JP5780843B2 - Powder detergent composition - Google Patents

Description

  The present invention relates to a powder detergent composition.

  The powder detergent for clothing is required to have excellent cleaning performance for quickly removing dirt, dissolution performance for quick dissolution / dispersion in water, storage stability performance that does not deteriorate even when stored under severe conditions, and the like.

  However, when washed under harsh conditions, such as when the laundry exceeds the specified amount, the powder detergent sandwiched between clothing will reduce the efficiency of contact with water and the surrounding solution Since the saturated concentration is reached, undissolved residue may be generated. Furthermore, as described in Patent Document 1, when the detergent is stored, the zeolite may be solidified under the influence of an acid by carbon dioxide in the air, and may remain in the fiber. In order to solve these problems, Patent Document 2 proposes a detergent with little undissolved residue by dividing the detergent particles into a plurality of specific particle size ranges and then reblending the particles having excellent solubility in each fraction. ing. In addition, as disclosed in Patent Document 3, there is a technique that attempts to solve the problem by devising, for example, strictly adjusting the particle size of two types of granules containing a cellulosic polymer while limiting the blending amount of zeolite. However, there is a difficulty that the degree of freedom is low in the formulation and particle design of the powder detergent.

  On the other hand, attempts to blend carboxymethyl cellulose into a powder detergent composition are cases where blending is carried out to prevent recontamination as in Patent Document 4, or as a disintegration aid for pellet detergent extruded and granulated as in Patent Document 5. However, to date, there has been no study on the use of carboxymethylcellulose from the viewpoint of preventing stain-like undissolved residue due to zeolite during stuffing and washing, and therefore, a sufficient effect has been found. There wasn't. Also, among powder detergent compositions, a dough-like material is formed by kneading and mixing detergent components, and the dough-like material is extruded through a perforated screen while being continuously cut at the tip. For high bulk density powder detergents obtained by pulverizing and then granulating granular high bulk density powder detergents and bulk detergents, the washing ingredients are tightly and compacted, so the problem of undissolved matter is sufficient. It was not something to solve.

JP-A-61-85494 Republished WO00 / 042162 Special table 2008-527159 gazette JP 2009-173917 A Special table 2010-526202 gazette

  An object of the present invention is to provide a powder detergent composition that not only has excellent anti-recontamination properties but also does not cause stains on textiles when unmelted.

  As described above, carboxymethyl cellulose (hereinafter sometimes referred to as CMC) is known to be used in detergents as a recontamination inhibitor. The anti-recontamination agent is an agent that suppresses mud dirt or the like released from the laundry during washing and washing from adhering to the laundry again from the washing liquid. However, CMC blended for this purpose is effective in preventing re-contamination of dirt evenly dispersed in the washing liquid. Zeolite is also difficult to adhere to laundry if it is a zeolite in the washing liquid. Even if it doesn't stand out. On the other hand, as pointed out as the problem of the present invention, the powder detergent sandwiched between the laundry packed more than specified may not be sufficiently dispersed and may remain dissolved in the laundry. For stains generated in this way, the effect of CMC is unknown. The occurrence of stains spoils the appearance of low-lightness textiles such as black and dark blue.

  In order to solve the above problems, the present inventors have proceeded with an analysis of stains that occur when laundry is overfilled. As a result, it was found that the particles causing the stain do not remain on the surface of the fiber product, but the particles causing the stain enter the inside of the fiber product. Then, the present inventors have considered a mechanism in which the stain-causing particles do not enter the inside of the fiber product, and have provided the present invention here.

  That is, the present invention provides (A) an anionic surfactant (hereinafter referred to as component (A)), (B) a nonionic surfactant (hereinafter referred to as component (B)), and (C) an average particle size of 3. ˜50 μm zeolite (hereinafter referred to as “component (C)”) 5-60 mass%, (D) carboxymethylcellulose having a weight average molecular weight of 200,000 to 2,000,000 and a degree of etherification of 0.18 to 0.65 or a salt thereof [ Hereinafter referred to as the component (D)] 0.1 to 10% by mass, the total content of (A) and (B) is 5 to 60% by mass, and the (A) / (B) mass ratio is The present invention relates to a powder detergent composition having an average particle diameter of 4/6 to 6/4 and an average particle diameter of 100 to 1000 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the powder detergent composition excellent in the recontamination prevention property which does not generate | occur | produce the stain | pollution | contamination by the undissolved residue in textiles is provided.

<(A) component>
Examples of the anionic surfactant include a sulfate ester salt of an alcohol having 10 to 18 carbon atoms, a sulfate ester salt of an alkoxylate of an alcohol having 8 to 20 carbon atoms, an alkyl (10 to 16 carbon atoms) benzenesulfonate, paraffin ( C10-18) sulfonate and fatty acid salt are mentioned. These salts include alkali metal salts, ammonium salts, amine salts and the like. In the present invention, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms is preferred, and the counter ion is preferably an alkali metal or amine, and more preferably a sodium ion or Preference is given to potassium ions, and sodium alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain is more preferred. The powder detergent composition of the present invention preferably contains an alkyl (carbon number 10 to 16) benzene sulfonate as the main surfactant from the viewpoint of improving the dispersibility of the zeolite which is the blend thereof. In the ionic surfactant, alkyl (10 to 16 carbon atoms) benzene sulfonate, and further a linear alkyl group having 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms. Preferably, the alkylbenzene sulfonate having a ratio of 90% by mass or more, more preferably 95% by mass or more.

<(B) component>
Nonionic surfactants include, for example, higher alcohol ethylene oxide (hereinafter referred to as “EO”) adducts, higher alcohol EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. Can be mentioned. More specifically, polyoxyalkylene alkyl (10 to 16 carbon atoms) ether, polyoxyalkylene alkyl (10 to 16 carbon atoms) phenyl ether, alkyl (8 to 16 carbon atoms) polyglycoside, polyoxyalkylene sorbitan fatty acid ( C10-18) ester, polyoxyalkylene glycol fatty acid (C10-18) ester, polyoxyethylene polyoxypropylene block polymer, polyoxyalkylene alkylol (fatty acid) (C10-18) amide, etc. Is done. As the nonionic surfactant of the component (B), polyoxyethylene alkyl ether which is an EO adduct of a higher alcohol is preferable. Further, from the viewpoint of dispersing the component (D) itself, the carbon number of the alkyl group is A polyoxyethylene alkyl ether having 10 to 16 and an average added mole number of EO of 3 to 30 is preferred.

<(C) component>
The zeolite used in the present invention includes A-type, X-type, Y-type, P-type and the like. Among them, A-type zeolite which is generally excellent in cation exchange ability is preferable as a builder for detergents. A-type zeolite has an X-ray diffraction pattern at a position indicated by 4A-type zeolite (No. 38-241) presented by JCPDS (Joint Committee on Powder Diffraction Standards). expression _{xM 2 O · ySiO 2 · Al} 2 O 3 ( however, M represents an alkali metal, x = 0.5 to 1.5, a y = 0.5 to 6) are of.

  The average particle size of the component (C) is preferably 3 μm or more, and more preferably 5 μm or more, from the viewpoint of preventing penetration into the deep gaps of the fibers. Moreover, from a viewpoint of preventing the undissolved residue of the stain, 50 μm or less is preferable, 30 μm or less is more preferable, and 20 μm or less is still more preferable. The average particle size of the component (C) was measured using a laser diffraction / scattering particle size distribution analyzer (“LA950” manufactured by Horiba, Ltd.), with water having a refractive index of 1.30 as a dispersion medium and a circulation rate of 4 The value of the volume median particle size (D50) when measured after circulation for 1 minute without ultrasonic irradiation is defined as the average particle size.

<(D) component>
The powder detergent composition of the present invention has a weight average molecular weight of 200,000 to 2,000,000 and a degree of etherification (hereinafter referred to as DS) as component (D) from the viewpoint of reducing stain due to undissolved residue and preventing recontamination. 0.18 to 0.65 carboxymethylcellulose or a salt thereof.

  Carboxymethyl cellulose is obtained by, for example, mixing cellulose raw materials such as pulp with alcohol solvent and caustic to form a slurry and arserating (activating cellulose), reacting with chloroacetic acid, and carrying out a carboxylation reaction. The molecular weight and DS of carboxymethylcellulose obtained by selection of the raw material pulp and the amount of chloroacetic acid treated are determined.

  Component (D) has a weight average molecular weight of 200,000 to 2,000,000, preferably 250,000 to 2,000,000, more preferably 250,000 to 1,000,000, from the viewpoint of suppression of stain due to undissolved residue and re-contamination prevention. 250,000 to 500,000 is more preferable.

The weight average molecular weight of the component (D) can be measured by gel permeation chromatography (GPC) equipped with an RI and UV detector. Sample injection volume is 100 μL, eluent 0.2 M phosphate buffer / CH ₃ CN = 9/1 The measurement is performed at a column temperature of 40 ° C. using GMPWXL + GMPWXL (anion) as a column at a flow rate of 1 ml / min. The weight average molecular weight is a molecular weight in terms of polyethylene glycol.

  The degree of etherification (DS) of component (D) is from 0.18 to 0.65, preferably from 0.18 to 0.50, preferably from 0.18 to 0.30, from the viewpoint of suppression of stains due to undissolved components. Is more preferable. (D) DS about a component is described by the method of the below-mentioned Example.

  As described above, the present inventors have found that as a cause of the stain, particles that become a stain enter the fiber. As a reason for this, it was considered that particles permeate into the inside of the fiber by allowing water to permeate through the fiber by dehydration after the washing step or dehydration after rinsing. That is, by suppressing the undissolved residue from entering the inside of the fiber during dehydration, the particles causing the stain can be kept on the fiber surface, and it has been found that the stain due to the undissolved residue is difficult to occur. As a means for solving the problem, an important component is the component (D). That is, in the present invention, the gel produced by the component (D) coats the fiber surface, and the undissolved residue is prevented from entering the depth of the fiber so that the undissolved residue cannot be easily washed away in the rinsing process. Reduces stains caused by The component (D) used in the present invention is used for forming a gel-like film on the cloth surface and preventing the undissolved residue from penetrating deep into the cloth fibers. When carboxymethylcellulose suitable for developing such an action is treated on a cloth, a phenomenon that the passage speed of water passing through the cloth is delayed is observed. In the present invention, the component (D) preferably has a filtration rate described in the examples below of 80 to 450 seconds. In the present invention, component (D) is a carboxymethyl cellulose having a specific weight average molecular weight and a specific degree of etherification, or a salt thereof, which is used to suppress the occurrence of stain stains during washing. It has been found that the effect of the component (D) is remarkably exhibited at a specific (A) / (B) mass ratio.

<Powder detergent composition>
In the powder detergent composition of the present invention, the mass ratio (A) / (B) is 4/6 to 6/4, and preferably 4/6 to 5/5, from the viewpoint of stain prevention due to undissolved residue and cleaning performance. It is.

  Moreover, in the powder detergent composition of this invention, the sum total of content of (A) and (B) is 5-60 mass%. 10 mass% or more is preferable from a viewpoint of washing | cleaning performance, and 20 mass% or more is more preferable. Moreover, from a fluid viewpoint of a powder detergent composition, it is 60 mass% or less, 40 mass% or less is preferable and 30 mass% or less is still more preferable.

  Moreover, the powder detergent composition of this invention contains 5-60 mass% of (C) component. From the viewpoint of improving the washing performance and powder physical properties, it is 5% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, from a viewpoint of reducing the stain | pollution | contamination by an undissolved residue, it is 60 mass% or less, 50 mass% or less is preferable and 40 mass% or less is still more preferable.

  Moreover, the powder detergent composition of this invention contains 0.1-10 mass% of (D) component. From the viewpoint of reducing a stain due to undissolved residue, the content is 0.1% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Further, from the viewpoint of preventing undissolved carboxymethylcellulose itself, it is 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less.

  The powder detergent composition of the present invention is a detergent component usually added, for example, various surfactants, builders, enzymes, bleaching agents (percarbonate, perborate, bleach activator, etc.), softening agents. , A reducing agent (sulfite, etc.), a fluorescent brightener, a foam suppressor (silicone, etc.) and a fragrance.

  The average particle size of the powder detergent composition of the present invention is preferably 100 μm or more, more preferably 150 μm or more, and even more preferably 200 μm or more from the viewpoint of powdering. Moreover, from a soluble viewpoint, 1000 micrometers or less are preferable, 800 micrometers or less are more preferable, and 700 micrometers or less are still more preferable.

  The use of the powder detergent composition of the present invention is suitable as a powder detergent composition for clothing in the sense of including not only household clothing but also cloth products such as towels, sheets, shoes and mats. In the case of the powder detergent composition for clothing, the apparent density (bulk density) is preferably 0.5 to 1.0 g / ml, more preferably 0.6 to 0.9 g / ml.

  A preferred composition for clothing is shown below.

(Surfactant)
As the surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be blended as necessary. Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or alkyls thereof. Examples thereof include ester salts and fatty acid salts. Furthermore, a linear alkylbenzene sulfonate having 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms is preferable.

  Examples of the nonionic surfactant include ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. Further, an EO 1 to 10 mol adduct of an alcohol having 10 to 16 carbon atoms is preferable in terms of removal of sebum soil, hard water resistance, biodegradability, and compatibility with a linear alkylbenzene sulfonate.

  Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid aminopropyl betaines, and examples of cationic surfactants include mono (or di) long chain alkyl quaternary ammonium salts.

  As for the compounding quantity of surfactant in a composition, 1-60 mass% is preferable. The upper limit is more preferably 50% by mass or less, still more preferably 40% by mass or less, and the lower limit of the amount is more preferably 5% by mass or more, still more preferably 10% by mass or more. In addition, in blending the surfactant, it is necessary to consider that the quantitative relationship between the component (A) and the component (B) satisfies the conditions of the present invention.

(builder)
Builders include inorganic builders and organic builders. Examples of inorganic builders include alkaline inorganic salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, crystalline layered sodium silicate, sodium silicate, and water such as sulfate, sulfite, hydrogen sulfate, hydrochloride, and phosphate. Inorganic salts and the like can be blended. Examples of the organic builder include nitrilotriacetate (NTA), water-soluble organic acid salts such as ethylenediaminetetraacetate (EDTA) citrate and fumarate, and carboxylic acid polymers. 1-50 mass% is preferable and, as for the compounding quantity of the builder in a composition, 1-40 mass% is more preferable. In addition, in blending the builder, it is necessary to consider that the blending amount of the component (C) satisfies the conditions of the present invention.

(Other ingredients)
Other cleaning ingredients include enzymes, bleaches, percarbonates, perborates, bleach activators, recontamination inhibitors (carboxymethylcellulose other than component (D), etc.), softeners, reducing agents ( Sulfites, etc.), optical brighteners, antifoaming agents (silicone, etc.), fragrances and the like can be contained, but the blending amount thereof is preferably 0.1 to 60% by mass, and 0.1 to 50% by mass. % Is more preferable.

  In addition, a cationic polymer known as a dye transfer inhibitor or the like in a laundry detergent for clothes and a cationic polymer having a diallyldialkylammonium salt as a monomer constituent unit inhibits the effects of the present invention, so its inclusion The amount is preferably 0.01% by mass or less, and further preferably not contained.

  Preferably, the powder detergent containing the following component is mentioned. The preferred range of the concentration of each component may be the concentration range described above.

  In addition to the components in the table, a cleaning aid can be contained. For example, cleaning enzymes such as protease, cellulase, amylase or lipase, hydrogen peroxide releasing materials such as sodium percarbonate or sodium perborate as bleaching agents, sodium alkanoyloxy (8 to 18 carbon atoms) sodium benzenesulfonate or tetraacetylethylenediamine It is preferable to use one or more of bleaching activators such as (TAED), softening agents such as bentonite particles, and alkali agents such as crystalline layered sodium silicate.

Synthesis example of carboxymethyl cellulose (1)
A biaxial kneader whose rotational speed is adjusted to 100 rpm is added with 911 parts of 99% isopropyl alcohol and 78.7 parts of sodium hydroxide dissolved in 189 parts of water, and a commercially available cellulose (cotton linter PCS2400, manufactured by Shandong Takami Chemical Co., Ltd.) ) Was charged in an amount of 200 parts (parts by mass). After stirring and mixing at 30 ° C for 90 minutes to prepare alkali cellulose, 20 parts of monochloroacetic acid dissolved in 90 parts of 90% isopropyl alcohol is added with further stirring, and the temperature is raised to 70 ° C in 30 minutes and allowed to react for 90 minutes. It was. After completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried and pulverized to obtain carboxymethylcellulose (CMC-A) having a DS of 0.10 and a weight average molecular weight of 300,000.

Synthesis example of carboxymethyl cellulose (2)
A carboxymethyl cellulose (CMC-B) having a DS of 0.20 and a weight average molecular weight of 300,000 was obtained in the same manner as in the synthesis example of (1) except that the amount of monochloroacetic acid dissolved in 90 parts of 90% isopropyl alcohol was 28 parts. Obtained.

Synthesis example of carboxymethyl cellulose (3)
A biaxial kneader whose rotational speed is adjusted to 100 rpm is added with 1044 parts of 99% isopropyl alcohol and 69.8 parts of sodium hydroxide dissolved in 162 parts of water, and commercially available cellulose (cotton linter PCS2400, manufactured by Shandong Takami Chemical Co., Ltd.) ) 200 copies. After stirring and mixing at 30 ° C for 90 minutes to prepare alkali cellulose, 32 parts of monochloroacetic acid dissolved in 90 parts of 90% isopropyl alcohol is added with further stirring, and the temperature is raised to 70 ° C in 30 minutes and allowed to react for 90 minutes. It was. After completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried and pulverized to obtain carboxymethylcellulose (CMC-C) having a DS of 0.24 and a weight average molecular weight of 300,000.

Synthesis example of carboxymethyl cellulose (4)
A carboxymethyl cellulose (CMC-D) having a DS of 0.18 and a weight average molecular weight of 300,000 was obtained in the same manner as in the synthesis example (1) except that the amount of monochloroacetic acid dissolved in 90 parts of 90% isopropyl alcohol was 25 parts. Obtained.

(I) Degree of etherification of carboxymethyl cellulose (DS)
2 g of the sample was precisely weighed and placed in a 300 mL conical flask with a stopper. A nitric acid solution (a solution obtained by adding 100 mL of special concentrated nitric acid to 1000 mL of methanol) was added and stirred for 3 hours to convert the carboxymethyl cellulose (CMC) into an acid form (hereinafter referred to as H-CMC). 1.5-2.0 g of the absolutely dry H-CMC was weighed and placed in a 300 mL conical flask with a stopper. H-CMC was moistened with 15 mL of 80% methanol, 100 mL of 0.1N NaOH was added, and the mixture was stirred at room temperature for 3 hours. Using phenolphthalein as an indicator, it was back titrated excess NaOH with 0.1N-H ₂ SO _4. The DS of CMC was calculated by the following formula.
A = [(100 × FB × F ′) × 0.1] / (H-CMC absolute dry mass (g))
DS = 0.162 × A / (1-0.058 × A)
A: 0.1N-NaOH amount (mL) required for neutralizing 1 g of H-CMC
B: 0.1N-H ₂ SO ₄ titration value (mL) (mL)
F: Factor of 0.1N—H ₂ SO ₄ F ′: Factor of 0.1N—NaOH

(II) Filtration speed of carboxymethylcellulose 55φmm in a filter holder with a filter size of 25φmm (type of glass filter separated into a base equipped with a funnel and a support screen, with a filter in between and fixed with a clamp) The qualitative filter paper (No. 2) was sandwiched, 150 mL of an aqueous solution of carboxymethylcellulose (concentration 6.7 ppm) was added to the funnel portion, and the mixture was naturally filtered. The time (seconds) required for the amount of the aqueous solution remaining in the funnel portion to change from 150 mL to 125 mL was defined as the filtration rate.

Examples 1-7 and Comparative Examples 1-10
Each component was mix | blended in the ratio shown in Table 2, and powder detergent composition ae was prepared. Each composition was prepared by mixing carboxymethyl cellulose in Table 3 with a composition (base detergent) containing other components. The average particle size and cloth residue (whiteness) of the obtained powder detergent composition were measured and evaluated by the following methods. The results are shown in Table 3.

(1) Average particle diameter of the powder detergent composition Using a 9-stage sieve having a mesh size of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm Stack in order, add 100 g of granules from the top of the top 2000 μm sieve, cover and roll tap sieve shaker (manufactured by Hiraiko Seisakusho, tapping 156 times / minute, rolling: 290 times / minute) After being attached to the plate and vibrated for 5 minutes, the mass of particles remaining on each sieve and the saucer was measured, and the mass ratio (%) of the particles on each sieve was calculated. The mass ratio of the particles on the sieve with small openings is accumulated in order from the saucer. When the opening of the first sieve with a weight frequency of 50% or more is aμm and the opening of the sieve that is one step larger than aμm is bμm, the cumulative weight frequency from the pan to the aμm sieve is c%, When the weight frequency on the a μm sieve is d%, the average particle diameter can be obtained from the following equation.

(2) Cloth persistence test In the cloth persistence test, the powder detergent used was left in a room at 30 ° C and 70% RH for 3 days. Further, as a test cloth, a black dyed cotton broad 40 (plain weave black cloth) from Tanigami Shoten Co., Ltd., cut into a circle having a diameter of 8 cm was used. Create Filled in a 1 liter beaker (inner diameter 105 mm, height 150 mm, for example, manufactured by Iwaki Glass Co., Ltd.) with the exchanged water at 25 ° C., and the water temperature at 25 ° C. was kept constant in a water bath. Stirring is performed at a rotational speed (1000 rpm) at which the depth of the vortex with respect to the water depth is approximately 1/3 with a child (length 35 mm, diameter 8 mm, for example, model: manufactured by ADVANTEC, Teflon (registered trademark) round thin type). The powder detergent composition weighed so as to be 0.6667 ± 0.0010 g is charged and dispersed in water with stirring, and stirring is continued. 10 minutes after charging, the dispersion is poured into a black cloth set in a suction filter in advance and suction filtered (suction filter = 90 mm diameter Buchner funnel / suction bottle with a black cloth cut to 8 cm in diameter) thing). Next, a cloth is added to a tartometer containing 1 L of tap water (20 ° C.), and after stirring at 85 rpm for 1 minute, stirring of the tartometer is stopped, the cloth is taken out, and the wash surface is filled with tap water. Lightly rinse in a bowl. The fabric is dried for 30 minutes in a 105 ° C. dryer. The whiteness (L ^* value) of the dried cloth was measured with a spectroscopic color difference meter (SE-2000 manufactured by Nippon Denshoku) to obtain the whiteness of the cloth. Smaller whiteness means less residual amount. In this evaluation, the whiteness is preferably 21.5 or less. When the whiteness exceeds 21.5, a white stain is clearly noticeable on the black cloth in the visual evaluation.

(3) Prevention of recontamination (carbon)
The powder detergent composition was added to 1 L of 4 ° hard water at 20 ° C. and stirred sufficiently to obtain a cleaning solution. After 0.25 g of carbon black selected by the Japan Oil Chemistry Association (Asahi Carbon Co., Ltd., carbon black for Asahi cleaning) was added to this cleaning liquid and dispersed, this liquid was placed in a sample cup of a Terg-O-Tometer. Transfer 5 pieces of 6cm x 6cm cotton white cloth (standard product selected by Japan Oil Chemical Association, # 2023 cloth sold by Laundry Science Association) as evaluation cloth and 48g of 6cm x 6cm white cotton cloth as adjustment cloth Then, carbon was recontaminated by stirring for 10 minutes at a temperature of 20 ° C. and a rotational speed of 80 rpm.

Next, the evaluation fabric was taken out, thoroughly rinsed and dried, and the recontamination prevention rate was calculated by the following formula.
Recontamination prevention rate (%) = [(reflectance of white cotton cloth after test) / (reflectance of white cotton cloth before test)] × 100
The reflectance was measured with a color difference meter (SE2000) manufactured by Nippon Denshoku Industries Co., Ltd. (measurement wavelength: 550 nm).
The recontamination prevention rate of each detergent composition was compared with Comparative Example 1 and evaluated according to the following criteria.

Evaluation criteria A: 10% (10 points) or more higher than the recontamination prevention rate of Comparative Example 1 ○: 5% or more and less than 10% (5 points or more and less than 10 points) higher than the recontamination prevention rate of Comparative Example 1 : 0% or more and less than 5% (0 point or more and less than 5 points) higher than the recontamination prevention rate of Comparative Example 1 ×: Difference from the recontamination prevention rate of Comparative Example 1 is less than 0% (minus point) (Comparative Example 1 is lower than the recontamination prevention rate)

(4) Prevention of recontamination (mud)
Instead of 0.25 g of the carbon black described above, 2.5 g of mud particles (Kanuma Akado for gardening that passed through a 200-mesh sieve (purchased from Kuniyukien (10, Zensho-cho, Izumi City, Osaka))) was used. Except for the above, mud re-contamination was evaluated in the same manner as carbon re-contamination evaluation. The evaluation criteria for mud dirt are shown below.
◎: 5% (5 points) or more higher than the recontamination prevention rate of Comparative Example 1 ○: 1% or more and less than 5% (1 point or more and less than 5 points) higher than the recontamination prevention rate of Comparative Example 1 △: Comparison 0% or more and less than 1% (0 point or more and less than 5 points) higher than the recontamination prevention rate of Example 1 ×: The difference from the recontamination prevention rate of Comparative Example 1 is less than 0% (minus point) (of Comparative Example 1 Lower than recontamination prevention rate)

* 1 In Comparative Example 1, carboxymethylcellulose was 0% by mass and sodium sulfate was 11% by mass.

The components in Table 2 are as follows.
・ LAS-Na: alkyl group sodium alkylbenzene sulfonate having 12 to 14 carbon atoms ・ Non-ionic surfactant: a mixture of 10 to 14 carbon primary alcohol with an average of 8 mol of EO ・ Fatty acid sodium : Fatty acid sodium / zeolite having an alkyl group having 14 to 18 carbon atoms: “Zeobuilder” (type 4A, average particle size 4 μm) manufactured by Zeobuilder
AA / MA polymer: acrylic acid-maleic acid copolymer (sodium salt (70 mol% neutralized), monomer ratio is acrylic acid / maleic acid = 3/7 (molar ratio), average molecular weight 70000)
・ Crystalline silicate: crystalline layered sodium silicate [Product name Prefeed 6N, manufactured by Tokuyama Siltech Co., Ltd.]
PEG: polyethylene glycol (weight average molecular weight 8500)
-Fluorescent dye: "Chino Pearl CBS-X" manufactured by Ciba Geigy Co., Ltd. and "Wytex SA" manufactured by Sumitomo Chemical Co., Ltd., blended in 1/1 (mass ratio)-Enzyme: Cellulase K (JP-A 63-264699) Issue)
The average particle size of the zeolite was measured using a laser diffraction / scattering particle size distribution measuring device (“LA950” manufactured by Horiba, Ltd.), with water having a refractive index of 1.30 as a dispersion medium, After circulating for 1 minute without sonication, the value of the volume median particle size (D50) as measured was taken as the average particle size.

Claims (3)

(A) an anionic surfactant, (B) a nonionic surfactant, (C) average particle size of 5 to 60 wt% zeolite 3 to 50 [mu] m, (D) a weight average molecular weight from 250000 to 2000000 and, It contains 0.1 to 10% by mass of carboxymethyl cellulose having a degree of etherification of 0.18 to 0.65 or a salt thereof, and the total content of (A) and (B) is 5 to 60% by mass. ) / (B) A powder detergent composition having a mass ratio of 4/6 to 5/5 and an average particle size of 100 to 1000 μm. The powder detergent composition according to claim 1, wherein the alkylbenzene sulfonate having a linear alkyl group having 10 to 16 carbon atoms occupies 90% by mass or more in (A). The powder detergent composition according to claim 1 or 2, wherein (D) is carboxymethyl cellulose having a filtration rate of 80 to 450 seconds or a salt thereof as defined below.
Filtration speed: Qualitative filter paper of 55φmm (No.) with a filter holder of 25φmm filter size (type of glass filter separated by a base equipped with a funnel and support screen, with a filter in between and fixed with a clamp) 2), 150 mL of an aqueous solution of carboxymethylcellulose (concentration 6.7 ppm) is added to the funnel portion, and the mixture is naturally filtered. The time (seconds) required for the amount of the aqueous solution remaining in the funnel part to reach 150 mL to 125 mL is defined as the filtration rate.