JP2017119734A - Solid detergent composition for hand washing textile products - Google Patents

Abstract

[PROBLEMS] In particular, it is excellent in the feel of textile products during hand washing and washing, has a high detergency against oil stains partially adhered to foods, and reduces the sliminess of hand skin during washing. Provided is a solid detergent composition for hand-washing textiles, in which detergent components are less likely to remain on the textiles after washing. SOLUTION: (a) 5% by mass or more and 50% by mass or less of a surfactant, (b) a water-soluble inorganic carbonate, (c) a water-soluble inorganic sodium salt (however, those belonging to (b) and (d) (A) a solid detergent composition for hand-washing textile products, comprising (d) one or more inorganic metal ion trapping builders selected from aluminosilicates, crystalline silicates and phosphates; The mass ratio of (b) / (c) is 0 to 0.3, and the mass ratio of (d) / (c) is 0.1 to 3. 001 or more and 0.33 or less, and the cleaning composition is heated at a temperature of 20 ° C., a hardness of 10 ° dH, an alkalinity of 100 mg / L in terms of CaCO 3, and a pH of 7.5 using water. Solid for hand-washing textiles with a pH of 2.5 or more and 9 or less when diluted 200-fold Cleaning agent composition. [Selection diagram] None

Description

  The present invention relates to a solid detergent composition for hand washing textiles and a textile hand washing method.

  In laundry for washing textile products by hand, a laundry detergent is generally used. Especially in the Asian region, hand washing using powder detergent is still widely performed from the viewpoint of detergency, economical viewpoint, cultural background, washing awareness, and the like. In addition, washing by hand can be performed while checking the level of dirt removed by the workers themselves, so it is suitable for washing to remove not only the overall dirt attached to the fibers but also dirt such as partial spills. Yes.

  However, during washing by hand, the hands are kept in the washing solution for a long time, so it feels sticky to the hands due to the influence of alkali components and washing ingredients, and also becomes sticky due to dry hands and residual washing ingredients even after washing. May cause discomfort.

  Furthermore, since detergents are used at a low bath ratio and high concentration, inorganic salts such as aluminosilicates remain undissolved in fiber products, and excessive adsorption of activators occurs. Cleaning with a low washing liquid is desired.

  Patent Document 1 contains a specific anionic surfactant, a carboxylic acid such as citric acid, and an inorganic sulfate and / or inorganic halogen compound, and the content of the inorganic carbonate is 10% by mass or less. Disclosed is a powder detergent composition having an excellent feel at the time.

  Patent Document 2 discloses a powder detergent that contains a small amount of aluminosilicate and contains sodium carbonate and sodium sulfate and exhibits excellent detergency against dirt on the sleeves of clothes.

  Patent Document 3 discloses a powder detergent that contains aluminosilicate, sodium carbonate, and sodium sulfate and has excellent solubility.

  In Patent Document 4, a laundry detergent, in particular, a liquid detergent not containing an aluminosilicate capable of providing a pH of around 6 in washing water of a washing machine is excellent in removing dirt and leaving detergent components in clothing. It is disclosed not to.

JP2015-143329A JP 2014-141439 A International Publication No. 2005-078058 Special table 2015-508445 gazette

In addition to using a predetermined anionic surfactant, a predetermined carboxylic acid, and a predetermined inorganic compound, Patent Document 1 describes the conditions of washing pH after dilution with water and the content of enzyme granules. By prescribing, a powder detergent composition is obtained which is gentle to the hand skin and is less likely to remain moist on the object after washing. Patent Document 1 does not mention improving the feel of the textile product during the hand washing operation.
Patent Documents 2 and 3 are excellent in detergency because they contain a large amount of an alkali component, but there is room for improvement in terms of providing further comfort during hand washing operations in hand washing in the Asian region.
The detergent composition of Patent Document 4 is in a liquid state and is 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, the detergency against hand discomfort and partial stains is greatly influenced by the pH at the time of washing and the concentration of the surfactant. However, Patent Document 4 does not fully disclose the effect on the hand of the composition. Met.

  The present invention is particularly excellent in the feel of textile products during hand washing, has a high detergency against partially adhered oil stains derived from food, reduces the wetness of the hand skin during washing, and The present invention provides a solid detergent composition for washing textile products and a washing method for washing textile products, in which detergent components do not easily remain in the washed textile products.

The present invention includes (a) a surfactant of 5% by mass to 50% by mass, (b) a water-soluble inorganic carbonate, (c) a water-soluble inorganic sodium salt (provided that those belonging to (b) and (d) And (d) a solid detergent composition for hand washing of textile products containing one or more inorganic metal ion scavengers selected from aluminosilicate, crystalline silicate and phosphate,
The mass ratio of (a) / (c) is 0.1 or more and 3 or less,
The mass ratio of (b) / (c) is 0 or more and 0.3 or less,
(D) / (c) mass ratio is 0.001 or more and 0.33 or less,
PH when the cleaning composition is diluted 200 times by mass with water having a temperature of 20 ° C., a hardness of 10 ° dH, an alkalinity of 100 mg / L in terms of CaCO ₃ , and a pH of 7.5. Is not less than 2.5 and not more than 9.
The present invention relates to a solid detergent composition for hand washing textile products.

The present invention also relates to a method for washing and washing textile products having the following steps.
<Step 1>
(A) Surfactant 5 mass% or more and 50 mass% or less, (b) Water-soluble inorganic carbonate, (c) Water-soluble inorganic sodium salt (except for those belonging to (b) and (d)), ( d) containing at least one inorganic polyvalent metal ion capture builder selected from aluminosilicate, crystalline silicate and phosphate, and having a mass ratio of (a) / (c) of 0.1 to 3 Yes, solid washing for hand washing of textile products in which the mass ratio of (b) / (c) is 0 or more and 0.3 or less and the mass ratio of (d) / (c) is 0.001 or more and 0.33 or less A step of preparing a washing liquid for hand washing of textile products by mixing an agent composition and water.
<Process 2>
A step of washing the textile product by hand with the washing solution for washing the textile product prepared in Step 1.

  Hereinafter, (a) surfactant is component (a), (b) water-soluble inorganic carbonate is component (b), (c) water-soluble inorganic sodium salt (however, those belonging to (b) and (d)) (Excludes) is described as component (c), and (d) one or more inorganic metal ion trapping builders selected from aluminosilicates, crystalline silicates and phosphates as component (d).

According to the present invention, the fiber feel is particularly excellent when hand-washing a textile product, and it has excellent solubility in water, high detergency against food-derived oil stains, and comfort to the hand skin. Provided is a solid detergent composition for hand washing textiles, which is excellent and does not easily leave detergent components in the textiles after washing.
The solid detergent composition for hand washing of textile products according to the present invention uses aluminosilicate at a low concentration in the washing of textile products, and limits the use ratio of inorganic salts, so that the feel of the fibers during hand washing is reduced. It is excellent and can reduce residue of detergent components. Moreover, it has high detergency against food-derived oil stains. The solid detergent composition for hand washing textile products of the present invention can improve the comfort to the hand skin.

<Solid detergent composition for hand washing textile products>
[(A) component]
The component (a) is a surfactant. The component (a) has an action of washing dirt adhering to the textile product, but the comfort of the hand washing operation or the comfort of the textile product feel during the hand washing may be lowered.
Examples of the surfactant include one or more surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  Examples of the anionic surfactant include one or more anions selected from alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfate esters, polyoxyalkylene alkyl ether sulfates, α-sulfo fatty acid ester salts and fatty acid salts. An ionic surfactant is mentioned. Examples thereof include one or more anionic surfactants selected from alkyl benzene sulfonates, alkyl sulfate esters, and polyoxyalkylene alkyl ether sulfates. The number of carbon atoms 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, from the viewpoint of improving detergency. Is 16 or less, more preferably 14 or less. The oxyalkylene group is preferably an ethyleneoxy group. The average added mole number is preferably 0.5 or more, more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of improving detergency. The salt of the anionic surfactant is preferably an alkali metal salt such as sodium salt or potassium salt.

Examples of the anionic surfactant include one or more anionic surfactants selected from the following (a1) and (a2), and combinations thereof.
(A1): a polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an average added mole number of ethylene oxide of 1 to 5 and an alkylbenzene sulfonate having an alkyl group having 10 to 16 carbon atoms One or more surfactants selected from (a2): One or more surfactants selected from alkyl sulfates having 10 to 16 carbon atoms in the alkyl group

  When using (a1) and (a2), the mass ratio of (a2) / (a1), which is the mass ratio of the content of (a1) and the content of (a2), is the comfort of hand-washing work or From the viewpoint of further improving the comfort of the textile product during hand washing, it is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, still more preferably 0.20 or more, Preferably, it is 0.25 or more, and from the viewpoint of further improving the cleaning performance of soil, it is preferably 5 or less, more preferably 4 or less, more preferably 3 or less, more preferably 2 or less, more preferably 1. 5 or less, more preferably 1.2 or less, and even more preferably 1.0 or less.

  From the viewpoint of improving detergency in hard water, the total ratio of (a1) and (a2) in the anionic surfactant is preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and preferably 100% by mass or less, or 100% by mass.

From the viewpoint of further improving the comfort of hand-washing work, or the viewpoint of further improving the feel of the fiber when hand-washing the textile product, the solid detergent composition for hand washing textile products of the present invention, as the component (a), It is preferable to contain (a1) and (a2).
In addition, the solid detergent composition for hand washing of textile products of the present invention comprises a poly (A) component having a carbon number of 10 to 16 and an average number of moles of ethylene oxide added of 1 to 5 as the component (a1). It contains both an oxyethylene alkyl sulfate ester salt and an alkyl benzene sulfonate having an alkyl group having 10 to 16 carbon atoms, and an alkyl sulfate salt having (a2) an alkyl group having 10 to 16 carbon atoms. It is preferable from the viewpoint of improving the detergency.

  In the component (a), the solid detergent composition for hand washing of textile products of the present invention is easy to realize the effect of improving the comfort of hand washing work or the feeling of fiber when hand washing textile products. The total ratio of (a1) and (a2) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 100% by mass or less. Or it is 100 mass%.

  Nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, sucrose fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, fatty acid alkanolamides or alkylene oxide additions thereof. Products, alkyl glycosides, polyoxyalkylene alkyl phenyl ethers, glyceryl mono ethers and the like. As the nonionic surfactant, a polyoxyalkylene alkyl ether is preferable, and a polyoxyalkylene alkyl ether having an alkyl group having 10 to 20 carbon atoms and an average addition mole number of ethyleneoxy groups of 5 to 50 is preferred. More preferred.

Specific examples of the polyoxyalkylene alkyl ether include compounds represented by the following general formula (1).
R < ¹ > -O [(EO) _p / (PO) _q ] -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. p is an average number of added moles and is a number from 0 to 30; q is an average number of moles added and represents a number from 0 to 10; EO and PO may be either random polymerization or block polymerization. “/” Is a symbol indicating that the combination of EO and PO may be random or block. ]

In general formula (1), R ¹ is a straight chain or a branched chain. In R ¹ —O, the carbon atom bonded to the oxygen atom (O) of R ¹ is preferably primary.
In general formula (1), the average added mole number of p is preferably 5 or more, more preferably 7 or more, still more preferably 8 or more, and preferably 30 or less, more preferably 27 or less, and still more preferably 23 or less. It is.
Moreover, in general formula (1), the average added mole number of q is 0 or more, Preferably it is 10 or less, More preferably, it is 5 or less, More preferably, it is 3 or less. In the general formula (1), EO and PO may be arranged in any form of a random copolymer or a block copolymer.

When q in the general formula (1) is 0, the compound is represented by the following general formula (1 ′), and the definitions of R ¹ , EO, and p are the same as those in the general formula (1). It is the same as general formula (1).
R ¹ —O (EO) _p —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. p is an average added mole number, and is a number of 0 or more and 30 or less. ]

  Although it does not specifically limit as a cationic surfactant, A quaternary ammonium type surfactant or a tertiary amine type surfactant is mentioned, Furthermore, an ether bond, an oxyalkylene group, ester group, or Examples thereof include 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 an amide group.

  The amphoteric surfactant is not particularly limited. For example, an alkylamine oxide having an alkyl group having 8 to 18 carbon atoms, carbobetaine, amide betaine, sulfobetaine, amide sulfobetaine, imidazolinium betaine, Examples thereof include phosphobetaine. From the viewpoint of foaming, one or more amphoteric surfactants selected from the group consisting of sulfobetaine, amide betaine and carbobetaine can be mentioned.

The solid detergent composition for hand washing of textile products of the present invention preferably contains one or more surfactants selected from anionic surfactants and nonionic surfactants as component (a). It is more preferable to contain one or more surfactants selected from ionic surfactants.
In the solid detergent composition for hand washing of textile products of the present invention, the proportion of the anionic surfactant in the component (a) is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100%. It is below mass%. Or 100 mass% may be sufficient.

[Component (b)]
The component (b) is a water-soluble inorganic carbonate. One or more water-soluble inorganic carbonates can be used. Regarding the component (b), “water-soluble” means that 10 g or more is dissolved in 100 g of water at 25 ° C.
(B) As a component, 1 or more types of compounds chosen from alkali metal carbonate and alkali metal hydrogencarbonate are mentioned. Furthermore, 1 or more types of compounds chosen from sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate are mentioned.
The solid detergent composition for hand washing of textile products of the present invention contains at least one compound selected from alkali metal carbonates as the component (b). This is preferable because of its low persistence in clothing.

[Component (c)]
Component (c) is a water-soluble inorganic sodium salt (except for those belonging to (b) and (d)). The component (c) is used as a skeleton for forming a solid detergent composition. On the other hand, the comfort of hand-washing work may be reduced. One or more water-soluble inorganic sodium salts (excluding the component (a)) can be used. Regarding the component (c), “water-soluble” means that 10 g or more is dissolved in 100 g of water at 25 ° C.
(C) As a component, 1 or more types of compounds chosen from sodium sulfate and sodium halide are mentioned. Furthermore, 1 or more types of compounds chosen from sodium sulfate and sodium chloride are mentioned.
It is preferable that the solid detergent composition for hand washing of textile products of the present invention contains sodium sulfate as the component (c).

[Component (d)]
The component (d) is one or more inorganic polyvalent metal ion capture builders selected from aluminosilicates, crystalline silicates, and phosphates. By using a specific amount ratio of the component (d) and the component (c) in a small amount, the comfort of hand washing work or the comfort of the textile product at the time of hand washing can be further improved.

The aluminosilicate of the general formula _{^{(M I, M II 1/2)}} m (Al m Si n O 2 (m + n)) · xH compounds represented by ₂ O and the like. In the formula, M ^I is sodium, potassium, or lithium, M ^II is calcium, magnesium, or barium, m and n are integers, and n ≧ m.
M ^I is preferably sodium or potassium, more preferably sodium.
M ^II is preferably magnesium or calcium, more preferably magnesium.
Examples of the aluminosilicate include zeolite A type, zeolite P type, ferrierite, and mordenite, and zeolite A type is preferable.

Examples of the crystalline silicate include a compound represented by a general formula [ _pM ^I ₂ O · _q SiO ₂ ]. Wherein, M ^I is sodium, potassium, or lithium, preferably sodium. Examples of the crystalline silicate include compounds selected from orthosilicic acid, metasilicic acid, metadisilicic acid, and metal salts thereof.

  Examples of the phosphate include orthophosphate, pyrophosphate, tripolyphosphate, tetraphosphate, hexametaphosphate, and the like. Preferred is a phosphate selected from orthophosphate, pyrophosphate, and tripolyphosphate, and most preferred is tripolyphosphate. As the metal ion, sodium, potassium, lithium and the like can be obtained, and sodium is preferable.

  The solid detergent composition for hand washing of textile products of the present invention is selected from aluminosilicates as component (d) from the viewpoint of further improving the comfort of hand washing work or the comfort of textile products during hand washing. It is preferable to contain more than one compound.

[Composition, other ingredients, etc.]
In the solid detergent composition for hand washing textile products of the present invention, the component (a) is 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more in terms of improving detergency, and at the time of washing. It is contained in an amount of 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less in terms of reducing the hand-stickiness.

  In the solid detergent composition for hand washing of textile products of the present invention, the component (d) is preferably 0.1% by mass or more, more preferably from the viewpoint of further improving the comfort of the textile product during hand washing. 2 mass% or more, and preferably 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it contains 5 mass% or less.

  The solid detergent composition for hand washing of textile products of the present invention has a mass ratio of (a) / (c), which is a mass ratio of the content of the component (a) and the content of the component (c). It is 3 or less. The mass ratio of (a) / (c) is 0.1 or more, preferably 0.15 or more, more preferably 0.20 or more, from the viewpoint of improving detergency, improving the comfort of the hand skin, Or from a viewpoint of the improvement of the comfort of the textile product feel during hand-washing washing, it is 3 or less, Preferably it is 2.0 or less, More preferably, it is 1.0 or less, More preferably, it is 0.90 or less.

  In the solid detergent composition for hand washing of textile products of the present invention, the mass ratio of (b) / (c), which is the mass ratio of the content of component (b) and the content of component (c), is 0 or more and 0. .3 or less. The mass ratio of (b) / (c) is preferably 0.01 or more, more preferably 0.020 or more, and still more preferably 0.030 or more, from the viewpoint of suppressing residual in the fiber product. And from the point of improving the comfort of hand washing work, it is 0.3 or less, preferably 0.2 or less, more preferably 0.10 or less, even more preferably 0.050 or less, and even more preferably 0.040 or less. is there.

  The solid detergent composition for hand washing of textile products of the present invention has a mass ratio of (d) / (c), which is a mass ratio of the content of (d) component and the content of (c) component, 0.001. It is 0.33 or less. The mass ratio of (d) / (c) is preferably 0.0020 or more from the viewpoint of further improving the cleaning power, from the viewpoint of further improving the comfort of hand washing work, or from the viewpoint of further improving the comfort of the fibers. More preferably 0.0030 or more, and from the viewpoint that the detergent component is less likely to remain in the textile product after washing, from the viewpoint of further improving the comfort of hand washing work, or from the viewpoint of further improving the comfort of the fiber Is 0.1 or less, more preferably 0.070 or less.

  “Solid” in the solid detergent composition for hand washing of textile products of the present invention is a state in which the properties of the detergent composition for hand washing for textile products are selected from powder, granules, slurry and paste. Represents that.

  The solid detergent composition for hand washing textile products of the present invention has (e) a first acid dissociation constant of 1 to 5, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 to 5,000. Containing a certain carboxylic acid (hereinafter referred to as component (e)) is preferable from the viewpoint of further improving the comfort of hand-washing work.

The maximum acid dissociation constant (pKa _max ) of the component (e) is the most dissociation constant at 20 ° C. in water among carboxyl groups that are not neutralized as salts, among the substituents in the molecule. Points to high pKa. 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. By adding a compound having a pKa _max of 7 or less to such water, the pH can be effectively lowered. For example, in the case of citric acid, the first acid dissociation constant (pKa1) at 20 ° C. is 3.1, the second acid dissociation constant (pKa2) is 4.8, and the third acid dissociation constant (pKa3) is 6.4. PKa _max is 6.4, and in the case of monosodium citrate, pKa1 at 20 ° C. is 4.8 and 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 (e) 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.

  In addition, the component (e) has a molecular weight of 5,000 or less, preferably 3,000 or less, more preferably 1, from the viewpoint of solubility during washing when used in a solid composition. 000 or less, more preferably 500 or less, more preferably 250 or less. In addition, the component (e) has a molecular weight of 46 or more, preferably 80 or more, more preferably 100 or more, from the viewpoint of the safety or odor of the base.

  Furthermore, the component (e) 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, from the viewpoint of production of the solid detergent composition and storage stability. More preferably, it is 10 g or more, more preferably 30 g or more, more preferably 50 g or more, and preferably 500 g or less, more preferably 300 g or less.

Examples of the component (e) include citric acid (pKa 1: 3.1, pKa _max : 6.4, molecular weight: 192.1, solubility of 73 g in 100 g of water at 20 ° C.), malonic acid (pKa 1: 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.), flop Acid _{(pKa1: 4.9, pKa max:} 4.9, molecular weight: 74.1), lactic acid (pKa1: _{3.8, pKa} max: for 90.1,20 ° C. Water 100 g: 3.8, molecular weight solubility 88 g), acetic acid _{(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 ° C. solubility 56g for 100g water), 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, 20 ° C. Solubility in 100 g of water, benzoic acid (pKa 1: 4.2, pKa _max : 4.2, molecular weight: 122.1, solubility in 100 g of water at 20 ° C. 0.3 g), salicylic acid (pKa 1: 2.8, pKa _max : 2.8, molecular weight: 138.1, solubility in 100 g of water at 20 ° C .: 0.2 g), phthalic acid (pKa 1: 2.9, pKa _max : 5.1, molecular weight: 166.1, 20 ° C. Solubility 0.7 g in 100 g of water), 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), 1,2,4,5 benzene tetracarboxylic acid (pyromellitic _{acid, pKa1: 1.9, pKa max:} 5.6, molecular weight: 254.2,20 ℃ water 100g pairs And a carboxylic acid selected from these salts.
As the component (e), 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, Carboxylic acids selected from 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and salts thereof are preferred, citric acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid More preferably, carboxylic acid selected from malic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and salts thereof, citric acid, malonic acid, succinic acid, maleic acid More preferred are carboxylic acids selected from acids, 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and salts thereof. Arbitrariness. The salt is preferably an alkali metal salt such as sodium salt or potassium salt. The component (e) may be a hydrate or an anhydride.

  In the solid detergent composition for hand washing textile products of the present invention, the component (e) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 10% by mass. % Or less.

  When the solid detergent composition for hand washing textile products of the present invention contains the component (e), it is the mass ratio of the content of the component (b) and the content of the component (e), (b) / (e ) Is preferably 0 or more, more preferably 0.1 or more, still more preferably 0.2 or more, and preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.2. It is as follows.

From the viewpoint of improving the comfort of hand-washing work, the solid detergent composition for hand washing of textile products of the present invention has a temperature of 20 ° C., a hardness of 10 ° dH, and an alkalinity of CaCO ₃ equivalent. PH is 2.5 or more, preferably 2.6 or more, more preferably 2.8 or more, and still more preferably 100 mg / L, using water with a pH of 7.5 and diluted 200 times by mass. 3.0 or more, more preferably 3.2 or more, still more preferably 3.4 or more, still more preferably 3.6 or more, still more preferably 3.8 or more, and still more preferably 4.0 or more. And 9 or less, preferably 8.0 or less, more preferably 7.9 or less, and even more preferably 7 from the viewpoint of improving the comfort of hand-washing work or improving the cleaning power against oil stains derived from food. .8 or less, more preferred 7.6 or less, even more preferably 7.5 or less.

Regarding the pH, water used for diluting the cleaning composition is prepared as follows (hereinafter the same). A concentrated stock solution is prepared by dissolving 78.50 g of calcium chloride dihydrate and 73.58 g of magnesium chloride hexahydrate with 1 L of ion exchange water. This concentrated stock solution has a hardness component of calcium / magnesium = 6/4 (molar ratio). The obtained concentrated stock solution is diluted with water for dilution having an alkalinity of 100 mg / L (calculated as CaCO ₃ ) and pH 7.5, adjusted to 10 ° dH, and used as the water used for diluting the cleaning composition. The dilution water for diluting the concentrated stock solution is obtained by adding sodium hydrogen carbonate to ion exchange water to adjust the alkalinity, and adding hydrochloric acid to adjust the pH.

  The solid detergent composition for hand washing textile products of the present invention can be blended with known ingredients as detergent ingredients within a range that does not significantly affect the washing performance, hand feel 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 and the like.

  As a washing method using the solid detergent composition for hand washing of textile products of the present invention, a washing solution for hand washing of textile products obtained by mixing the solid detergent composition for hand washing of textile products of the present invention and water is used. A method for washing clothes, in which the clothes to which oil stains derived from foods adhere, is used. The washing | cleaning method of this invention can have the process of rinsing the clothing or tableware after washing | cleaning with water.

  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 index 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 lower 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.

For example, water having an alkalinity of 10 mg / L or more and 300 mg / L or less and a hardness of 1 ° dH or more and 50 ° dH or less can be used for the preparation of the textile washing solution for hand washing. 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 mass of calcium carbonate (calculated as CaCO ₃ ), and its unit is mg / L.

  Further, water used for cleaning generally contains hardness components such as calcium ions and magnesium ions, which affects the cleaning power and rinsability. 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 washing liquid for hand washing of the textile product contains (a) component in an amount of 5% by mass to 50% by mass, (b) component, (c) component, (d) component, and (a) / (c) mass. The ratio is 0.1 or more and 3 or less, the mass ratio (b) / (c) is 0 or more and 0.3 or less, and the mass ratio (d) / (c) is 0.001 or more and 0.33 or less. It can be prepared by mixing a solid detergent composition for hand washing textile products and water. In this case, 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 to 300 mg / L and a hardness of 1 ° dH to 50 ° dH.

  Further, the pH of the washing liquid for hand washing is preferably 2.5 or more, more preferably 2.6 or more, and still more preferably from the viewpoint of improving the comfort of hand washing work or improving the cleanability of food stains. 2.8 or more, more preferably 3.0 or more, still more preferably 3.2 or more, still more preferably 3.4 or more, still more preferably 3.6 or more, still more preferably 3.8 or more, Still more preferably, it is 4.0 or more, and preferably 9 or less, more preferably 8.0 or less, still more preferably 7.9 or less, still more preferably 7.8 or less, and even more preferably 7.6. Hereinafter, it is more preferably 7.5 or less. This pH is a pH at the temperature of the environment in which cleaning is performed, and may be a pH at 20 ° C.

<Hand wash method for textile products>
The present invention provides a method for washing and washing textiles having the following steps. In this washing method, the matters described in the washing liquid for hand washing of fiber products, such as preferred examples of the components (a), (b), (c), and (d), the content of each component, and the mass ratio, etc. It can be applied as appropriate.
<Step 1>
(A) Surfactant 5 mass% or more and 50 mass% or less, (b) Water-soluble inorganic carbonate, (c) Water-soluble inorganic sodium salt (except for those belonging to (b) and (d)), ( d) containing at least one inorganic polyvalent metal ion capture builder selected from aluminosilicate, crystalline silicate and phosphate, and having a mass ratio of (a) / (c) of 0.1 to 3 Yes, solid washing for hand washing of textile products in which the mass ratio of (b) / (c) is 0 or more and 0.3 or less and the mass ratio of (d) / (c) is 0.001 or more and 0.33 or less A step of preparing a washing liquid for hand washing of textile products by mixing an agent composition and water.
<Process 2>
A step of washing the textile product by hand with the washing solution for washing the textile product prepared in Step 1.

The solid detergent composition for hand washing of textile products used in Step 1 is preferably the solid detergent composition for hand washing textile products of the present invention. Therefore, the solid detergent composition for hand washing textile products in Step 1 uses water having a detergent composition of 20 ° C., hardness of 10 ° dH, alkalinity of 100 mg / L in terms of CaCO ₃ , and pH 7.5. The pH when diluted 200 times by mass is preferably 2.5 or more and 9 or less.

It is preferable that the solid detergent composition for hand washing of textile products used in Step 1 contains the following (a1) and (a2) as (a).
(A1): a polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an average added mole number of ethylene oxide of 1 to 3, and an alkylbenzene sulfonate having an alkyl group having 10 to 16 carbon atoms One or more surfactants selected from (a2): One or more surfactants selected from alkyl sulfates having 10 to 16 carbon atoms in the alkyl group

  When the solid detergent composition for hand washing textile products used in step 1 contains (a1) and (a2) as (a), the mass ratio of the content of (a1) and the content of (a2) The mass ratio of (a2) / (a1) is preferably 0.05 or more, more preferably from the viewpoint of further improving the comfort of hand-washing work or the comfort of the textile product during hand-washing. 1 or more, more preferably 0.15 or more, more preferably 0.20 or more, more preferably 0.25 or more, and preferably 5 or less, more preferably from the viewpoint of further improving the detergency of dirt. It is 4 or less, more preferably 3 or less, more preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less, and even more preferably 1.0 or less.

  The solid detergent composition for hand washing textile products in Step 1 has (e) a first acid dissociation constant of 1 to 5, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 to 5,000. A weight ratio of (b) / (e) in the solid detergent composition for hand washing of a textile product, which contains a certain carboxylic acid, is 0 or more and 1.5 or less; It is preferable to contain e) 20 ppm or more and 4000 ppm or less. (E) is (e) component of the solid cleaning composition for the hand washing of textile products.

  (E) 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 , 2,3-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid are preferably used.

The alkalinity of the water mixed with the solid detergent composition for washing textile products in Step 1 can be selected from 10 mgL to 300 mg / L.
Moreover, the hardness of the water mixed with the solid detergent composition for hand washing textiles in step 1 can be selected from 1 ° dH to 50 ° dH.
Therefore, water mixed with the solid detergent composition for hand washing of textile products in Step 1 includes water having an alkalinity of 10 mg / L or more and 300 mg / L or less and a hardness of 1 ° dH or more and 50 ° dH or less.

  Moreover, the pH of the washing liquid for hand washing of the textile product in step 1 is preferably 2.5 or more, more preferably 2.6 or more, still more preferably 2.8 or more, still more preferably 3.0 or more, and still more preferably. Is 3.2 or more, more preferably 3.4 or more, still more preferably 3.6 or more, still more preferably 3.8 or more, still more preferably 4.0 or more, and preferably 9 or less. More preferably, it is 8.0 or less, More preferably, it is 7.9 or less, More preferably, it is 7.8 or less, More preferably, it is 7.6 or less, More preferably, it is 7.5 or less. This pH is the pH at the temperature of the environment in which step 1 is performed, and may be the pH at 20 ° C.

  In step 2, the fiber product is washed by hand with the washing liquid for hand washing of the fiber product prepared in step 1.

  A solid detergent composition was prepared by the compaction granulation method using the following blending components and the components shown in Table 1. The form of the solid detergent composition was a powder. Specifically, (b) component, (c) component, (d) component and (e) component were mixed with a ribbon mixer, and then (a) component was sprayed and stirred to obtain the desired composition. 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 Table 1.

[1] pH measurement method A pH measurement composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (pH / ion meter F-23, manufactured by HORIBA), 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.

Using water with a hardness of 10 ° dH, alkalinity of 100 mg / L (calculated as CaCO ₃ ), pH 7.5, 20 ° C., the solid detergent composition shown in Table 1 was diluted to 5 g / L (200 times diluted by mass). A part thereof was filled in a 100 mL beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. The pH measuring electrode was immersed in a diluent adjusted to a constant temperature for 3 minutes, and the pH was measured. The results are shown in the table as the pH of 200-fold water dilution.
Water used for diluting the solid detergent composition was prepared as follows. A concentrated stock solution was prepared by dissolving 78.50 g of calcium chloride dihydrate and 73.58 g of magnesium chloride hexahydrate with 1 L of ion exchange water. This concentrated stock solution had a hardness component of calcium / magnesium = 6/4 (molar ratio). The obtained concentrated stock solution was diluted with water for dilution having an alkalinity of 100 mg / L (calculated as CaCO ₃ ) and pH 7.5, adjusted to 10 ° dH, and used as water used for diluting the cleaning composition. The dilution water for diluting the concentrated stock solution was obtained by adjusting the alkalinity by adding sodium hydrogen carbonate to ion-exchanged water, and adjusting the pH by adding hydrochloric acid.

[2] Clothing persistence evaluation 1 g of the solid detergent composition shown in Table 1 was sampled and 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. The solution was mixed and dissolved in a 2 L beaker to obtain a washing solution. Into it, 1 piece of underwear which measured the mass at the time of drying was thrown in, and it stirred at 800 rpm for 1 minute using the rod-shaped magnetic stirrer of length 5cm as a stirring element. Thereafter, the underwear was taken out, dehydrated in a two-layer washing machine for 1 minute without rinsing, and then dried overnight on a hanger at 25 ° C. and 50% humidity. After drying, the mass of the underwear was measured, and the clothing residual ratio of the detergent component was calculated by the following formula. The underwear used was Gunze YG (round neck T-shirt, M size, 100% cotton).
Residual ratio of clothing (%) = [(underwear mass after test−underwear mass before test (g)) / (underwear mass before test (g)] × 100

[3] Detergency Evaluation Method Hardness 10 ° dH, alkalinity 100mg / L (CaCO ₃ conversion), pH 7.5, 30 ° C of water 3L A washing solution was prepared by diluting and dissolving (Step 1).
Thereafter, one undergarment sewn with five litter oil-contaminated cloths prepared as described below and two undergarments of the same size for adjusting the bath ratio were placed in the cleaning solution, and the whole was stirred. The bath ratio was 8. The underwear used was Gunze YG (round neck T-shirt, M size, 100% cotton). Thereafter, the contaminated cloth was equally rubbed and cleaned by hand for 10 minutes (step 2).
Then, after rinsing twice with 3 L of water similar to the water used for diluting the solid detergent composition, it was squeezed by hand to dehydrate and dried.
The water used for washing and rinsing was prepared as follows. A concentrated stock solution was prepared by dissolving 78.50 g of calcium chloride dihydrate and 73.58 g of magnesium chloride hexahydrate with 1 L of ion exchange water. This concentrated stock solution had a hardness component of calcium / magnesium = 6/4 (molar ratio). The obtained concentrated stock solution was diluted with water for dilution having an alkalinity of 100 mg / L (calculated as CaCO ₃ ) and pH 7.5, adjusted to 10 ° dH, and used as water used for washing and rinsing. The dilution water for diluting the concentrated stock solution was obtained by adjusting the alkalinity by adding sodium hydrogen carbonate to ion-exchanged water, and adjusting the pH by adding hydrochloric acid.
The cleaning rate was measured by the following formula.
Washing rate (%) = [(reflectance after washing−reflectivity 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 using NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

<Preparation of ra oil-contaminated cloth>
Apply 0.1 mL of commercially available S & B oil oil (manufactured by SB Foods Co., Ltd., purchased in June 2013) onto 6 cm x 6 cm cotton knit fabric (cotton knitted silk, 100% cotton, Tanigami store) It was 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) Hand feel during scrubbing,
(II) After the rubbing, rinsing and dehydration, the hand feeling immediately after wiping the hand with a separately prepared towel, and (III) the hand feeling two minutes after wiping the hand 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 criteria for the above (I) were “very uncomfortable” or “slightly uncomfortable” when touching the hand, and “very comfortable” or “slightly 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. An average value of less than 3.0 was accepted. A smaller numerical value is more preferable.
5: Very uncomfortable 4: Slightly uncomfortable 3: Neither 2: Slightly comfortable 1: Very comfortable

[5] Evaluation of comfort of textile product feel during hand-washing work The comfort of textile product feel was evaluated based on the feel of the textile product during washing by the “detergency evaluation method” in [3] above.
Specifically, the comfort of the textile product was evaluated for “(I) During scrubbing” in “Evaluation of comfort of hand-washing work” in [4] above. Ten panelists made judgments based on the following criteria.
The criteria of (I) above are “very uncomfortable” or “slightly uncomfortable” when the textile product is strongly rubbed during rubbing, and the sensation when the textile product is rubbed with water only. Those that are close to are considered “very comfortable” or “somewhat comfortable”.
The average value of 10 panelists was calculated and shown in the table. An average value of less than 3.0 was accepted. A smaller numerical value is more preferable.
5: Very uncomfortable 4: Slightly uncomfortable 3: Neither 2: Slightly comfortable 1: Very comfortable

[6] Compounding component (a) component AES-Na (1): polyoxyethylene having a linear alkyl group having 10 to 16 carbon atoms (average number of added moles 2) alkyl ether sulfate ester sodium, oxygen of oxyethylene group The carbon atom of the alkyl group bonded to the atom is a primary carbon atom, EMAL 270S (manufactured by Kao Corporation)
AES-Na (2): polyoxyethylene having a linear alkyl group having 12 carbon atoms (average addition mole number 3) alkyl ether sulfate sodium, the carbon atom of the alkyl group bonded to the oxygen atom of the oxyethylene group is 1 Grade carbon atom, EMAL 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)
Nonionic surfactant: polyoxyethylene alkyl ether (12 carbon atoms of alkyl group, average number of added moles 10, Emulgen 110L; manufactured by Kao Corporation)

(B) Ingredients Sodium carbonate: Wako Pure Chemical Industries, Ltd. Sodium bicarbonate: Wako Pure Chemical Industries, Ltd.

(C) Ingredients Sodium sulfate: Wako Pure Chemical Industries, Ltd. Sodium chloride: Wako Pure Chemical Industries, Ltd.

(D) Component / Zeolite A type: manufactured by Zeobuilder, No. 2 silicate: “No. 2 silicate” manufactured by Fuji Chemical Co., Ltd. (pure content: 40%, the numbers in the table are pure values)
-Sodium tripolyphosphate: manufactured by Shimonoseki Mitsui Chemicals, trade name: sodium tripolyphosphate)

(E) 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)
Malic acid (pKa 1: 3.4, pKa _max : 5.1, molecular weight: 134.1, solubility 56 g in 100 g of water at 20 ° C.)
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)

・ Alkaline protease: KAP, manufactured by Kao Corporation, granulated product with protein content of 100 mg / enzyme granulated product ・ Cellulase: KAC, manufactured by Kao Corporation, protein content of 20 mg / enzyme granulated product of 1 g Granulated product)
Oligomer D: sodium polyacrylate, manufactured by Kao Corporation Bentonite: Landrosil DGA212, manufactured by Clariant, PEG 13000: polyoxyethylene glycol, molecular weight 13000, manufactured by SINO-Japan, perfume: Table described in JP-A-2005-314559 1 a-3 perfume composition

Claims (12)

(A) 5% by weight or more and 50% by weight or less of a surfactant, (b) a water-soluble inorganic carbonate, (c) a water-soluble inorganic sodium salt (excluding those belonging to (b) and (d)), and (D) a solid detergent composition for hand-washing textiles containing one or more inorganic metal ion scavengers selected from aluminosilicates, crystalline silicates and phosphates;
The mass ratio of (a) / (c) is 0.1 or more and 3 or less,
The mass ratio of (b) / (c) is 0 or more and 0.3 or less,
(D) / (c) mass ratio is 0.001 or more and 0.33 or less,
PH when the cleaning composition is diluted 200 times by mass with water having a temperature of 20 ° C., a hardness of 10 ° dH, an alkalinity of 100 mg / L in terms of CaCO ₃ , and a pH of 7.5. Is not less than 2.5 and not more than 9.
Solid detergent composition for hand washing textile products. The solid detergent composition for hand-washing textiles according to claim 1, comprising (a) including the following (a1) and (a2).
(A1): a polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an average added mole number of ethylene oxide of 1 to 3, and an alkylbenzene sulfonate having an alkyl group having 10 to 16 carbon atoms One or more surfactants selected from (a2): One or more surfactants selected from alkyl sulfates having 10 to 16 carbon atoms in the alkyl group   The solid detergent composition for hand washing textiles according to claim 2, wherein the mass ratio of (a1) and (a2) is 0.05 to 5 in terms of (a2) / (a1).   (E) a carboxylic acid having a primary acid dissociation constant of 1 to 5 and a maximum acid dissociation constant of 7 or less and a molecular weight of 46 to 5,000, and (b) / (e) The solid detergent composition for hand washing of textile products according to any one of claims 1 to 3, wherein the mass ratio is from 0 to 1.5.   (E) 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 solid detergent composition for hand washing textiles according to claim 4, which is at least one carboxylic acid selected from 2,3-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid or a salt thereof. object. A method for washing and washing textile products comprising the following steps.
<Step 1>
(A) Surfactant 5 mass% or more and 50 mass% or less, (b) Water-soluble inorganic carbonate, (c) Water-soluble inorganic sodium salt (except for those belonging to (b) and (d)), ( d) containing at least one inorganic polyvalent metal ion capture builder selected from aluminosilicate, crystalline silicate and phosphate, and having a mass ratio of (a) / (c) of 0.1 to 3 Yes, solid washing for hand washing of textile products in which the mass ratio of (b) / (c) is 0 or more and 0.3 or less and the mass ratio of (d) / (c) is 0.001 or more and 0.33 or less A step of preparing a washing liquid for hand washing of textile products by mixing an agent composition and water.
<Process 2>
A step of washing the textile product by hand with the washing solution for washing the textile product prepared in Step 1. The method for washing and washing textiles according to claim 6, wherein the solid detergent composition for washing textiles contains (a) the following (a1) and (a2).
(A1): a polyoxyethylene alkylsulfuric acid ester salt having an alkyl group having 10 to 16 carbon atoms and an average added mole number of ethylene oxide of 1 to 3, and an alkylbenzene sulfonate having an alkyl group having 10 to 16 carbon atoms One or more surfactants selected from (a2): One or more surfactants selected from alkyl sulfates having 10 to 16 carbon atoms in the alkyl group   The method for washing and washing textiles according to claim 7, wherein the mass ratio of (a1) and (a2) is 0.05 to 0.9 in terms of (a2) / (a1).   The solid detergent composition for hand washing textile products in Step 1 has (e) a first acid dissociation constant of 1 to 5, a maximum acid dissociation constant of 7 or less, and a molecular weight of 46 to 5,000. A certain carboxylic acid is contained, the mass ratio of (b) / (e) in the solid detergent composition is 0 or more and 1.5 or less, and the washing liquid for hand washing textile products in Step 1 contains 20 ppm or more of (e). The method for washing and washing textile products according to any one of claims 6 to 8, which is contained in an amount of 4000 ppm or less.   (E) 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 method for hand-washing a textile product according to claim 9, which is at least one carboxylic acid selected from 2,3-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid or a salt thereof. The solid cleaning composition for hand washing of textile products in Step 1 has a temperature of 20 ° C., a hardness of 10 ° dH, an alkalinity of 100 mg / L in terms of CaCO ₃ , and a pH of 7.5. The method for washing and washing textiles according to any one of claims 6 to 10, wherein the pH when diluted 200-fold by mass with water is 2.5 or more and 9 or less.   The method for washing and washing textiles according to any one of claims 6 to 11, wherein the pH of the washing liquid for washing textiles in Step 1 is 2.5 or more and 9 or less.