JP2010144147A - Powder detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powder detergent composition having a high alkali-buffering capacity and excellent in detergency, and to provide a method of washing clothing using the same. <P>SOLUTION: The powder detergent composition (1) is prepared by mixing an alkali granule (a), containing a surfactant and a crystalline alkali metal silicate and having an average particle diameter of 100-1,000 μm, with a granule (b), containing an acid source and a carbon dioxide source and having an average particle diameter of 100-1,000 μm, wherein the content of the crystalline alkali metal silicate is 28-65 mass% and the pH of 1 g/L concentration of an aqueous solution at 25°C is 10-11. In the method (2) of washing clothing using the composition, carbon dioxide generated by reacting the granule (a) with the granule (b) is discharged to the outside of the washing system. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a powder detergent composition having excellent detergency and a method for washing clothes using the same.

The sebum stain derived from the human body, which is the most typical stain that adheres to clothing, contains a large amount of free fatty acids, oils such as glycerides, etc. in the stain, and they contain carbon and mud in the dust, exfoliated keratin, etc. Observed as confinement, especially dirt such as wrinkles and sleeves. In these washings, a washing theory is known in which carbon, mud and keratin are removed from clothing mainly by solubilizing and removing these oils with surfactant micelles.
According to this cleaning theory, in order to obtain a high detergency, the detergent concentration (alkaline agent concentration) in the washing liquid may be increased to increase the pH. However, if the alkali agent concentration is too high, it will deviate from the category of weakly alkaline detergents (pH 8 to 11) stipulated in the Household Goods Quality Labeling Law, and there are measures and indications that encourage consumers to use them safely. It becomes inconvenient because it is not easy to use as a product.
For this reason, the amount of crystalline alkali metal silicate is conventionally limited, and there has been a limit to improving the cleaning power with a weak alkaline detergent.

For example, Patent Document 1 discloses that each component of a non-soap surfactant, a fatty acid and / or an alkali metal fatty acid, a crystalline alkali metal silicate, and a sequestering agent has a specific mass ratio, A laundry detergent composition having a bulk density is disclosed, and Patent Document 2 contains a surfactant, an alkali metal silicate, and a sequestering agent, and each ingredient has a specific mass ratio. A composition is disclosed.
According to Patent Documents 1 and 2, it is disclosed that a high detergency can be expressed even if the amount of the surfactant is small under specific high alkali / low hardness cleaning conditions. Crystalline alkali metal silicate which expresses high pH is blended.

By the way, Patent Document 3 discloses a controlled foaming system for a detergent composition, which includes foaming components that can form bubbles without stirring (foamable granules such as acid supply sources and carbonates) and a silicone foam inhibitor. Has been.
Patent Document 4 discloses a granule containing a foaming component containing an acid source and a carbon dioxide source, a binder, and a detergent activator, wherein the acid source and the carbon dioxide source have a specific particle size. In addition, it is disclosed that when this foaming component is diluted with water, it foams and thereby exhibits good solubility and dispersibility.
However, the detergent compositions containing the granules described in Patent Documents 3 and 4 are not sufficiently satisfactory in terms of substantial detergency and the like.

Japanese Patent Laid-Open No. 9-235591 Japanese Patent Laid-Open No. 11-269489 JP-T-2002-526640 Special Table 2002-53686 Publication

  This invention makes it a subject to provide the washing | cleaning method of the powder cleaning composition excellent in the detergency, and the clothing using the same.

The inventors of the present invention can solve the above problem by adjusting the pH by mixing granules containing an acid source and a carbon dioxide source into alkali granules containing a large amount of crystalline alkali metal silicate. I found out.
That is, the present invention provides the following (1) and (2).
(1) Alkali granules (a) having an average particle size of 100 to 1000 μm containing a surfactant and crystalline alkali metal silicate, and granules having an average particle size of 100 to 1000 μm containing an acid source and a carbon dioxide source A cleaning composition comprising (b) mixed, wherein the content of the crystalline alkali metal silicate is 28 to 65% by mass, and the pH of the aqueous solution having a concentration of 1 g / L at 25 ° C. is 10 to 11. A powder cleaning composition.
(2) A method of washing clothes using the powder cleaning composition of (1), wherein carbon dioxide gas generated by the reaction between alkali granules (a) and granules (b) is released out of the cleaning system. How to wash clothes.

  ADVANTAGE OF THE INVENTION According to this invention, the powder cleaning composition excellent in the detergency, especially the powder cleaning composition for clothing, and the washing | cleaning method of clothing using the same can be provided.

The powder cleaning composition of the present invention comprises an alkali granule (a) having an average particle size of 100 to 1000 μm containing a surfactant and a crystalline alkali metal silicate, and an average particle containing an acid source and a carbon dioxide source A detergent composition obtained by mixing granules (b) having a diameter of 100 to 1000 μm, wherein the content of the crystalline alkali metal silicate is 28 to 65% by mass, and an aqueous solution having a concentration of 1 g / L at 25 ° C. The pH is 10 to 11, and is particularly useful as a powder cleaning composition for clothing.
Hereinafter, each component of the powder cleaning composition of this invention is demonstrated one by one.

<Alkali granules (a)>
The alkali granule (a) used in the present invention is an alkali granule containing a surfactant and a crystalline alkali metal silicate and having an average particle size of 100 to 1000 μm.
The content of the alkali granule (a) in the powder cleaning composition of the present invention is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, from the viewpoint of cleaning performance and pH. What contains -80 mass% is more preferable.

(Surfactant)
The surfactant used in the present invention is not particularly limited, and examples thereof include one or more selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. For example, a plurality of nonionic surfactants may be used in combination, or a plurality of various anionic surfactants and nonionic surfactants may be selected and used in combination. Preferably, the surfactant contains 30 to 100% by mass of the nonionic surfactant, more preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene glycol fatty acid alkyl ester, Examples include polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, alkyl glucose amide, alkyl amine oxide and the like.
Among these, an ethylene oxide adduct of a monovalent or divalent alcohol having a linear or branched alkyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, having an average addition mole number of 3 A polyoxyethylene alkyl ether of ˜25, preferably 6-20, is preferred. Since those having an average added mole number of 0 to 1 tend to lower the powder physical properties, the content is preferably 20% by mass or less, more preferably 15% by mass or less.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate, Examples include amino acid type surfactants and N-acyl amino acid type surfactants. Among these, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, and the like are preferable.
Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylamine salts, and examples of the amphoteric surfactant include amphoteric surfactants such as carboxy type or sulfobetaine type.

  The content of the surfactant is preferably 1 to 40% by mass, more preferably 6 to 30% by mass in the entire composition. If the surfactant content is less than 1% by mass, sufficient detergency tends to be difficult to obtain, and if it exceeds 40% by mass, the amount of crystalline alkali metal silicate is relatively reduced and sufficient. Tends to be difficult to obtain.

(Crystalline alkali metal silicate)
Since the crystalline alkali metal silicate used in the present invention has alkali ability and ion exchange ability, the washing power and washing conditions of the powder detergent composition are suitably adjusted by appropriately adjusting the blending amount thereof. be able to.
As the crystalline alkali metal silicate, an alkali metal silicate having SiO ₂ / M ₂ O (wherein M represents an alkali metal) is preferably 0.5 to 2.6. Preferred examples thereof include those having the following composition formula (1).
_{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (1)
(In the formula, M represents a group Ia element in the periodic table, Me represents one or a combination of two or more selected from group IIa, IIb, IIIa, IVa or group VIII element, and y / x = 0.5 to 2 .6, z / x = 0.01-1.0, n / m = 0.5-2.0, w = 0-20.)

In the general formula (1), M is selected from group Ia elements of the periodic table, and examples of group Ia elements include Na and K. These may be used alone or, for example, Na ₂ O and K ₂ O may be mixed to constitute the M ₂ O component.
Me is selected from group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe. Among these, Mg and Ca are preferable from the viewpoint of resources and safety. These may be singly or as a mixture of two or more, for example MgO, may constitute the Me _m O _n component by mixing CaO and the like. Further, the crystalline alkali metal silicate in the present invention may be a hydrate, and the amount of hydration in this case is in the range of w = 0-20.

In the general formula (1), y / x is preferably 0.8 to 2.4, more preferably 1.0 to 2.2, from the viewpoints of detergency, solubility, and the like. Moreover, from a viewpoint of cation exchange ability, 1.5-2.1 are more preferable.
Z / x is preferably 0.01 to 1.0, more preferably 0.02 to 0.9, from the viewpoint of detergency, solubility, and the like. x, y, and z are not particularly limited as long as they are in the relationship shown in the above y / x and z / x.
As described above, when xM ₂ O is, for example, x′Na ₂ O · x ″ K ₂ O, x is x ′ + x ″. This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. N / m = 0.5 to 2.0 represents the number of oxygen ions coordinated with the element, and is substantially 0.5, 1.0, 1.5, or 2.0. .

Examples of the crystalline alkali metal silicate other than that represented by the composition formula (1) include those having the composition formula (2).
M ₂ O · x'SiO ₂ · y'H ₂ O (2)
(In the formula, M represents an alkali metal, and x ′ = 0.5 to 2.6 and y ′ = 0 to 20).
In the formula (2), x ′ is preferably 0.8 to 2.4, more preferably 1.0 to 2.2 from the viewpoints of detergency, solubility and the like. Moreover, from a viewpoint of cation exchange ability, 1.5-2.1 are more preferable. y ′ is preferably y ′ = 0.

Crystalline alkali metal silicates in the present invention, the M ₂ O having a composition formula (1), consists of three components SiO _2, Me _m O _n, those having the formula (2) is M ₂ O , Composed of two components of SiO ₂ . Therefore, in order to produce the crystalline alkali metal silicate in the present invention, each component is required as a raw material, but in the present invention, a known compound can be appropriately used without particular limitation.
For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. More specifically, as a raw material of M ₂ O _{component, NaOH, KOH, Na 2 CO} 3, K 2 CO 3, Na 2 SO 4 and the like, and as the raw material of Me _m O _n component, CaCO ₃ MgCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO, ZrO ₂ , dolomite and the like. Examples of the SiO ₂ component include silica, kaolin, talc, fused silica, and sodium silicate.

As an example of preparing a crystalline alkali metal silicate, the above-mentioned raw material components are added in a predetermined amount so as to have the x, y, z or x ′, y ′ values of the target crystalline alkali metal silicate. A method of mixing at a ratio and firing and crystallizing in a heating furnace such as an electric furnace or a gas furnace, usually at a temperature of 300 to 1500 ° C, preferably 500 to 1000 ° C, more preferably 600 to 900 ° C. If heating temperature is in the said range, a detergency and an ion exchange capacity will not fall significantly. The heating time is usually 0.1 to 24 hours, although it depends on the heating temperature.
More specifically, JP-A-60-227895, JP-A-7-187655, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristallogr., 129, 396-404 (1969). ) And the like. Examples of commercially available products, K.K. Tokuyama Siltech: such pre-feed (SiO ₂ / Na ₂ O (mole ratio) = 2.0) and the like. Alternatively, sodium metasilicate (SiO ₂ / Na ₂ O (molar ratio) = 1.0) may be used.
Said crystalline alkali metal silicate can be used individually or in combination of 2 or more types.

The crystalline alkali metal silicate thus obtained exhibits a pH of 11 or higher in a 0.1% by mass dispersion, and exhibits an excellent alkaline ability as compared with sodium carbonate or potassium carbonate. Further, the crystalline alkali metal silicate is particularly excellent in the alkali buffering effect.
When the crystalline alkali metal silicate is ion-exchanged for 10 minutes at a concentration of 0.4 g / L with respect to a 100 ppm CaCl ₂ aqueous solution in terms of CaCO ₃ , the Ca ion-exchange capacity is 100 CaCO ₃ mg / g. As described above, those having 180 mg / g to 250 mg / g are preferable.

The crystalline alkali metal silicate has an average particle size of preferably 0.1 to 200 μm, more preferably 1 to 50 μm, and still more preferably 1 to 20 μm from the viewpoints of detergency and stability. Here, the average particle diameter is the median diameter of the particle size distribution.
The crystalline alkali metal silicate having such an average particle diameter can be pulverized using a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill, etc., and adjusted to an appropriate average particle diameter.
The content of the crystalline alkali metal silicate in the powder detergent composition of the present invention is preferably 28 to 65% by mass, more preferably 35 to 60% by mass, and still more preferably 40 to 60% by mass.
In addition to the surfactant and the crystalline alkali metal silicate, the alkali granule (a) used in the present invention has the purpose of delaying the storage stability and solubility of the alkali granule (a) and the stain of the surfactant. You may mix | blend well-known cleaning agent base materials (other mixing | blending base materials), such as a builder mix | blended with a detergent, in order to prevent taking out. The blending ratio of the other blend base in the alkali granule (a) is preferably 20% or less, and more preferably 10% or less, from the viewpoint of the alkali ability of the alkali granule.

<Granule (b)>
The granule (b) used in the present invention is a granule containing an acid source and a carbon dioxide source and having an average particle size of 100 to 1000 μm.
The content of the granule (b) in the powder detergent composition of the present invention is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, more preferably 20 to 50% from the viewpoint of foamability. % Containing is more preferable.

(Acid source)
The acid source is a compound that reacts with the acid itself or another compound to form an acid.
Examples of the acid source include one or more selected from mono- or polycarboxylic acids, or hydrates or anhydrides of carboxylic acid polymers. Among them, those having an acid dissociation constant (pKa) at 25 ° C. of 2.0 to 10.0, more preferably 3.0 to 8.0, and further 4.0 to 7.0 are preferably used.
In these, the polymer of mono- or polycarboxylic acid is preferable, and what can act as a chelating agent which has calcium capture ability by becoming Na salt is preferable.
Specifically, the organic acid is preferably a mono-, di- or triprotic acid, and suitable examples of the organic acid include citric acid, adipic acid, glutaric acid, 3-cetoglutaric acid, citramalic acid, tartaric acid, Examples thereof include sulfonic acids such as maleic acid, fumaric acid, malic acid, succinic acid, malonic acid, and toluenesulfonic acid. Such acids are preferably used in their acid form, anhydrous form or mixtures.
Among these, from the viewpoints of alkaline buffer capacity, storage stability, and solubility, one or more selected from citric acid, tartaric acid, maleic acid, fumaric acid, malic acid, and anhydrides thereof are more preferable, and citric acid is preferred. Particularly preferred.

Specific examples of the polymer of carboxylic acid include, for example, polymerization reaction of acrylic acid, (anhydrous) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid, and salts thereof, and copolymerization of each monomer. Those synthesized by a reaction or a copolymerization reaction with other polymerizable monomers may be mentioned. Examples of other copolymerization monomers used for copolymerization include, for example, aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, Examples include propylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol when hydrolyzed after copolymerization), and acrylic acid esters. Further, polyacetal carboxylic acid polymers such as polyglyoxylic acid described in JP-A-54-52196 can also be used. As said polymer and a copolymer, a thing with a weight average molecular weight of 800-1 million is used, Preferably a 5000-200,000 thing is used.
Among these, an acrylic acid polymer having a molecular weight of 5,000 to 10,000 or a copolymer of acrylic acid and maleic acid having a molecular weight of 50,000 to 100,000 is preferably used from the viewpoint of cleaning performance and storage stability.

0
Any acid source may be used as long as it reacts with an alkali carbonate to generate carbon dioxide gas. If it has such a function, a part of the acid source may be neutralized with Na, ammonium salt or ka salt.
The acid source itself or the neutralized product works as a chelating agent, and the higher the function of softening water, the more preferable. The acid source itself or the neutralized product preferably has a pKca of 1.8 or more, preferably 2 Two or more are more preferable.
Also, acid source, an ion exchange capacity of itself or its neutralized product Ca is preferably 180mgCaCO ₃ / g or more, 200mgCaCO ₃ / g or more of is more preferably used.

The particle size of the acid source, preferably the acid itself, preferably has a volume median particle size of 1-800 μm, more preferably 5-500 μm, more preferably 5-60 μm, more preferably 5-30 μm. preferable.
Such an acid source is preferably obtained by pulverizing or pulverizing a coarse acid source material having a particle size larger than that of the acid source immediately before blending into the foaming component. That is, the handling of fine particle size acid sources after storage can cause problems, so it is advantageous to store the acid source in a coarse form and grind this material before use.
The content of the acid source in the cleaning composition of the present invention is preferably 2 to 75% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 28% by mass.

(Carbon dioxide source)
A carbon dioxide source refers to a substance that can generate carbon dioxide when it reacts with an acid source in contact with water. Examples of the carbon dioxide source include carbonates, and carbonates, bicarbonates and percarbonates or mixtures thereof are particularly preferable.
Examples of the carbonate include alkali metal salts such as potassium, lithium, and sodium. Among them, sodium carbonate and potassium are preferable, and sodium carbonate is more preferable.
Examples of the bicarbonate include alkali metal salts such as lithium, sodium, and potassium. Among them, sodium bicarbonate and potassium are preferable, and sodium bicarbonate is more preferable.
The choice of carbonate, bicarbonate or mixtures thereof in the dry granules (b) can be made depending on the pH desired in the aqueous medium in which the dry granules (b) are dissolved. For example, when a relatively high pH (eg, pH 9.5 or higher) is desired in an aqueous medium, it is preferable to use the carbonate alone or a combination of carbonate and bicarbonate, later in the case Is typically from 0.1 to 10, more preferably from 1 to 5, most preferably from 1 to 2 carbonate to bicarbonate, wherein the carbonate level is higher than the bicarbonate level. .

The particle size of the carbon dioxide source is preferably 1 to 800 μm, more preferably 5 to 500 μm, more preferably 5 to 60 μm, and still more preferably 5 to 30 μm.
It should be noted that the volume median particle size of the acid source and the carbon dioxide source is determined by a known method, particularly a laser light scattering device or diffractometer programmed to show the volume median particle size, for example, a Malvern 2600 or Sympatec Helos laser. It can be measured by a light scattering device (or diffractometer).
The content of the carbon dioxide source in the cleaning composition of the present invention is preferably 2 to 75% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 28% by mass.
In the granule (b) of the present invention, in addition to the acid source and the carbon dioxide source, for the purpose of improving the storage stability of the granule (b), a builder or the like blended in a coating material such as a surfactant or a polymer or a detergent is used. You may mix | blend a well-known cleaning agent base material (other compounding base materials). The blending ratio of the other blend base in the granule (b) is preferably 20% or less, more preferably 10% or less, from the viewpoint of the alkalinity of the alkali granule.

<Manufacture of alkali granules (a) and granules (b)>
There is no restriction | limiting in particular in the manufacturing method of the alkali granule (a) and granule (b) used by this invention, After mixing each component, extrusion granulation method, rolling granulation method, fluidized bed granulation method, spray granulation It can be produced by a known method such as a granulation method or a crushing granulation method. Examples of granulators that can be used include Fukae Powtech Co., Ltd. High Speed Mixer, High Flex Gral, Henschel Mixer, Powrec Vertical Granulator, Taiheiyo Kiko Co., Ltd. Apex Granulator, Proshare Mixer , Julia mixer manufactured by Deoksugaku Kogyo Co., Ltd., Redige mixer manufactured by Matsubo Co., Ltd., intensive mixer manufactured by Nihon Eirich Co., Ltd., Malmerizer manufactured by Fuji Powdal Co., Ltd. Fine disc pelleter, roller compactor manufactured by Freund Sangyo Co., Ltd., roller compactor manufactured by Turbo Industry Co., Ltd., briquette manufactured by Shinto Kogyo Co., Ltd., briquetting manufactured by Hosokawa Micron Co., Ltd. Shin, and the like.

More specifically, the alkali granule (a) is preferably produced from a surfactant and a crystalline alkali metal silicate by a rolling granulation method. Among the rolling granulation methods, the stirring rolling granulation method is particularly preferable from the viewpoint of granulation yield and the like.
The stirring tumbling granulator generally has a main stirring shaft having a main stirring shaft provided with stirring blades, and further assisting mixing and suppressing the generation of coarse particles. And having a structure protruding from the wall surface in a direction perpendicular to the surface.
In the production of the alkali granule (a), from the viewpoint of using a liquid or paste surfactant as a binder, a high speed mixer, a Henschel mixer, a Redige mixer, and an intensive mixer are preferable, and the particle size distribution of the granulated particles is uniform. Therefore, a high speed mixer or a Redige mixer having a rotating blade and a chopper device is more preferable.
The granule (b) is preferably dry granulated. For example, a commercially available acid source material having a large particle size is pulverized to adjust the particle size, and mixed with a carbon dioxide source. Preferably, other ingredients are added to form a mixture and granulated using a roller compactor.
A roller compactor is composed of a feed hopper equipped with a feed screw, a roll press, a granulator (pulverizer / granulator), etc., and compresses the powder raw material between two rolls rotating at the same speed to achieve a high density. This is a dry crushing and granulating apparatus that forms a plate-like molded product (flakes) and crushes it with a granulator to form granules of several mm or less.

The average particle diameter of the alkali granule (a) is preferably 100 to 1000 μm, more preferably 200 to 800 μm, still more preferably 300 to 700 μm, from the viewpoints of solubility and fluidity. The average particle diameter of the granule (b) is preferably 100 to 1000 μm, more preferably 200 to 800 μm, still more preferably 300 to 700 μm, from the viewpoints of fluidity and storage stability.
The mixing device for mixing the granules (a) and (b) of the present invention is not limited as long as it can be uniformly mixed. For example, a horizontal cylindrical type, V type mixer, A stirring granulator or a rolling granulator can be used.
The blending ratio (a) / (b) between the alkali granule (a) and the granule (b) is preferably 85/15 to 30/70, more preferably 80/20 to 35/65, from the viewpoint of foamability and cleaning performance. 80/20 to 40/60 is particularly preferable.

<Powder cleaning composition>
The powder cleaning composition of the present invention is a powder cleaning composition obtained by mixing alkali granules (a) and granules (b), and the content of crystalline alkali metal silicate is 28 to 65% by mass. The pH of an aqueous solution having a concentration of 1 g / L at 25 ° C. is 10 to 11.
The powder detergent composition of the present invention can be used without particular limitation as long as it is an application using a powder detergent, but can be particularly suitably used as a powder detergent for clothing.
The powder detergent composition of the present invention includes, for example, known detergent base materials such as builder granules, bleach (percarbonate, perborate, bleach activator, etc.), bleach activator, recontamination An inhibitor (such as carboxymethyl cellulose), a softening agent, a reducing agent (such as sulfite), a fluorescent brightener, an antifoaming agent (such as silicone), an enzyme such as cellulase or protease, a dye, a fragrance, etc. may be appropriately blended. it can.
The content of the crystalline alkali metal silicate in the alkali granule (a) in the powder detergent composition is preferably 30 to 62% by mass, more preferably 35 to 60% by mass, from the viewpoint of cleaning ability. is there. Moreover, pH of the aqueous solution with a density | concentration of 1 g / L in 25 degreeC is 10-11, Preferably it is 10.3-10.9. Adjustment of pH of this aqueous solution can be performed by adjusting content etc. of the acid source of a granule (b).

<How to wash clothes>
The method for washing clothes of the present invention is a method for washing clothes using the powder detergent composition of the present invention, wherein the carbon dioxide generated by the neutralization reaction of the granules (b) in water is removed from the washing system. It is characterized by being discharged and washed. As a result, the acidic gas goes out of the washing system, so that the washing bath becomes alkaline and the washing performance is improved.
Further, due to the foaming of the granules (b), the granules (b) are dispersed and dissolved in a much shorter time than the alkali granules (a). As a result, when the product upon completion of the neutralization reaction of the granules (b) has a Ca ion exchange capacity, Ca ions in the cleaning system are captured faster than usual.
In general, in water with high hardness under high alkali, dirt such as fatty acid tends to form scum, and such dirt is difficult to remove by washing. Therefore, in order to perform ideal washing with good stain removal, first reduce the hardness in the washing system with a chelating agent, then increase the alkali amount to change the fatty acid and other dirt to fatty acid sodium (soap), and emulsify the dirt. A washing mode with an alkali delay that is allowed to occur is preferable. In the cleaning method of the present invention, the granule (b) having a Ca-capturing ability dissolves quickly while foaming, and then the alkali granule (a) dissolves and exhibits alkalinity. Therefore, the effect of alkali retardation is easily exhibited.

Furthermore, when an acid source having a pKa of 2 to 10, more preferably 4 to 7 is used for the granule (b), the pH is not so high after dissolution of the alkali granule (around pH = 7 to 8) In this region), the buffering action works and the increase in pH is suppressed. By this action, the alkali retardation effect is further promoted, and the effect of further improving the cleaning performance can be obtained. As a specific degree of the alkali delay, the time to reach the maximum pH is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, and more preferably 40 seconds to 2 minutes. In the washing method of the present invention, the generated acidic carbon dioxide gas is released to the outside of the cleaning system, and the cleaning performance is improved by two actions of pH increase and alkali delay effect. Since the washing method of the present invention is a cleaning method that exhibits these two effects, it can exhibit excellent cleaning power.
In the clothes washing method of the present invention, the amount of the powder detergent composition to be used is not particularly limited, but usually 15 to 30 g, preferably 18 to 25 g per 30 L of water, will exhibit sufficient detergency. Can do.

  In the following preparation examples, examples and comparative examples, “parts” and “%” are “parts by mass” and “% by mass” unless otherwise specified. Various physical properties were measured by the following methods.

(1) Measurement of average particle diameter Using a 9-stage sieve and a tray having a mesh size of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm, the sieves are stacked in order from a sieve with a small mesh size. Add 100 g of granules from the top of the top 2000 μm sieve, cover and attach to a low-tap sieve shaker (manufactured by Hiraiko Seisakusho, tapping 156 times / minute, rolling: 290 times / minute) After vibrating for 5 minutes, the mass of the particles remaining on each sieve and the saucer was measured, and the mass ratio (%) of the particles on each sieve was calculated. The average particle size was determined by accumulating the mass ratios of the particles on the sieve having a small mesh size in order from the saucer to give a total of 50%.
(2) Measurement of pH 1 L of ion-exchanged water at 25 ° C. was added to a beaker having a capacity of 1 L, and a stirrer piece having a length of 35 mm was added thereto and stirred at 950 rpm. When the pH electrode was set and the pH was stable, 1 g of a test sample was added, and the maximum pH was measured.

(3) Measurement of cleaning rate An artificial contamination liquid having the following composition is attached to the cloth by the following method to prepare an artificial contamination cloth, and a stirring type detergency tester (manufactured by Ueshima Seisakusho Co., Ltd., trade name: Targotometer) is used. Use the following method to wash 5 contaminated cloths under the conditions of a rotational speed of 85 rpm, a washing time of 10 minutes, a temperature of 20 ° C., and water of use of 4 ° DH (Ca / Mg = 8/2). Asked.
(Composition of artificial contamination liquid)
Lauric acid 0.44%, myristic acid 3.09%, pentadecanoic acid 2.31%, palmitic acid 6.18%, heptadecanoic acid 0.44%, stearic acid 1.57%, oleic acid 7.75%, trio Rain acid 13.06%, n-hexadecyl palmitate 2.18%, squalene 6.53%, yolk lecithin liquid crystal 1.94%, Kanuma red soil 8.11%, carbon black 0.01%, tap water balance amount.

(Method of adhering artificial contamination liquid to cloth: for details, see the example of JP-A-7-270395)
It is composed of a cloth unwinding part, a gravure contaminated part, a drying part, a brushing part, and a cloth winding part. Between the cloth unwinding part and the gravure contaminated part, a meander adjustment device, and between the gravure contaminated part and the drying part A gravure type contamination machine equipped with a tension control device that adjusts the tension of the cloth in between was prepared. The cloth [cotton gold width 2003 cloth (made by Tanigami Shoten)] is unloaded from the unwinding section through the sheet feeding roll and the meandering adjusting section, and conveyed to the gravure contaminated section. The contaminated part is composed of a gravure roll A, a pressing roll B, and a contaminated bath C. The cloth passed between rolls A and B, and the dirt adhering to roll A was pressed by roll B and applied to the cloth.
The gravure roll A (cell capacity: 58 cm ³ / cm ² ) is engraved (concave portion with a groove), and after soaking it in the dirt liquid, excess dirt adhered to the roll surface other than the concave portion Was scraped off with a doctor knife, and the dirt in the groove of the roll was applied to the cloth (application speed: 1.0 m / min). Then, it dried at 100 degreeC for 1 minute, wound up the dirt cloth through the brushing process.
(Measurement of cleaning rate)
Measure the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after cleaning with a self-recording color meter (manufactured by Shimadzu Corporation), determine the cleaning rate (%) by the following formula, and measure the cleaning rate of five sheets The average value was shown as the cleaning power.
Washing rate (%) = [(reflectance of contaminated cloth after washing−reflectance of contaminated cloth before washing) / (reflectance of raw cloth−reflectance of contaminated cloth before washing)] × 100

Preparation Example 1 (Preparation of Granule A-1)
(1) Preparation of activator mixed solution Polyoxyethylene alkyl ether (nonionic surfactant, manufactured by Kao Corporation, trade name: Emulgen 106KM) at a temperature of 80 ° C., sodium alkylbenzene sulfonate ( Anionic surfactant, alkyl group having 12 to 14 carbon atoms, Kao Corporation, trade name: Neoperex G-15, linear alkylbenzene sulfonic acid precursor corresponding to 20 parts by mass (Kao Corporation, trade name) : Neopex FS) and a sodium hydroxide aqueous solution as a neutralizing agent were mixed to prepare a surfactant mixed solution.
(2) Preparation of Granule A-1 Crystalline alkali metal silicate having an average particle size of 13 μm (manufactured by Tokuyama Siltech Co., Ltd., pre-made by a high speed mixer (Fukae Pautech Co., Ltd., trade name: LFS-GS-2J) 200 g of feed) was added and mixed at a blade rotation speed of 600 rpm and a chopper rotation speed of 800 rpm. The surfactant mixed solution 55g was added there over 1 minute. Stir for 1 minute after the end of the addition, 3 g of florite (made by Tokuyama Corporation, special calcium silicate, 2CaO.3SiO ₂ .mSiO ₂ .nH ₂ O (1 <m <2, 2 <n <3)) Added and surface modified. The obtained granules were classified with a two-stage sieve equipped with a 125 μm sieve at the lower part and a 1,000 μm sieve at the upper part, and granules having a particle size of 125 to 1000 μm were collected to obtain granules A-1.

Preparation Example 2 (Preparation of granule A-2)
(1) Preparation of base granule Ion exchange water was added to a mixing tank (capacity: 180 L) having a stirring blade having a length of 200 mm and heated while stirring. After the water temperature reaches 55 ° C., 31.8 parts by mass of sodium carbonate (Dens ash, manufactured by Central Glass Co., Ltd.) is added, and then sodium sulfate (anhydrous neutral bow glass, manufactured by Shikoku Kasei Co., Ltd.) 21.2 A part by mass was added and stirred for 15 minutes. Thereafter, 40 parts by mass of a sodium polyacrylate aqueous solution (mass average molecular weight 10,000, manufactured by Kao Corporation) is added in an amount of 15 parts by mass. Part) was added and stirred for 15 minutes, then 24.1 parts by weight of 4A-type zeolite (Silton B, manufactured by Mizusawa Chemical Co., Ltd.) was added and stirred for 30 minutes to give a homogeneous slurry (water content 53% by weight) 60 kg. Got. This slurry was spray-dried to obtain base granules having a water content of 1.2% by mass.
(2) Granulation of granule A-2 48.1 parts by mass of crystalline alkali metal silicate (manufactured by Tokuyama Siltec Co., Ltd., pre-feed) having an average particle size of 13 μm and 19.2 parts by mass of the base granule The mixture was added to a Redige mixer (capacity 20 L, manufactured by Matsubo Co., Ltd.), and the main shaft was stirred at 80 rpm. Thereto, 23.1 parts by mass of the activator mixed solution was added and granulated for 1 minute. Thereafter, the main shaft rotation speed is 150 rpm, the chopper rotation speed is 3500 rpm, and the surface modification is performed with 9.6 parts by mass of crystalline alkali metal silicate having an average particle diameter of 13 μm (manufactured by Tokuyama Siltech Co., Ltd., pre-feed). 5 kg of granules were obtained. The obtained granules were classified with a two-stage sieve having a 125 μm sieve attached to the lower part and a 1,000 μm sieve attached to the upper part, and 125 to 1,000 μm particle size granules were collected to obtain granules A-2. The results are shown in Table 1.

Preparation Example 3 (Preparation of granules B-1 to B-7)
The raw materials shown in Table 2 (all manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in the proportions shown in Table 2, and a roller compactor (Freund Sangyo Co., Ltd., trade name: TF-MINI) was used. Compression granulation was performed at a roller pressure of 80 kg / cm ² . The obtained granules were classified with a two-stage sieve having a 125 μm sieve attached to the lower part and a 1,000 μm sieve attached to the upper part, and 125 to 1,000 μm granular particles were collected to obtain granules B-1 to B-7. did. The results are shown in Table 2.

Examples 1-8 and Comparative Examples 1-3
Granule A-1 and granule B were mixed at a blending ratio shown in Table 3, a detergent composition was prepared, and pH and washing rate were measured.
In all examples, the pH was in the range of 10-11. Further, in Comparative Example 1, the pH was below 10, and the cleaning performance was lower than that of the Example. In Comparative Examples 2 and 3, the washing rate was the same as that of the Example, but the pH exceeded 11 in both cases. The results are shown in Table 3.

Using the granules A-2 and the granules B-2 and B-4, the cleaning compositions (test detergent 1 and test detergent 2 (comparative example)) having the composition shown in Table 4 were prepared, and the following test examples 1 to 6 were prepared. A cleaning test was conducted.
Test Example 1 (Example 9)
900 mL of 20 ° C. ion exchange water was added to a stirring type detergency tester (trade name: Targometer, manufactured by Ueshima Seisakusho Co., Ltd.) and stirred at 85 rpm, and 0.667 g of test detergent 1 was added during the stirring. After stirring for 1 minute, 100 mL of 40 ° hard water (Ca: Mg = 8: 2) and 5 sheets of contaminated cloth were added, and washing was started. Thereafter, washing was performed for 10 minutes, and the cleaning power was evaluated. Moreover, when 5 minutes passed after washing | cleaning, the pH meter was put in the bath and pH of the washing | cleaning liquid was measured. Table 5 shows the pH and washing rate after 5 minutes of washing.
In the case of this example, since the generated carbon dioxide gas was redissolved in the cleaning system, foaming was not recognized. Further, since the redissolved carbon dioxide functioned as an acid, the pH did not increase.
Test Example 2 (Example 10)
900 mL of ion-exchanged water at 20 ° C. was added to the targotometer and stirred at 85 rpm, and 0.667 g of test detergent 1 was added during the stirring. Immediately thereafter, in the same manner as in Test Example 1, hard water and a contaminated cloth were added and washed for 10 minutes. The pH and washing rate are shown in Table 5.
In the case of this example, since the generated carbon dioxide gas was redissolved in the cleaning system, foaming was not recognized. Further, since the redissolved carbon dioxide functioned as an acid, the pH did not increase.

Test Example 3 (Example 11)
When 900 mL of 20 ° C. ion exchange water was added to the targotometer and 0.667 g of test detergent 1 was added therein, foaming was observed. Thereafter, the targotometer was stirred at 85 rpm for 1 minute, and then, as in Test Example 1, hard water and a contaminated cloth were added and washed for 10 minutes. The pH and washing rate are shown in Table 5.
In the case of this example, carbon dioxide gas was generated by the reaction of the granule B-1 containing citric acid and sodium carbonate, and foamed and released out of the system. Since carbon dioxide is an acidic gas, the pH of the cleaning system is increased, and as a result, the cleaning performance is considered to be improved.
Test Example 4 (Example 12)
When 900 mL of ion-exchanged water at 20 ° C. was added to the targotometer, and 0.667 g of test detergent 1 was added therein, foaming was observed. Immediately thereafter, as in Test Example 1, hard water and a contaminated cloth were added and washed for 10 minutes. The pH and washing rate are shown in Table 5.
In the case of this example, carbon dioxide gas was generated by the reaction of the granule B-1 containing citric acid and sodium carbonate, and foamed and released out of the system. As a result, it is considered that the pH of the cleaning system increased and the cleaning performance was improved.

Test Example 5 (Comparative Example 4)
900 mL of ion exchange water at 20 ° C. was added to the targot meter, and 0.667 g of test detergent 2 was added therein. Since test detergent 2 (comparative example) did not contain an acid source (citric acid), foaming was not observed. Immediately thereafter, in the same manner as in Test Example 1, hard water and a contaminated cloth were added and washed for 10 minutes. As a result, the cleaning rate was excellent, but the pH exceeded 11. The results are shown in Table 5.
Test Example 6 (Comparative Example 5)
900 mL of ion exchange water at 20 ° C. was added to the targotometer, and 0.667 g of a commercial detergent (trade name: Attack, manufactured by Kao Corporation) was added therein. Since this commercial detergent does not contain an acid source (citric acid), no foaming was observed. Immediately thereafter, in the same manner as in Test Example 1, hard water and a contaminated cloth were added and washed for 10 minutes. As a result, the cleaning rate was insufficient as compared with Test Examples 3 and 4. The results are shown in Table 5.

Table 5 shows the following.
(1) Comparison between Test Example 1 (Example 9) and Test Example 3 (Example 11) From the comparison between Test Example 1 and Test Example 3, when the test detergent was introduced, the case where there was foaming, It can be seen that the cleaning performance is excellent. This is presumably because the acidic carbon dioxide gas escaped out of the cleaning system and the pH of the cleaning system rose.
(2) Comparison between Test Example 1 (Example 9) and Test Example 2 (Example 10) FIG. 1 shows that test detergent 1, test detergent 2, and commercially available detergent were each placed in 1 L of ion-exchanged water at 25 ° C. It is a figure which shows the pH change over time when 667g is added. Test detergent 1 has a moderate increase in pH compared to test detergent 2 and commercially available detergents, and the pH becomes constant in about 60 seconds.
The difference between Test Example 1 and Test Example 2 is whether or not the sample was stirred for 1 minute before putting the contaminated cloth. Test Example 1 was washed with hard water after the pH had risen sufficiently, whereas Test Example 2 was washed under alkaline delay conditions such that the pH finally increased in about 60 seconds after the start of washing. Therefore, it is considered that a higher detergency than Test Example 1 was expressed due to the alkali retardation effect.
(3) About Test Example 4 (Example 12) Test Example 4 was changed to Test Example 5 in which the cleaning pH exceeded 11 due to two actions of pH increase and alkali delay effect due to the release of the generated carbon dioxide gas outside the cleaning system. Near detergency was expressed.

It is a figure which shows the pH change over time when 0.667 g of test detergent 1, test detergent 2, and commercially available detergent are added to 1 L of ion exchange water at 25 ° C., respectively.

Claims (4)

  Alkali granules (a) having an average particle diameter of 100 to 1000 μm containing a surfactant and crystalline alkali metal silicate, and granules (b) having an average particle diameter of 100 to 1000 μm containing an acid source and a carbon dioxide source A powder composition, wherein the content of the crystalline alkali metal silicate is 28 to 65% by mass, and the pH of the aqueous solution having a concentration of 1 g / L at 25 ° C. is 10 to 11. Cleaning composition.   The powder cleaning composition according to claim 1, wherein the acid source is at least one selected from mono- or polycarboxylic acids, or hydrates or anhydrides of carboxylic acid polymers.   The powder cleaning composition of Claim 1 or 2 whose carbon dioxide source is carbonate.   A method for washing clothes using the powder detergent composition according to any one of claims 1 to 3, wherein carbon dioxide generated by the reaction between the alkali granules (a) and the granules (b) is removed from the washing system. How to wash clothes that are released and washed.

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