or less, and 0% by mass or more, and may be 0% by mass. The lower limit of the total content in the case of containing a protease or cellulase is the content as a protein, preferably 0.001% by mass or more, more preferably 0.01% by mass or more in the composition, 0.02 The mass% or more is more preferable.

The powder cleaning composition of the present invention is suitable for clothing and includes an embodiment as a powder cleaning composition for clothing. In the case of clothing, it can be used for hand-washing, and the concentration at the time of washing is preferably 1.0 g or more, more preferably 1.5 g as the concentration for 1 L of water, from the viewpoint of detergency against oil stains and rinsing properties. Above, more preferably 2.0 g or more, and preferably 20 g or less, more preferably 15 g or less, more preferably 10 g or less. Depending on the purpose, it can also be used in a washing machine. When used in a washing machine, the concentration with respect to 1 L of water is preferably 0.3 g or more, more preferably 0.5 g or more, from the viewpoint of detergency against oil stains and pH during use. , More preferably 0.7 g or more, and preferably 10 g or less, more preferably 5 g or less, more preferably 3 g or less.

The powder cleaning composition of the present invention is suitable for hard surfaces and further for tableware, and includes an embodiment as a powder cleaning composition for tableware. Since the powder detergent composition of the present invention is excellent in removing dirt from dietary oil, it can be used as a dishwashing detergent for hand washing or a dishwashing detergent for an automatic dishwasher. When used as a dishwashing detergent for an automatic dishwashing machine, the concentration with respect to 1 L of water is preferably 1 g or more, more preferably 1.5 g or more, and preferably from the viewpoint of reducing the sliminess of the dishes after washing. Is 5 g or less, more preferably 2 g or less.

As a cleaning method using the powder cleaning composition of the present invention, using a cleaning water having a pH of 2.5 or more and 6.5 or less obtained by mixing the powder cleaning composition of the present invention and water, it is derived from food. A method for washing clothing or tableware, in which clothing or tableware to which oil stains adhere is washed. Food-derived oil stains include those containing pigments, and are not particularly limited, but examples include lulla oil. The washing | cleaning method of this invention can have the process of rinsing the clothing or tableware after washing | cleaning with water. The alkalinity of the water mixed with the composition can be selected from 10 mgL to 300 mg / L. The hardness of water mixed with the composition can be selected from 1 ° DH to 50 ° DH. Therefore, the water mixed with the composition includes water having an alkalinity of 10 mg / L or more and 300 mg / L or less, a hardness of 1 ° DH or more and 50 ° DH or less.

The water used for washing is known to contain carbonic acid, carbonate ion and hydrogen carbonate ion due to the influence of geology and the presence of microorganisms, and alkalinity is used as an indicator of the amount of these ions. Since the pKa of carbonate ion and hydrogen carbonate ion in water is 10.3 and 6.3 (20 ° C.), respectively, the pH of the cleaning solution is different because the pH buffer capacity is around pH 10.3 and 6.3. As pKa is approached, changes in pH are less likely to occur with small amounts of acid and alkali components.

Considering that the pH of water used for general washing is 6-8, the main factor of alkalinity is bicarbonate ion, and buffering around pH 6.3 when washing pH is lowered than water Exerts an effect. Since the alkalinity in the Asian region is generally high and is 50 to 200 mg / L, it is water whose pH hardly changes even when an acidic component is added.

Also, the water used for cleaning generally contains hardness components such as calcium ions and magnesium ions, which affects the cleaning power and rinsability. These metal ions are captured by a compound having a carboxyl group such as component (b). In addition, since the component (b) releases hydrogen ions, the washing pH can be lowered. Even if the hardness of water used for washing is 1 ° dH or higher, further 2 ° dH or higher, further 3 ° dH or higher, and further 5 ° dH or higher from the viewpoint of lowering the pH of water used for cleaning. it can. On the other hand, the hardness of water is 50 ° dH or less, preferably 40 ° dH or less, more preferably 30 ° dH or less, more preferably 25 ° dH or less from the viewpoint of detergency.

The method for producing the powder detergent composition of the present invention is not particularly limited, but for example, extrusion granulation method, compression granulation method, melt granulation method, spray drying granulation method, fluidized bed granulation method, Examples thereof include a crushing granulation method, a stirring granulation method, a liquid crystal granulation method, a vacuum freeze-drying granulation method, and a dry neutralization granulation method, and these production methods may be used singly or in combination. The bulk density varies depending on the production method, but is preferably 200 g / L or more, more preferably 300 g / L or more, more preferably 350 g / L or more, and preferably 1000 g / L or less, more preferably 900 g / L or less. More preferably, it is 800 g / L or less. The average particle diameter is preferably 100 μm or more, more preferably 150 μm or more, more preferably 200 μm or more, preferably 800 μm or less, more preferably 750 μm or less, and more preferably 700 μm or less. The spray-drying granulation method is suitable for obtaining a composition having a bulk density or an average particle size in the above range.

More specific embodiments of the present invention are exemplified below.
<1>
(A) component: Anionic surfactant 0.1 mass% or more, 50 mass% or less,
Component (b): a carboxylic acid having a primary acid dissociation constant of 1 or more and 5 or less, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 or more and 5,000 or less 1% by mass or more and 15% by mass And (c) component: one or more compounds selected from inorganic sulfates and inorganic halogen compounds 30% by mass or more and 80% by mass or less of a powder detergent composition,
As component (a), the carbon number of the alkyl group is 10 or more and 16 or less, the polyoxyethylene alkylsulfuric acid ester salt having an ethylene oxide average addition mole number of 1 or more and 3 or less, and the carbon number of the alkyl group is 10 or more and 16 or less. 1 or more types chosen from alkylbenzene sulfonate, and the alkyl sulfate ester salt whose carbon number of an alkyl group is 10 or more and 16 or less,
A polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an ethylene oxide average addition mole number of 1 to 3 is represented as (a) _AES, and the alkyl group has 10 to 16 carbon atoms. the following alkylbenzene sulfonate indicated as (a) _LAS, the number of carbon atoms in the alkyl group is 10 or more, and the display 16 following the alkyl sulfate and (a) _aS, (a) _aS / [(a) _AES + (a) _LAS ] is a mass ratio of 0.05 or more and 0.9 or less,
The mass ratio of (a) component / (b) component is 1 or more and 40 or less,
The content of inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 10% by mass or less,
Protein content is 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less protease granulation product and protein content 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less The total content of cellulase granulate is 4% by mass or less,
When the powder detergent composition is diluted 300 times with water at 20 ° C., the pH is 2.5 or more and 6.5 or less.
Powder cleaning composition.

<2>
When the powder detergent composition is diluted 300 times with 20 ° C. water having an alkalinity of 100 mg / L and a hardness of 10 ° DH, the pH is 2.5 or more, preferably 2.6 or more, more preferably 2 0.8 or more, more preferably 3.0 or more, more preferably 3.2 or more, more preferably 3.4 or more, more preferably 3.6 or more, more preferably 3.8 or more, more preferably 4.0. It is above, And it is 6.5 or less, Preferably it is 6.0 or less, More preferably, it is 5.5 or less, More preferably, it is 5.0 or less, The powder cleaning composition as described in said <1>.

<3>
Among the components (a), an anionic surfactant other than (a) _AES , (a) _LAS and (a) _AS has an alkenyl benzene sulfonate having an alkenyl group having 10 to 18 carbon atoms, carbon number A polyoxyalkylene alkenyl ether sulfate salt having an alkenyl group having 10 to 18 carbon atoms and an alkyleneoxy group having an average addition mole number of 1 to 10, an alkenyl sulfate salt having an alkenyl group having 10 to 18 carbon atoms, carbon number An α-olefin sulfonate having an alkyl group or an alkenyl group having 10 or more and 18 or less, an α-sulfo fatty acid salt having 10 or more and 18 or less carbon atoms, a fatty acid portion having 10 to 18 carbon atoms, and an ester moiety Α-sulfo fatty acid lower alkyl ester salts having from 1 to 5 carbon atoms and higher grades having from 12 to 16 carbon atoms Fatty acid or one or more anionic surfactant selected from the salts (soaps), wherein <1> or <2> powder detergent composition.

<4>
The total content of protease and cellulase is 0.2% by mass or less, preferably 0.1% by mass or less, more preferably 0.08% by mass or less, and preferably 0% by mass as protein content. Any of the above <1> to <3>, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, more preferably 0.02% by mass or more, or 0% by mass A powder cleaning composition according to claim 1.

<5>
The mass ratio of (a) _AS to the total amount of (a) _AES and (a) _LAS is (a) _AS / [(a) _AES + (a) _LAS ], 0.05 or more, preferably 0.1 Or more, more preferably 0.15 or more, more preferably 0.2 or more, and 0.9 or less, preferably 0.7 or less, more preferably 0.5 or less, more preferably 0.3 or less. The powder cleaning composition according to any one of <1> to <4>.

<6>
In the component (a), the proportions of (a) _AES , (a) _LAS, and (a) _AS are 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and 100% by mass or less. Or the powder cleaning composition according to any one of <1> to <5>, wherein the composition is 100% by mass.

<7>
Component (a) is 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, and 50% by mass. The powder cleaning composition according to any one of <1> to <6>, which is preferably contained in an amount of 45% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass or less.

<8>
In the component (b), the number of carboxyl groups in the molecule is 2 or more, and preferably 10 or less, more preferably 8 or less, more preferably 6 or less, <1> to <7> A powder cleaning composition according to any one of the above.

<9>
The powder cleaning composition according to any one of <1> to <8>, wherein the component (b) has a pKa _max of 7 or less, preferably 6.8 or less, more preferably 6.6 or less.

<10>
Component (b) has a molecular weight of 46 or more, preferably 80 or more, more preferably 100 or more, and 5,000 or less, preferably 3,000 or less, more preferably 1,000 or less, more The powder cleaning composition according to any one of <1> to <9>, which is preferably 500 or less, more preferably 250 or less.

<11>
The solubility of the component (b) in 100 g of water at 20 ° C. is 0.2 g or more, preferably 1 g or more, more preferably 5 g or more, more preferably 10 g or more, more preferably 30 g or more, more preferably 50 g or more, The powder cleaning composition according to any one of <1> to <10>, preferably 500 g or less, more preferably 300 g or less.

<12>
Component (b) is citric acid, malonic acid, maleic acid, fumaric acid, formic acid, oxalic acid, propionic acid, lactic acid, acetic acid, malic acid, tartaric acid, succinic acid, glycolic acid, benzoic acid, salicylic acid, phthalic acid, 1 The powder cleaning agent according to any one of <1> to <11>, which is a carboxylic acid selected from 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and salts thereof Composition.

<13>
The component (b) contains 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and 15% by mass or less, preferably 13% by mass or less, more preferably 10% by mass or less. The powder cleaning composition according to any one of <1> to <12>.

<14>
The mass ratio of component (a) / component (b) is 1 or more, preferably 2 or more, more preferably 3 or more, and 40 or less, preferably 20 or less, more preferably 10 or less, more preferably 7 The powder cleaning composition according to any one of <1> to <13>, more preferably 5 or less.

<15>
(C) The powder cleaning composition according to any one of <1> to <14>, wherein the component is a compound selected from sodium sulfate, magnesium sulfate, sodium chloride and magnesium chloride.

<16>
(C) It contains sodium sulfate and sodium chloride as components, and the mass ratio of sodium sulfate / (sodium sulfate + sodium chloride) is 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, The powder cleaning according to any one of <1> to <15>, more preferably 0.8 or more, more preferably 0.9 or more, and 0.99 or less, preferably 0.97 or less. Agent composition.

<17>
Component (c) is 30% by mass or more, preferably 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more. The powder cleaning agent according to any one of <1> to <16>, which is contained in an amount of 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and more preferably 65% by mass or less. Composition.

<18>
The nonionic surfactant is contained in an amount of 0% by mass to 30% by mass as the component (d), and the mass ratio of the component (d) / the component (a) is 0/100 or more and 70/30 or less, <1 The powder cleaning composition according to any one of> to <17>.

<19>
(D) Powder cleaning composition as described in said <18> whose component is a compound of the following general formula (1).
R ¹ —O [(EO) _a / (PO) _b ] —H (1)
[Wherein, R ¹ represents an alkyl group or an alkenyl group having 10 or more carbon atoms, preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less. EO is an ethyleneoxy group and PO is a propyleneoxy group. a is the number average addition mole number and is a number of 0 or more and 30 or less, b is the number average addition mole number and is a number of 0 or more and 10 or less, and the case where both a and b are 0 is excluded. ]

<20>
The content of the component (d) in the composition is 1% by mass or more, more preferably 3% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass. % Or less, More preferably, it is 5 mass% or less, The powder cleaning composition as described in said <18> or <19>.

<21>
The mass ratio of component (d) / component (a) is 5/95 or more, preferably 10/90 or more, more preferably 15/85 or more, and preferably 60/40 or less, more preferably 50 / The powder cleaning composition according to any one of the above items <18> to <20>, which is 50 or less, more preferably 40/60 or less, and more preferably 30/70 or less.

<22>
In the total amount of the surfactant, the content of the component (a) is 20% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and 100% by mass or less, or 100% by mass. %, Or 100% by mass, according to any one of <1> to <21> above.

<23>
Protein content is 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less protease granulation product and protein content 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less The powder cleaning agent according to any one of <1> to <22>, wherein the total content of cellulase granules is 4% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. Composition.

<24>
The content of the protease is preferably 2% by mass or less, more preferably 1% by mass as a granulated product having a protein content of 1 mg / g enzyme granulated product or more and 300 mg / gase enzyme granulated product 1 g or less in the composition. Hereinafter, the powder cleaning composition according to any one of <1> to <23>, more preferably 0.8% by mass or less.

<25>
The cellulase content in the composition is 3% by mass or less, more preferably 2% by mass or less as an enzyme granulated product having a protein content of 1 mg / enzyme granulated product 1 g or more and 300 mg / enzyme granulated product 1 g or less. The powder detergent composition according to any one of <1> to <24>, more preferably 1% by mass or less.

<26>
Any one of the above items <1> to <25>, wherein the content of the inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 8% by mass or less, preferably 4% by mass or less. A powder cleaning composition according to claim 1.

<27>
The powder cleaning composition according to any one of <1> to <26>, which is used for washing clothes.

<28>
A method for washing clothes by hand using the powder detergent composition according to any one of <1> to <26>.

<29>
The powder cleaning composition according to any one of <1> to <26>, which is used for cleaning dishes.

The present invention
(A) component: Anionic surfactant 0.1 mass% or more, 50 mass% or less,
Component (b): a carboxylic acid having a primary acid dissociation constant of 1 or more and 5 or less, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 or more and 5,000 or less 1% by mass or more and 15% by mass And (c) component: one or more compounds selected from inorganic sulfates and inorganic halogen compounds 30% by mass or more and 80% by mass or less of a powder detergent composition,
The content of inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 10% by mass or less,
Protein content is 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less protease granulation product and protein content 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less The total content of cellulase granulate is 4% by mass or less,
The total content of protease and cellulase is 0.2% by mass or less as protein content,
The pH when the powder cleaning composition is diluted 300 times with water at 20 ° C. is 2.5 or more and less than 7.0,
Provided are a powder cleaning composition and a method for washing clothes by hand using the powder cleaning composition. The above-mentioned matters such as preferable compounds and preferable mass ratios can be applied to this powder cleaning composition.
Example

The following examples describe the implementation of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.

Using the following blending components and the components shown in Tables 1 to 4, powder detergent compositions shown in Tables 1 to 4 were prepared by the compaction granulation method. Specifically, after mixing the component (b) or the component (b ′) and the component (c) with a ribbon mixer, the desired composition was obtained by spraying and stirring the component (a) and the component (d). . Optionally, in the final step, ingredients other than those described above were mixed and stirred. Evaluation was performed by the following method. The results are shown in Tables 1 to 4.

[1] pH measurement method A pH measurement composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution.

Next, a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) were each filled in a 100 mL beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.

Fill a 100 mL beaker with a sample (diluted powder detergent composition) diluted 300 times using water of hardness 10 ° dH, alkalinity 100 mg / L (CaCO ₃ conversion), pH 7.5, 20 ° C. And it adjusted to 20 degreeC in a 20 degreeC thermostat. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured. The results are shown in the table as the pH of the water dilution.

[2] Solubility Evaluation In a beaker with a capacity of 2 L, 1 g of the powder cleaning composition in the table was used with 1 L of water having a hardness of 10 ° dH, an alkalinity of 100 mg / L (calculated as CaCO ₃ ), pH 7.5, and 20 ° C. Mixed. A bar-shaped magnetic stirrer having a length of 5 cm was used as a stirrer and stirred for 1 minute at 800 rpm to dissolve. Then, after filtering using a metal mesh with an opening of 74 mm, it was dried at 105 ° C. for 2 hours, and the amount of residue (g) remaining on the metal mesh was measured. The dissolution rate was calculated by the following formula to evaluate the solubility of the powder cleaning composition.
Dissolution rate (%) = [(Amount of powder detergent composition before dissolution (1 g) −Amount of residue after dissolution (g)) / (Powder detergent composition before dissolution (1 g))] × 100

[3] Detergency Evaluation Method Hardness 10 ° dH, Alkalinity 100mg / L (CaCO ₃ conversion), pH 7.5, 20 ° C 3L of water Diluted and dissolved. Thereafter, one undergarment sewn with five litter oil-contaminated cloths prepared as described below and two underwears of the same size for adjusting the bath ratio were put, and the whole was stirred. Thereafter, the contaminated cloth was uniformly rubbed by hand for 10 minutes. After rinsing twice with 3 L of water similar to the water used to dilute the composition, it was squeezed by hand to dehydrate and dried. The cleaning rate was measured by the following formula. The water used for washing and rinsing is 1 L of ion-exchanged water with 78.50 g of calcium chloride dihydrate and 73.58 g of magnesium chloride hexahydrate to make calcium / magnesium = 6/4 as a hardness component. It was dissolved in The obtained concentrated stock solution was diluted with water adjusted in alkalinity and pH, and adjusted to 10 ° dH. The alkalinity was adjusted to 100 mg / L using sodium bicarbonate, and then the pH was adjusted to 7.5 using hydrochloric acid. Washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectance of white cloth−reflectivity before washing)] × 100
The white cloth is an unstained cloth of the cotton knitted cloth used for the preparation of the ra oil-contaminated cloth.
The reflectance was measured with NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

<Preparation of ra oil-contaminated cloth>
0.1 mL of commercially available S & B oil oil (manufactured by SB Foods Co., Ltd., purchased in June 2013) was uniformly applied onto a 6 cm × 6 cm cotton knitted cloth and dried at a temperature of 25 ° C. and a humidity of 65 RH% for 15 hours. This was used for the test.

[4] Evaluation of the comfort of hand-washing work The comfort of the hand-washing work was evaluated based on the feel of the hand during and after washing in the “method for evaluating washing power” of [3] above.
Specifically, in the “detergent evaluation method” in [3] above,
(I) During scrub cleaning,
(II) Immediately after rubbing, rinsing and wiping hands with a towel after dehydration, and (III) 2 minutes after wiping hands with the towel,
The comfort was evaluated for these three periods. Ten panelists each judged the comfort of hand-washing work according to the following criteria.
The above criteria (I) were determined to be “very uncomfortable” or “slightly uncomfortable” when nullified in the hand, and “very comfortable” or “somewhat comfortable” with the same feel as water alone. In addition, the criteria of the above (II) and (III) are “very uncomfortable” or “slightly uncomfortable” when there is a residual feeling of the cleaning composition component, and no residual feeling of the cleaning composition component. Was “very comfortable” or “slightly comfortable”.
The results of three periods were collected from one panelist and the average value was obtained. The average value was collected for 10 persons, and the average value was further determined and shown in the table.
5: Very uncomfortable 4: Slightly uncomfortable 3: Neither 2: Slightly comfortable 1: Very comfortable

[5] Evaluation of anti-sticking residue on tableware An automatic dishwasher (NP-60SS5) manufactured by Panasonic Corporation was used. Contaminated dishes were washed by the automatic dishwasher speed course under the following conditions. This washing machine is of a type in which 2.2 L of water is gradually heated from 20 ° C. to 60 ° C. for washing, then rinsed once, and then dried. Three contaminated dishes were used and arranged vertically on the upper plate of the dish washer. At that time, the interval between the first and second sheets was 13 mm, and the interval between the second and third sheets was 5 mm. Further, five dishes (obstruction dishes) with a diameter of 230 mm were arranged at equal intervals of 25 mm on the lower stage of the tableware receiver. In addition, the space | interval of a dish here is the distance from the bottom part of the outer surface (back surface) of one dish to the edge of the other inner surface (surface). This test assumes a non-ideal condition in which the distance between adjacent dishes is reduced, and at the same time assumes a situation in which it is difficult for water to flow due to the installation of obstacle dishes. After the operation was completed, the degree of sliminess when each tableware was rubbed with a finger was determined by the 10 panelists in the following five stages, and the average value was calculated.
5: Very slim 4: Slightly slippery 3: Can't say either 2: Slightly slim 1: Not slimy at all

Contaminated dish: 0.7 g of egg yolk applied as uniformly as possible to a ceramic dish with a diameter of 103 mm and denatured at 115 ° C. for 1 hour Water used: hardness 10 ° dH, alkalinity 100 mg / L (CaCO ₃ equivalent), pH 7.5 Water, 2.2L
Washing machine: Panasonic dishwasher (model NP-60SS5)
Cleaning course: Speed course detergent composition added amount: 6g

[6] Rinse evaluation Three pieces of underwear were soaked in a cleaning solution in which the powder detergent composition was dissolved in water at a concentration of 750 ppm for 15 minutes, and then the underwear was rinsed 50 times, and the water content was about 100 to 140%. Squeezed to become.
On the other hand, 5 L of hard water having a water temperature of 20 ° C. and a calcium carbonate equivalent of 179 mg / L was injected as a rinse water into a model circular basin (a cylindrical acrylic container having a bottom diameter (inner diameter) of 25 cm and a height of 15 cm). This hard water corresponds to 10 ° DH hard water in German hardness. Further, this hard water is obtained by adding ion exchange water to 1.58 g of calcium chloride CaCl ₂ .2H ₂ O and 1.45 g of magnesium sulfate MgSO ₄ .6H ₂ O to make 10 L, and Ca / Mg = 6/4 (molar ratio).
These three underwears were put into the basin into which rinse water was poured. After rinsing these undergarments in water, lift one of the undergarments from the bath with the ridges, that is, lift the entire garment from the bath to a height of about 5 cm above the basin, and then Returned to the bath again. After rinsing by such up-and-down movement was repeated 10 times for each undergarment, it was squeezed 10 cm above the basin so that the moisture content of the undergarment was about 100 to 140% of the undergarment. The squeezed underwear was taken out of the basin. The level of rinse water immediately after the third undergarment was squeezed was observed, and points were assigned according to the following criteria.
Point 6: Bubbles with a bubble height of 1 cm or more remain on the entire liquid surface. 5: Bubbles remain on the entire liquid surface (bubble height of less than 1 cm).
4: Bubbles (bubble height less than 1 cm) remain about 1/2 of the liquid level 3: Bubbles (bubble height less than 1 cm) remain about 1/4 of the liquid level 2: Fine on the liquid level Bubbles remain 1: No bubbles remain on the liquid surface

[7] Compounding component (a) component AES-Na (1): polyoxyethylene having a linear primary alkyl group having 10 to 16 carbon atoms (average addition mole number 2) alkyl ether sulfate sodium salt, Emar 270S ( (Kao Corporation)
AES-Na (2): polyoxyethylene having a linear primary alkyl group having 12 carbon atoms (average addition mole number 3) sodium alkyl ether sulfate, Emar 20C (manufactured by Kao Corporation)
・ LAS-Na: Sodium laurylbenzenesulfonate, Neoperex G-15 (manufactured by Kao Corporation)
AS-Na: sodium lauryl sulfate ester, Emar 0 (manufactured by Kao Corporation)
MES-Na: α-sulfo fatty acid methyl ester sodium having 14 carbon atoms FA-Na: higher fatty acid sodium having 12 carbon atoms (manufactured by Kao Corporation)

(B) Component citric acid (pKa1 = 3.1, pKa2 = 4.8, pKa3 = 6.4 (pKa _max ), molecular weight 192.1, solubility in 100 g of water at 20 ° C. 73 g)
Malonic acid (pKa1 = 2.9, pKa2 = 5.7 (pKa _max ), molecular weight 104.1, solubility in 100 g of water at 20 ° C., 139 g)
Pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, pKa1 = 1.9, pKa2 = 2.9, pKa3 = 4.5, pKa4 = 5.6 (pKa _max ), molecular weight 254.2 , 1.5g solubility in 100g water at 20 ° C)
Maleate _{(pKa1: 1.9, pKa max:} 6.6, molecular weight: 116.1,20 solubility 78g for 100g water in ° C.)
Fumaric acid (pKa 1: 3.0, pKa _max : 4.5, molecular weight: 116.1, solubility in 100 g of water at 20 ° C., 0.6 g)
- formic acid _{(pKa1: 3.8, pKa max:} 3.8, molecular weight: 46.0)
Oxalic acid (pKa 1: 1.3, pKa _max : 4.3, molecular weight: 90.0, solubility 10 g in 100 g of water at 20 ° C.)
Propionic acid (pKa 1: 4.9, pKa _max : 4.9, molecular weight: 74.1, solubility 37 g in 100 g of water at 20 ° C.)
Lactic acid (pKa 1: 3.8, pKa _max : 3.8, molecular weight: 90.1, solubility in 100 g of water at 20 ° C. 88 g)
Acetate _{(pKa1: 4.6, pKa max:} 4.6, molecular weight: 60.1)
- malic acid _{(pKa1: 3.4, pKa max:} 5.1, molecular weight: 134.1,20 solubility 56g for 100g water in ° C.)
Tartaric acid (pKa 1: 3.2, pKa _max : 4.8, molecular weight: 150.1, solubility of 21 g in 100 g of water at 20 ° C.)
・ Succinic acid (pKa 1: 4.2, pKa _max : 5.6, molecular weight: 118.1, solubility in 100 g of water at 20 ° C., 5.8 g)
Glycolic acid (pKa 1: 3.8, pKa _max : 3.8, molecular weight: 76.1, solubility in 100 g of water at 20 ° C. 10 g)
Benzoic acid (pKa 1: 4.2, pKa _max : 4.2, molecular weight: 122.1, solubility 0.3 g in 100 g of water at 20 ° C.)
Salicylic acid _{(pKa1: 2.8, pKa max:} 2.8, molecular weight: 138.1,20 dissolved in water 100g of ℃ degree 0.2g)
・ Phthalic acid (pKa 1: 2.9, pKa _max : 5.1, molecular weight: 166.1, solubility in 100 g of water at 20 ° C .: 0.7 g)
1,2,3-benzenetricarboxylic acid (pKa 1: 2.8, pKa _max : 5.9, molecular weight: 210.1, solubility in 100 g of water at 20 ° C., 1.5 g)

Component (b ′) Glycine (pKa1 = 2.3, pKa2 = 9.6 (pKa _max ), molecular weight 75, solubility 25 g in 100 g of water at 20 ° C.)
Lysine (pKa1 = 2.2, pKa2 = 9.0 (pKa _max ), molecular weight 146.2, solubility in 100 g of water at 20 ° C. 10 g)

(C) ingredient, sodium sulfate, sodium chloride

Component (d) Nonionic surfactant 1: Polyoxyethylene alkyl ether (12 carbon atoms in alkyl group, average number of added moles 10, Emulgen 110 L; manufactured by Kao Corporation)
Nonionic surfactant 2: polyoxyethylene alkyl ether (12 carbon atoms in alkyl group, 20 average added moles, Emulgen 121; manufactured by Kao Corporation)

(E) Component / sodium carbonate / alkaline protease (KAP; manufactured by Kao Corporation, protein content: 100 mg / granulated granule of enzyme granule 1 g)
Cellulase (KAC; manufactured by Kao Corporation, granulated product with a protein content of 20 mg / enzyme granulated product 1 g)
・ Carboxymethylcellulose sodium salt (CMC)
・ Activated clay (Galleon Earth NV; Mizusawa Chemical Co., Ltd.)
PEG 13000 (polyoxyethylene glycol, molecular weight 13000, manufactured by SINO-Japan)
・ Perfume

In the table, the content of the enzyme is the content as an enzyme protein.

Claims (7)

(A) component: Anionic surfactant 0.1 mass% or more, 50 mass% or less,
Component (b): a carboxylic acid having a primary acid dissociation constant of 1 or more and 5 or less, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 or more and 5,000 or less 1% by mass or more and 15% by mass And (c) component: one or more compounds selected from inorganic sulfates and inorganic halogen compounds 30% by mass or more and 80% by mass or less of a powder detergent composition,
As component (a), the carbon number of the alkyl group is 10 or more and 16 or less, the polyoxyethylene alkylsulfuric acid ester salt having an ethylene oxide average addition mole number of 1 or more and 3 or less, and the carbon number of the alkyl group is 10 or more and 16 or less. 1 or more types chosen from alkylbenzene sulfonate, and the alkyl sulfate ester salt whose carbon number of an alkyl group is 10 or more and 16 or less,
A polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an ethylene oxide average addition mole number of 1 to 3 is represented as (a) _AES, and the alkyl group has 10 to 16 carbon atoms. the following alkylbenzene sulfonate indicated as (a) _LAS, the number of carbon atoms in the alkyl group is 10 or more, and the display 16 following the alkyl sulfate and (a) _aS, (a) _aS / [(a) _AES + (a) _LAS ] is a mass ratio of 0.05 or more and 0.9 or less,
The mass ratio of (a) component / (b) component is 1 or more and 40 or less,
The content of inorganic carbonate having a solubility in 100 g of water at 20 ° C. of 0.1 g or more is 10% by mass or less,
Protein content is 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less protease granulation product and protein content 1 mg / enzyme granulation 1 g or more, 300 mg / enzyme granulation 1 g or less The total content of cellulase granulate is 4% by mass or less,
When the powder detergent composition is diluted 300 times with water at 20 ° C., the pH is 2.5 or more and 6.5 or less.
Powder cleaning composition. The pH of the powder detergent composition is 2.5 or more and 6.5 or less when diluted 300 times with 20 ° C water having an alkalinity of 100 mg / L and a hardness of 10 ° DH. Powder cleaning composition. The powder detergent composition according to claim 1 or 2, wherein the total content of protease and cellulase is 0.2% by mass or less in terms of protein content. The powder cleaning composition according to any one of claims 1 to 3, wherein the component (b) is a carboxylic acid having a solubility in 100 g of water at 20 ° C of 0.2 g or more. (B) component is citric acid, malonic acid, maleic acid, fumaric acid, formic acid, oxalic acid, propionic acid, lactic acid, acetic acid, malic acid, tartaric acid, succinic acid, glycolic acid, benzoic acid, salicylic acid, phthalic acid, 1 The powder detergent composition according to any one of claims 1 to 4, which is a carboxylic acid selected from 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and salts thereof. The nonionic surfactant is contained in an amount of 0% by mass to 30% by mass as the component (d), and the mass ratio of the component (d) / (a) is 0/100 or more and 70/30 or less. 6. The powder cleaning composition according to any one of 5 above. A method for washing clothes by hand using the powder detergent composition according to any one of claims 1 to 6.