JP2013213185A - Powder detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition capable of more effectively removing fouling such as stains and yellowing of foods adhered to clothing.SOLUTION: A powder detergent composition contains, by mass, ≥10% and ≤45% of (a) an anionic surfactant, ≥0% and ≤9% of (b) a nonionic surfactant, ≥10% and ≤30% of (c) an alkaline metal carbonate salt, ≥10% and ≤40% of (d) an alkaline metal hydrogencarbonate salt, ≥0.1% and ≤10% of (e) a percarbonate salt, and ≥0.1% and ≤3% of (f) a bleach activator represented by the following formula (1) (wherein R is H, 1-17C alkyl or the like; and L is a leaving group), wherein the mass ratio of (b)/(a) is ≥0/1 and ≤1/3; the ratio of [(c)+ (e)]/(d) is ≥1/2 and ≤2/1; and the pH at 25°C of a 0.5-mass% solution of the composition prepared using a 0.01-mass% glacial acetic acid aqueous solution is ≥9 and ≤10.4.

Description

  The present invention relates to a powder detergent composition having high bleaching performance.

  Bleaching agents can be divided into chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaching agents are limited in the fibers that can be used, cannot be used for colors and patterns, and have a unique odor. Recently, oxygen-based bleaching agents that do not have these drawbacks have been remarkably widespread. Of these oxygen bleaches, sodium percarbonate and sodium perborate are used as powder oxygen bleaches, but they have lower bleaching power than chlorine bleaches. A bleaching agent (Patent Document 1) containing a bleaching activator is known. In addition, from the viewpoint of improving detergent cleaning and bleaching performance, a powder detergent containing a bleach activator is also known (Patent Document 2).

  JP-A-10-512601 (Patent Document 3) discloses a composition containing an anionic activator, a bleach activator having a specific structure such as lactam, a carbonate, and a bicarbonate. However, the carbonate and hydrogen carbonate concentrations are low, and the high performance of the bleach activator having a specific structure such as lactam can be expressed, but as represented by the following general formula (1) The sufficient performance of the bleach activator is not expressed. In addition to the technique of Patent Document 3, in any of the techniques so far, the performance expression of the bleach activator in which the blending amount and pH of the carbonate and bicarbonate are represented by the general formula (1) In consideration of the effects on the performance, there was no one that developed the performance.

Japanese Patent Laid-Open No. 10-245593 JP-A-8-21094 Japanese National Patent Publication No. 10-512601

  The subject of this invention is providing the powder cleaning composition which can remove stains, such as a stain and yellowing of food adhering to clothing, more effectively.

  As a result of repeated studies by the present inventors, in a system containing an anionic surfactant, an alkali metal carbonate, a percarbonate, and a bleach activator, a wide variety of components constituting the powder detergent composition Focusing on the amount of hydrogen carbonate from the inside, alkali metal carbonate and percarbonate and hydrogen carbonate alkali metal salt satisfy a specific mass ratio and control pH, so that sebum washing with high alkali metal carbonate is possible. The present inventors have found that high bleaching performance is exhibited by changing the dissociation state of peracid while ensuring the performance and the production amount of peracid, and completed the present invention.

That is, the gist of the present invention is as follows.
(A) 10 mass% or more and 45 mass% or less of anionic surfactant,
(B) 0% by mass or more and 9% by mass or less of nonionic surfactant,
(C) 10% by mass or more and 30% by mass or less of alkali metal carbonate,
(D) 10% by weight or more and 40% by weight or less of alkali hydrogen carbonate,
(E) 0.1 to 10% by mass of percarbonate, and (f) 0.1 to 3% by mass of a bleach activator represented by the following general formula (1) A powder cleaning composition comprising:
The mass ratio of (b) / (a) is 0/1 or more and 1/3 or less,
The mass ratio of [(c) + (e)] / (d) is ½ or more and 2/1 or less,
A powder detergent composition having a pH of 9 or more and 10.4 or less at 25 ° C. of a 0.5 mass% solution of the above composition prepared using a 0.01 mass% glacial acetic acid aqueous solution.

(In the formula, R is H, an alkyl or alkenyl group having 1 to 17 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group composed of two or more annelated benzenoid rings, and two or more aryl or The arylene substituent is selected from the group consisting of covalently bonded groups, and L is a leaving group, and the anionic conjugate acid produced on L has a pKa in the range of 4-13. ).

  The powder detergent composition of the present invention contains an alkali metal carbonate, an alkali metal bicarbonate, and a percarbonate in a specific ratio, and the effect of the bleach activator is remarkably improved by controlling the pH. Thus, a very high bleaching performance can be expressed against stains such as food stains and yellowing on the clothes.

Component (a) The anionic surfactant of component (a) is not particularly limited. For example, a higher alcohol sulfate, a higher alcohol ethoxylate sulfate, an alkylbenzene sulfonate, Paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt thereof, or fatty acid salt may be mentioned.

  From the viewpoint of improving the cleaning performance, in particular, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 18 carbon atoms (preferably 12 to 14), and an alkyl chain having 10 to 18 carbon atoms (preferably 12 to 16). Of the higher alcohols, or α-sulfo fatty acid alkyl ester salts having 10 to 20 carbon atoms in the alkyl chain, and in particular, linear chains having 10 to 18 carbon atoms (preferably 12 to 14) in the alkyl chain. Alkyl benzene sulfonates and higher alcohol sulfates having 10 to 18 (preferably 12 to 16) carbon atoms in the alkyl chain are preferred. Examples of the counter ion include alkali metals, alkaline earth metals, ammonia, alkanolamines, and the like, but alkali metals are preferable.

  The anionic surfactant is contained in the powder detergent composition in an amount of 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass from the viewpoint of enzyme performance. % Or more. Further, the anionic surfactant is contained in the powder detergent composition in an amount of 10 to 45% by mass, preferably 15 to 40% by mass, from the viewpoint of achieving both improvement in the effect of the bleaching activator and production suitability. More preferably, it is contained in an amount of 20 to 40% by mass, and further preferably 25 to 40% by mass. As the component (a), one type of component may be used, or a plurality of components may be used in combination.

(B) Component The powder detergent composition of the present invention contains the nonionic surfactant (b) in a certain range from the viewpoint of maintaining the bleaching performance by peracid generation and improving the sebum cleaning performance. However, the content of the nonionic surfactant is 0% by mass or more in the powder cleaning composition of the cleaning composition, particularly from the viewpoint of expressing the bleaching performance by peracid generation and maintaining the expression of enzyme performance. 9% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0% by mass, that is, even if not contained. good.

  The nonionic surfactant is not particularly limited, and examples thereof include an ethylene oxide (hereinafter referred to as “EO”) adduct of higher alcohol or an EO / propylene oxide (hereinafter referred to as “PO”) adduct. It is done. In particular, a compound obtained by adding 1 to 25 moles, preferably 10 to 20 moles of EO to an alcohol having 10 to 16 carbon atoms, preferably 12 to 14 carbon atoms, removes sebum dirt, hard water resistance, biodegradability, and It is preferable in terms of compatibility with a linear alkylbenzene sulfonate.

  Here, the mass ratio of (b) / (a) is 0/1 or more and 1/3 or less. From the viewpoint of achieving both a bleaching performance expression by improving peracid generation and a high sebum detergency, it is preferably 1/5 or less, more preferably 1 / 6.7 or less, and even more preferably 1/10 or less. The mass ratio of (b) / (a) is preferably 0/1 or more and 1/5 or less, more preferably from the viewpoint of developing the bleaching performance by peracid generation and maintaining the expression of enzyme performance. It is 0/1 or more and 1 / 6.7 or less, more preferably 0/1 or more and 1/10 or less. From the viewpoint of improving sebum cleaning performance, it is preferable that the component (b) is contained in the powder detergent composition. However, when the content ratio of the nonionic activator is increased, the bleach activator is contained in the activator micelle. The upper limit of the mass ratio of (b) / (a) is preferably set to 1/3 because it tends to be difficult to produce organic peracid and decrease the bleaching performance.

(C) Component The alkali metal carbonate (c) is not particularly limited, and examples thereof include sodium carbonate and potassium carbonate. Component (c) is contained in the powder detergent composition in an amount of 10% by mass or more, preferably 12% by mass or more, more preferably 14% by mass or more from the viewpoint of enzyme activation. Moreover, (c) component is 10 mass% or more and 30 mass% or less in a powder detergent composition from a viewpoint of the sebum washing performance improvement in an actual washing scene, and enzyme activation, Preferably it is 12 mass% or more, 25 It is contained by mass% or less, more preferably 14% by mass or more and 23% by mass or less.

(D) Component Although it does not specifically limit as an alkali metal hydrogencarbonate (d), For example, sodium hydrogencarbonate or potassium hydrogencarbonate etc. are mentioned. (D) A component is 10 mass% or more in a powder detergent composition, Preferably it is 12 mass% or more, More preferably, 14 mass% or more is contained. Further, the component (d) is contained in the powder cleaning composition in an amount of 10% by mass to 40% by mass, preferably 12% by mass to 30% by mass, more preferably 14% by mass to 25% by mass. Is done.

(E) Component In the present invention, the percarbonate is not particularly limited, and examples thereof include sodium percarbonate and potassium percarbonate. The component (e) is 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more in the powder cleaning composition from the viewpoint of achieving both the stability of the powder cleaning composition and the expression of bleaching performance. It is preferable to contain 5 mass% or less.

  The mass ratio [(c) + (e)] / (d) is ½ or more and 2/1 or less. Here, from the viewpoint of expressing the bleaching performance by improving the production of peracid, it is preferably 1 / 1.5 or more, more preferably 1/1 or more, more preferably 1.1 / 1 or more. Further, from the viewpoint of improving the bleaching performance by making the dissociation state of the peracid into an acid type, it is preferably 1.5 / 1 or less, more preferably 1.4 / 1 or less, more preferably 1.3 / 1 or less. It is. Further, from the viewpoint of improving the peracid production and the dissociation state of the peracid to improve the bleaching performance, preferably 1 / 1.5 or more, 1.5 / 1 or less, more preferably 1/1 or more, 1 .4 / 1 or less, more preferably 1.1 / 1 or more and 1.3 / 1 or less. By containing a high proportion of alkali metal carbonates with a high degree of dissociation in the washing liquid and alkali metal hydrogen carbonates with a low degree of dissociation at a specific ratio, the dissociated state of the organic peracid generated from the bleach activator is bleached. It is presumed that the powder detergent composition of the present invention can exhibit very high bleaching performance by changing to an acid type with high performance.

(F) Component In this invention, the bleaching activator represented by following General formula (1) is contained.

Wherein R is H, an alkyl group or alkenyl group having 1 to 17 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, a cyclic alkyl group or alkenyl group having 3 to 18 carbon atoms, aryl Selected from the group consisting of a group, an aromatic heterocyclic group, a polyarylene group comprising two or more annelated benzenoid rings, and a group to which two or more aryl or arylene substituents are covalently bonded, and L is eliminated And the anionic conjugate acid produced on L has a pKa in the range of 4-13.)

  The leaving group L is a group that is displaced from the bleach activator as a result of a nucleophilic attack on the bleach activator by the anion of the peroxycarboxylic acid, and is essentially any leaving group. Can be used. Leaving groups that exhibit this type of behavior are those whose conjugate acids have a pKa in the range of 4-13. Examples of the bleach activator include tetraacetylethylenediamine.

  As the bleach activator, a bleach activator represented by the following general formula (2) is more preferable from the viewpoint of high peracid generating ability.

[Wherein, R represents an alkyl group of 7 to 15 and Y represents —SO ₃ M or —COOM (where M represents a hydrogen atom or an alkali metal atom). ]

  In the general formula (2), an alkyl group represented by R, preferably a linear alkyl group, has sufficient carbon number to ensure sufficient solubility under normal washing conditions and to provide sufficient adsorption power for dirt components. Is preferably 7-15. Further, examples of the alkali metal atom represented by M include a sodium atom and a potassium atom.

  As such a bleach activator, what is represented by following formula (3) is especially preferable.

[Wherein R represents a linear alkyl group having 11 to 15 carbon atoms, and M represents a sodium atom or a potassium atom]

  Specific examples of the bleach activator represented by the formula (3) include sodium lauroyloxybenzenesulfonate and sodium nonanoyloxybenzenesulfonate.

  The component (f) is preferably 0.1% by mass, 3% by mass or less, and more preferably 0.2% by mass or more in the powder cleaning composition from the viewpoint of achieving both bleaching performance and fragrance at the time of use. 2% by mass or less, more preferably 0.3% by mass or more and 1% by mass or less, more preferably 0.4% by mass or more and 0.8% by mass or less.

(Other ingredients)
Other surfactants such as nonionic surfactants such as fatty acid alkanolamides and alkylpolyglycosides, amphoteric surfactants and cationic surfactants can be added to the powder detergent composition of the present invention.

(G) Phosphate builder The powder cleaning composition of this invention contains a phosphate builder (g) in a fixed range from a viewpoint of a sebum cleaning performance improvement. However, the content of the phosphate builder is 0% by mass or more, 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass of the detergent composition, particularly from the viewpoint of not adversely affecting the production of peracid. % Or less, more preferably 0% by mass, that is, it may not be contained.

  Although it does not specifically limit as a phosphate builder, For example, 1 or more types chosen from a tripolyphosphate, an orthophosphate, a pyrophosphate, etc. are mentioned. The amount of tripolyphosphate in the total phosphate builder is preferably 80 to 97% by mass, the amount of orthophosphate is 1 to 10% by mass, and the amount of pyrophosphate is 2 to 10% by mass (the amount is Calculated as anhydride). Moreover, as a counter ion, an alkali metal ion is preferable and especially a sodium ion and a potassium ion are preferable. In all counter ions, the amount of sodium ions and potassium ions is preferably 70% by mass or more, and more preferably 85% by mass or more.

Cation Exchange Type Polymer In addition, the detergent composition of the present invention is blended with a cation exchange type polymer having a carboxylic acid group and / or a sulfonic acid group in terms of sequestering ability and dispersibility of solid particle dirt. Is preferred. Molecular weight of 1,000 to 80,000, preferably 60,000 to 70,000 acrylic acid-maleic acid copolymer salt, polyacrylate, and molecular weight described in JP-A No. 54-52196, preferably 8 to 1,000,000 May include 5,000 to 200,000 polyacetal carboxylates such as polyglyoxylic acid. The cation exchange polymer is preferably from 0.1 to 7% by mass, more preferably from 0.3 to 5% by mass, and particularly preferably from 0.5 to 3% by mass of the powder detergent composition from the viewpoint of detergency. Contained.

Crystalline Aluminosilicate The powder detergent composition of the present invention can contain crystalline aluminosilicate such as A-type, X-type, and P-type zeolite. The average primary particle diameter is 0.1 to 10 μm, preferably 1 to 5 μm. The content of the crystalline aluminosilicate is preferably from 10 to 40% by mass, more preferably from 15 to 35% by mass, and more preferably from 20 to 30% by mass, from the viewpoint of achieving both detergency and expression of enzyme effect. Is more preferable. Preferred as the crystalline aluminosilicate is A-type zeolite (for example, trade name “Toyo Builder”: manufactured by Tosoh Corporation, oil absorption capacity by JIS K 5101 method: 40 mL / 100 g or more). In addition, P type (for example, trade name “Ducil A24”, “ZSEO64”, etc .; manufactured by Crosfield; oil absorption capacity 60 to 150 mL / 100 g), X type (for example, trade name “WessalithXD”; manufactured by Degussa; A hybrid zeolite described in International Publication No. 9842622 is also preferable as an oil absorption capacity of 80 to 100 mL / 100 g).

  Further, surface modification may be performed from the viewpoint of fluidity and non-caking property of the detergent particles. Examples of the surface coating agent include bentonite, talc, clay, metal soap, fine powder such as powder surfactant, carboxymethyl cellulose, polyethylene glycol, polyacrylic acid or a salt thereof, a copolymer of acrylic acid and maleic acid or a salt thereof. Water-soluble polymers such as polycarboxylates such as fatty acids and fatty acids.

[PH]
The pH at 25 ° C. of a 0.5 mass% solution of the above composition prepared by using a 0.01 mass% glacial acetic acid aqueous solution of the powder detergent composition of the present invention is 9 or more, 10.4 or less, preferably 9 4 or more and 10.3 or less, more preferably 9.5 or more and 10.2 or less. When the pH is within this range, the organic peracid generation rate can be improved, and excellent bleach cleaning performance can be exhibited.

  In an actual laundry scene where a powder detergent composition is used, fatty acids derived from sweat, sebum, etc. of clothes are present in the wash water, and the washing pH can be lowered. Therefore, in the composition solution using 0.01% by mass glacial acetic acid aqueous solution as a model of washing water in which fatty acids are present, taking the above pH range is one of the very important factors for the development of bleaching performance. is there.

Usually, organic peracids are generated by the reaction of bleach activator and hydrogen peroxide, but hydrogen peroxide is more activated in the high pH region, and the reactivity with bleach activator is improved and organic Peracid is generated efficiently. On the other hand, the produced organic peracid exhibits a high bleaching performance by changing the dissociation state to an acid form in a low pH region and improving the permeability to dirt. That is, a high pH is effective for efficiently generating an organic peracid, and a low pH is effective for the generated organic peracid to exhibit higher bleaching performance. Thus, it has been extremely difficult to achieve both efficient generation of organic peracid and higher bleaching performance by organic peracid.
In the present invention, the bleaching activator is pushed out into the bulk by improving the reactivity with hydrogen peroxide by adding a (specific) anionic surfactant at a high level in the production of organic peracid. An organic peracid can be produced effectively even in a low pH range. As a result, in situations where bleaching performance is manifested by organic peracids, a low pH is stably maintained by blending high amounts of alkali metal carbonates and bicarbonates at a specific ratio, and organic peracids change to acid forms and are high. Bleaching performance can be expressed. The pH is measured using a pH meter F52 manufactured by HORIBA, Ltd. and a pH electrode 6367-S004.

[Electric conductivity]
The electrical conductivity at 25 ° C. of the 0.1% by mass aqueous solution of the composition of the present invention is preferably 0.2 to 0.75 S / m from the viewpoint of expressing the cleaning performance against dirt on the collar and sleeve, 0.3 -0.7 S / m is more preferable, and 0.3-0.65 S / m is more preferable. The electrical conductivity is measured by CM-21P manufactured by Toa DKK Co., Ltd.

  The value of electrical conductivity is greatly affected by the type of salt contained in the composition. A salt having a multivalent ion shows a high electric conductivity, and a salt having a monovalent ion hardly affects the electric conductivity. Examples of the salt having a polyvalent ion include magnesium sulfate, sodium sulfate, calcium carbonate, and magnesium carbonate. Examples of the salt having a monovalent ion include sodium chloride and potassium chloride. In the cleaning composition of the present invention, it is important to adjust the content of the salts listed above in order to improve the cleaning performance against dirt on the collar and sleeve by setting the electric conductivity within a specific range. .

Washing method The present invention has a step of washing an object to be washed in washing water containing the above-described powder detergent composition. More specifically, for example, washing by a washing machine or hand washing, preferably It includes a washing method for performing hand-washing washing in which the concentration of the detergent used is high. The invention of the present application is a washing water containing the above-described powder cleaning composition, wherein the washing object is washed in the washing water having an electric conductivity of 0.2 S / m or more and 3.5 S / m or less. Includes the washing method to be performed.

  Here, regarding the electrical conductivity of the washing water, for example, 0.35-3.5 S / m, further 0.8-3.5 S / m, further 1.5-3.5 S / m Even under washing conditions where the concentration used is high and the electrical conductivity is higher, the performance of the bleach activator can be sufficiently exerted.

  This invention discloses the following compositions further regarding embodiment mentioned above.

<1> (a) Anionic surfactant is contained in an amount of 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more and 45% by mass or less, preferably 40%. Mass% or less,
(B) 0% by mass or more and 9% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1% by mass or less, More preferably 0% by mass
(C) Alkali metal carbonate is 10% by mass or more, preferably 12% by mass or more, more preferably 14% by mass or more, 30% by mass or less, preferably 25% by mass or less, more preferably 23% by mass or less,
(D) 10% by weight or more, preferably 12% by weight or more, more preferably 14% by weight or more, 40% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less, of alkali hydrogen carbonate.
(E) 0.1% by weight or more, preferably 1% by weight or more and 10% by weight or less, preferably 5% by weight or less of percarbonate, and (f) Bleach activation represented by the following general formula (1) 0.1 mass%, preferably 0.2 mass% or more, more preferably 0.3 mass% or more, more preferably 0.4 mass% or more, 3 mass% or less, preferably 2 mass% or less, more preferably Is a powder detergent composition containing 1% by mass or less, more preferably 0.8% by mass or less,
The mass ratio of (b) / (a) is 0/1 or more and 1/3 or less,
The mass ratio of [(c) + (e)] / (d) is ½ or more and 2/1 or less,
The pH at 25 ° C. of a 0.5 mass% solution of the above composition prepared using a 0.01 mass% glacial acetic acid aqueous solution is 9 or more, preferably 9.4 or more, more preferably 9.5 or more, 10.4. Hereinafter, a powder cleaning composition, which is preferably 10.3 or less, more preferably 10.2 or less.

(In the formula, R is H, an alkyl or alkenyl group having 1 to 17 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group composed of two or more annelated benzenoid rings, and two or more aryl or The arylene substituent is selected from the group consisting of covalently bonded groups, and L is a leaving group, and the anionic conjugate acid produced on L has a pKa in the range of 4-13. )

<2> The powder cleaning composition according to <1>, wherein the mass ratio of (c) / (d) is 1/3 or more and 2/1 or less.
<3> The component (a) is selected from the group consisting of a linear alkylbenzene sulfonate having 10 to 18 carbon atoms in the alkyl chain and a sulfate ester salt of a higher alcohol having 10 to 18 carbon atoms in the alkyl chain. The powder cleaning composition according to <1> or <2>, which is a component of more than seeds.
<4> The component (b) is a compound obtained by adding an average of 1 to 25 moles, preferably 10 to 20 moles of ethylene oxide to an alcohol having 10 to 16, preferably 12 to 14 carbon atoms, <1> to <3 > The powder cleaning composition of any one of>.
<5> The powder cleaning composition according to any one of <1> to <4>, wherein the component (f) is a bleach activator represented by the following general formula (2).

[Wherein, R represents an alkyl group of 7 to 15 and Y represents —SO ₃ M or —COOM (where M represents a hydrogen atom or an alkali metal atom). ]
<6> The mass ratio of (b) / (a) is 0/1 or more and 1/5 or less, preferably 1 / 6.7 or less, more preferably 1/10 or less, <1> to <5> The powder cleaning composition of any one of these.
<7> The mass ratio of [(c) + (e)] / (d) is 1 / 1.5 or more, preferably 1/1 or more, more preferably 1.1 / 1 or more and 1.5 / 1 or less. The powder cleaning composition according to any one of <1> to <6>, preferably 1.4 / 1 or less, more preferably 1.3 / 1 or less.
<8> Further, (g) phosphate builder, preferably 1% or more phosphate builder selected from tripolyphosphate, orthophosphate, pyrophosphate, etc. The powder cleaning composition according to any one of <1> to <7>, which contains 3% by mass or less, more preferably 1% by mass or less, and more preferably 0% by mass.

  In the following, aspects of the invention will be further described and disclosed by means of examples. These examples are merely illustrative of the invention and are not meant to be limiting in any way.

<Example 1>
Among the components of Example 1 shown in Table 1, sodium carbonate 8.84 kg, fluorescent brightening agent 0.07 kg using a Redige mixer FKM-130D (manufactured by Matsubo Co., Ltd.) and stirring blades at a peripheral speed of 3.4 m / S, mixing at a shearing machine peripheral speed of 27 m / s for 1 minute. While operating the mixer under the same conditions, a mixture of 7.98 kg of linear alkyl (carbon number 12-14) benzenesulfonic acid (water content 0.5 mass%, sulfuric acid content 1%) and sulfuric acid was added over 4 minutes, The neutralization reaction was performed by operating for 5 minutes. Next, while operating the mixer under the same conditions, 2.8 kg of a nonionic surfactant and 2.45 kg of zeolite were added and granulated by operating for 2 minutes.

  Then, while operating the mixer under the same conditions, 1.75 kg of zeolite was added, 0.175 kg of polyethylene glycol (PEG13000), 0.875 kg of 40 mass% aqueous solution of maleic acrylate copolymer (AA / MA copolymer), No. 2 silicate 2.625 kg was added in 1 minute and granulated by operating for an additional 2 minutes. Subsequently, 1.75 kg of zeolite was added, and the surface was modified by further operating for 2 minutes, and passed through a 2000 μm sieve to obtain powder detergent particles. Next, using a rotating drum, 1.75 kg of the remaining zeolite, 0.7 kg of enzyme, 0.175 kg of bleach activator, 1.05 kg of PC, 2.2 kg of sodium sulfate, and 5.25 kg of sodium hydrogen carbonate are added to the detergent particles. Were mixed to obtain 35 kg of a powder cleaning composition having the final composition shown in Table 1.

<Examples 2 to 12>
Among the components of Examples 2 to 12 shown in Table 1, 8% by mass of zeolite in the composition, 4% by mass of sodium carbonate (or potassium carbonate), sodium hydrogen carbonate (or potassium hydrogen carbonate) and enzyme A slurry was prepared from the removed components and spray-dried to obtain a spray-dried composition. To this, 5% by mass of zeolite in the composition and 4% by mass of sodium hydrogen carbonate (or potassium hydrogen carbonate) were added to a ribbon mixer for mixing. The obtained mixture was extruded into a columnar shape having a diameter of 10 mm with a pre-extrusion type twin-screw type extrusion granulator (Peletter Double: manufactured by Fuji Powder Co., Ltd.) to be consolidated. The obtained pellets were pulverized and granulated with a flash mill (produced by Fuji Powder Co., Ltd.) together with 2% by mass of zeolite in the total detergent composition, surface-coated, passed through a 2000 μm sieve, Density detergent particles were obtained. After this, transfer to V blender and mix the zeolite, sodium carbonate (or potassium carbonate), sodium bicarbonate (or potassium bicarbonate), enzyme, PC, bleach activator, phosphate builder in the remaining composition. Thus, a powder cleaning composition was obtained.

<Comparative Examples 1-5>
In the same manner as in Examples 2 to 12, powder cleaning compositions having the compositions shown in Table 1 were obtained.

[Measurement of pH]
A 0.5 mass% solution of a powder detergent composition was prepared using a 0.01 mass% glacial acetic acid aqueous solution, and the pH at 25 ° C was adjusted with a pH meter F52 manufactured by Horiba, Ltd., and a pH electrode 6367-S004. And measured. The water used for preparing the glacial acetic acid aqueous solution is distilled water (manufactured by Wako Pure Chemical Industries).

<Performance evaluation>
The following evaluation was performed about the powder detergent composition obtained by the Example and the comparative example. The results are shown in Table 1.

  The rate of organic peracid generation from the bleach activator was evaluated by the following method. The results are shown in Table 1.

<Organic peracid generation rate evaluation method>
A test solution was prepared by adding 4 g of powder cleaning composition (corresponding to the amount used during immersion cleaning) to 1000 mL of ion-exchanged water at 25 ° C. and stirring. After 30 minutes, 1.5 mL of a 1% by weight catalase solution was added to the test solution, and after stirring for another 3 minutes, 10 mL of 20% by weight sulfuric acid aqueous solution was added, and the amount of organic peracid was titrated according to the iodometry method. The generation rate of organic peracid was determined.

  Organic peracid generation rate (%) = (organic peracid generation amount (μM) / bleach activator content (μM)) × 100

<Evaluation method of bleaching performance>
After mixing 1 g of powder detergent composition and 1000 mL of water adjusted to 4 ° DH, the meat sauce contaminated cloth (4 sheets) prepared by the following method is put there, and bleached at 20 ° C. and 80 rpm for 10 minutes using a tartometer. Processed. The reflectance of the cloth surface before and after the treatment was measured, and the bleaching rate was determined by the following formula (II).

-Preparation of meat sauce-contaminated cloth Solid content of meat sauce (meat sauce of ripe tomato (May 27, 2012 expiration date, lot number: D0527JF) / canned content of 259 g) manufactured by Kagome Co., Ltd. (mesh opening; 500 μm) ), And the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for 15 minutes. After removing from the fire as it was for about 2 hours and leaving it to 30 ° C., the cloth was taken out and the excess liquid was removed with a spatula and allowed to dry naturally. Thereafter, it was pressed and subjected to an experiment as a 10 × 10 cm test cloth.

  The reflectance of the cloth surface was measured by using a Spectro Color Meter manufactured by Nippon Denshoku Industries Co., Ltd. and measuring the reflectance at a wavelength of 460 nm in a state where four contaminated cloths were stacked.

  Here, tetraacetylethylenediamine (TAED) was used as the bleaching activator A, and sodium lauroyloxybenzenesulfonate was used as the bleaching activator B. As bleach activator C, sodium nonanoyloxybenzenesulfonate was used. Furthermore, LAS-Na is linear alkyl (C12-14) sodium benzenesulfonate, and AS-Na is alkyl (C12-16) sodium sulfate. Nonionic surfactant is polyoxyethylene (EO average addition mole number 7) alkyl (carbon number 12-14) ether, AA / MA copolymer is sodium salt of acrylic acid-maleic acid copolymer (70 mol% neutralization) The monomer ratio is acrylic acid / maleic acid = 3/7 (molar ratio), and the average molecular weight is 70000. The fluorescent whitening agent used was a 1/1 mass ratio mixture of Tinopearl CBS-X and Tinopearl AMS-GX (Ciba Specialty Chemicals). As the zeolite, 4A-type zeolite having an average particle size of 3 μm (manufactured by Tosoh Corporation) was used. The enzyme used was a mixture of cellulase K (described in JP-A 63-264699) and lipolase 100T (manufactured by Novo) at a mass ratio of 3: 1. As for PC, based on Example 1 of JP-A-59-196399, sodium metaborate tetrahydrate coated with 5% by mass with respect to sodium percarbonate is a 125 μm sieve having a small particle size. The removed one was used. As the No. 2 silicate, sodium silicate (43% by mass) (manufactured by TOKUYAMA SIAM SILICA CO. LTD.) Was used. The PEG used was PEG13000-L60 (Mitsui Chemicals). The phosphate builder was sodium tripolyphosphate (manufactured by Thai polyphosphate & Chemicals Co., Ltd.).

  From the results of Examples in Table 1, it was found that the powder detergent composition of the present invention was excellent in bleaching performance.

  On the other hand, the powder cleaning composition of the comparative example was clearly inferior in bleaching performance to that of the example. In Comparative Example 1, the organic peracid generation rate was similar to that in the example, but the bleaching performance was inferior. This is presumably because component (d) was too small and the abundance of dissociated organic peracid was high. Furthermore, in Comparative Example 2, both the organic peracid generation rate and the bleaching performance were inferior to those of the Examples. This is considered to be because the organic peracid generation rate has been remarkably reduced because the component (c) was too small. Further, in Comparative Example 4, since the component (c) and the component (d) were too small, both the organic peracid generation rate and the bleaching performance were inferior to those of the examples.

  In Comparative Example 3, since the amount of the component (b) was excessive as compared with the component (a), both the organic peracid generation rate and the bleaching performance were inferior to those of the examples. In Comparative Example 5, since the amount of component (a) was too small, both the organic peracid generation rate and the bleaching performance were inferior to those of the Examples.

  The powder detergent composition of the present invention can be used for washing clothes.

Claims (8)

(A) 10 mass% or more and 45 mass% or less of anionic surfactant,
(B) 0% by mass or more and 9% by mass or less of nonionic surfactant,
(C) 10% by mass or more and 30% by mass or less of alkali metal carbonate,
(D) 10% by weight or more and 40% by weight or less of alkali hydrogen carbonate,
(E) 0.1 to 10% by mass of percarbonate, and (f) 0.1 to 3% by mass of a bleach activator represented by the following general formula (1) A powder cleaning composition comprising:
The mass ratio of (b) / (a) is 0/1 or more and 1/3 or less,
The mass ratio of [(c) + (e)] / (d) is ½ or more and 2/1 or less,
A powder detergent composition having a pH of 9 or more and 10.4 or less at 25 ° C. of a 0.5 mass% solution of the above composition prepared using a 0.01 mass% glacial acetic acid aqueous solution.

(In the formula, R is H, an alkyl or alkenyl group having 1 to 17 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group composed of two or more annelated benzenoid rings, and two or more aryl or The arylene substituent is selected from the group consisting of covalently bonded groups, and L is a leaving group, and the anionic conjugate acid produced on L has a pKa in the range of 4-13. )   The powder cleaning composition of Claim 1 whose mass ratio of (c) / (d) is 1/3 or more and 2/1 or less.   The component (a) is one or more selected from the group consisting of a linear alkylbenzene sulfonate having 10 to 18 carbon atoms in the alkyl chain and a sulfate ester of a higher alcohol having 10 to 18 carbon atoms in the alkyl chain. The powder cleaning composition of Claim 1 or 2 which is a component.   The powder cleaning composition according to any one of claims 1 to 3, wherein the component (b) is a compound obtained by adding an average of 1 to 25 moles of ethylene oxide to an alcohol having 10 to 16 carbon atoms. (F) Powder cleaning composition in any one of Claims 1-4 whose component is a bleaching activator represented by following General formula (2).

[Wherein, R represents an alkyl group of 7 to 15 and Y represents —SO ₃ M or —COOM (where M represents a hydrogen atom or an alkali metal atom). ]   The powder cleaning composition in any one of Claims 1-5 whose mass ratio of (b) / (a) is 0/1 or more and 1/5 or less.   The powder cleaning composition according to any one of claims 1 to 6, wherein a mass ratio of [(c) + (e)] / (d) is from 1 / 1.5 to 1.5 / 1. .   Furthermore, the powder cleaning composition in any one of Claims 1-7 containing 0 mass% or more and 5 mass% or less of (g) phosphate builder.