WO2013027515A1

WO2013027515A1 - Solid bleaching agent composition

Info

Publication number: WO2013027515A1
Application number: PCT/JP2012/068405
Authority: WO
Inventors: 鈴木信行; 吉川清章; 川村卓司
Original assignee: 花王株式会社
Priority date: 2011-08-24
Filing date: 2012-07-20
Publication date: 2013-02-28
Also published as: JP2013060579A; CN103781895A; JP6068846B2

Abstract

The present invention is a solid bleaching agent composition which is obtained by blending (A) 1.5-5% by mass (inclusive) of sodium dichloroisocyanurate dihydrate, (B) one or more kinds of powders that are selected from among amorphous silica and crystalline calcium silicate and have liquid-supporting ability, (C) an anhydride of an inorganic alkali metal salt, and (D) 0.5-2.5% by mass (inclusive) of a nonionic surfactant. The solid bleaching agent composition has a water content of 5-10% by mass (inclusive).

Description

Solid bleach composition

The present invention relates to solid bleach compositions. In particular, it relates to a solid bleach composition suitable for use in commercial dishwashers.
Background art

The dishwasher is a facility for washing dishes such as dirty dishes, glasses, and cooking utensils, and is used in kitchens such as homes, restaurants, and coffee shops. In general, dishwashing is performed in the order of a washing process-a rinsing process. In the washing process, a non-foaming or low-foaming dishwasher cleaner different from a dishwashing detergent for hand washing is used. Furthermore, in the detergent for dishwashers, a bleaching agent may be blended for bleaching performance against discolored stains such as tea astringent and coffee and to prevent redeposition of pigment stains present in the cleaning liquid.

In the case of washing with a commercial dishwasher, washing is repeatedly performed with a cleaning solution containing foodstuffs and beverage stains (proteins, lipids, pigments) brought into the washing tank. For this reason, the dirt (pigment) gradually reattaches to the tableware and the like, and progresses to a state that requires bleaching. In commercial dishwashing agents, it is important to prevent redeposition of pigment stains present in the cleaning liquid.

JP 2008-133453 describes a bleaching composition containing sodium hypochlorite and having excellent bleaching power against mold. Japanese Patent Laid-Open No. 52-127483 discloses a chlorinated donor solid composition of hydrated di (dichloroisocyanuric acid) calcium, and sodium dichloroisocyanurate dihydrate has problems such as autolysis. There is a statement to that effect. US Pat. No. 5,205,954 also discloses a powder detergent for automatic dishwashers containing a specific organic or inorganic detergent builder, an alkali metal silicate, a nonionic surfactant, a chlorine bleaching compound, a silica defoamer and the like. A composition is described.

SUMMARY OF THE INVENTION The present invention provides (A) 1.5 to 5% by mass of sodium dichloroisocyanurate dihydrate, (B) one or more liquids selected from amorphous silica and crystalline calcium silicate. And (C) a solid bleaching composition comprising an inorganic alkali metal salt anhydride and having a water content of 5 to 10% by mass. Moreover, it is related with the said solid bleaching agent composition which mix | blends (D) nonionic surfactant.

The present invention also provides (A) sodium dichloroisocyanurate dihydrate (hereinafter referred to as “component (A)”) in an amount of 1.5% by mass or more and 5% by mass or less, (B) amorphous silica, and crystals. A powder having the ability to carry one or more liquids selected from crystalline calcium silicate (hereinafter referred to as component (B)), (C) an inorganic alkali metal salt anhydride (hereinafter referred to as component (C)), and ( D) A nonionic surfactant (hereinafter referred to as component (D)) is blended in an amount of 0.5% by mass or more and 2.5% by mass or less, and has a water content of 5% by mass or more and 10% by mass or less. The present invention relates to a bleaching composition.

This invention provides the use which uses the said solid bleaching composition for the washing | cleaning of tableware.

Detailed Description of the Invention Japanese Patent Application Laid-Open No. 2008-133453 is a liquid system, and further has a sodium hypochlorite ratio as high as 73% (in terms of solid content), and has a composition specialized for mold bleaching power. It is difficult to maintain sex. Japanese Patent Laid-Open No. 52-127483 discloses a composition containing sodium dichloroisocyanurate dihydrate and anhydrous sodium metasilicate as a comparative example, which is mainly composed of anhydrous raw materials. This comparative example only suggests that sodium dichloroisocyanurate dihydrate is relatively stable under suitable conditions that are less susceptible to water. Moreover, the cleaning power against complex dirt adhering to tableware cannot be foreseen from the comparative example as well as the example of Japanese Patent Application Laid-Open No. Sho 52-127483. U.S. Pat. No. 5,205,954 does not disclose any cleaning power against complex dirt adhering to tableware.

That is, Japanese Patent Application Laid-Open No. 2008-133453, Japanese Patent Application Laid-Open No. 52-127483 and US Pat. No. 5,205,954 do not suggest a configuration for obtaining excellent cleaning properties against tableware stains. In order to secure residual chlorine, it is necessary to make the composition mainly composed of anhydrous raw materials.

The present invention is excellent in storage stability even when a solid bleaching composition containing a water-containing raw material and a liquid component is stored in a harsh state, and has excellent cleaning properties and anti-reattachment property of pigment stains. A solid bleach composition is provided.

ADVANTAGE OF THE INVENTION According to this invention, the solid bleaching agent composition which is excellent in storage stability even when preserve | saved in a severe state, and has the outstanding washing | cleaning property, bleaching property, and the reattachment prevention property of pigment | dye stain is provided. .

<(A) component>
The solid bleaching agent composition of the present invention contains sodium dichloroisocyanurate dihydrate as the component (A). Anhydrous acid is known for sodium dichloroisocyanurate, but by using dihydrate, excellent bleaching and storage stability can be obtained.

<(B) component>
The solid bleaching agent composition of the present invention contains, as component (B), a powder having at least one liquid supporting ability selected from amorphous silica and crystalline calcium silicate. (B) As a liquid which can carry | support a component, a water | moisture content, a polymer component, surfactant, etc. are mentioned. Further, in the present invention, the component (B) “having liquid carrying ability” means that the oil absorption ability by the method described in JIS K6220 (−1995) is 120 ml / 100 g or more. The component (B) preferably has an oil absorption capacity of 120 ml / 100 g or more, 1000 ml / 100 g or less, and more preferably 600 ml / 100 g or less. The component (B) preferably has an oil absorption capacity of 120 to 1000 ml / 100 g, more preferably 120 to 600 ml / 100 g.

The average particle size of the component (B) is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 300 μm or less, and more preferably 150 μm or less. The average particle size of the component (B) is preferably 0.5 to 300 μm, more preferably 1 to 150 μm. This particle size is measured by a dry shaking sieve method (low tap).

The specific surface area of the component (B) is preferably 30 (m ² / g) or more, more preferably 50 (m ² / g) or more, and 600 (m ² / g) or less, further 400 (m ² / g) or less. Is preferred. The specific surface area of the component (B) is preferably 30 to 600 (m ² / g), more preferably 50 to 400 (m ² / g). It is measured by this BET surface area meter.

As the amorphous silica of the component (B) of the present invention, various synthetic amorphous silicas that are commercially available as Tokusil series and Fine seal series (Tokuyama Corporation) can be used. Here, the amorphous silica refers to one having a Si—O network structure and having no fixed crystal structure.

The crystalline calcium silicate of the component (B) of the present invention is represented by 2CaO.3SiO ₂ .mSiO ₂ .nH ₂ O (m, n is 1 <m <2, 2 <n <3). The crystalline calcium silicate variously marketed as a florite series (Tokuyama Co., Ltd.) can be used.

Among these, from the viewpoint of storage stability, it is preferable to use amorphous silica as the component (B).

<(C) component>
The solid bleaching agent composition of the present invention contains an inorganic alkali metal salt anhydride as the component (C). (C) As a component, 1 or more types chosen from the anhydride of an alkali metal silicate salt and the anhydride of an alkali metal carbonate are preferable. Specific examples include anhydrides of alkali metal salts such as anhydrous sodium carbonate, anhydrous potassium carbonate, and anhydrous sodium silicate. Furthermore, 1 type, or 2 or more types chosen from anhydrous sodium carbonate, anhydrous potassium carbonate, and anhydrous sodium silicate can be used.

From the viewpoint of detergency and storage stability, the component (C) comprises (C1) an anhydride of an alkali metal silicate, especially anhydrous sodium silicate, and (C2) an anhydride of an alkali metal carbonate, especially anhydrous sodium carbonate. It is preferable to use together. That is, from the viewpoints of detergency and storage stability, the component (C) is one or more selected from (C1) an anhydride of an alkali metal silicate, and in particular, anhydrous sodium silicate and (C2) an anhydrous alkali metal carbonate. It is preferable that it is 1 or more types chosen from a thing, and it is an anhydrous sodium carbonate especially. When (C1) and (C2) are used in combination, the mass ratio (C1) / (C2) between the blending amount of (C1) and the blending amount of (C2) is 10/90 or more, more preferably 20/80 or more. And preferably 50/50 or less, more preferably 40/60 or less. When (C1) and (C2) are used in combination, the mass ratio between the blending amount of (C1) and the blending amount of (C2) is (C1) / (C2) = 10/90 to 50/50. Is preferable, and 20/80 to 40/60 is more preferable.

<(D) component>
From the viewpoint of detergency, the solid bleaching composition of the present invention preferably contains a nonionic surfactant as the component (D). Therefore, this invention also discloses the solid bleaching composition containing (D) component.

(D) Component nonionic surfactants include glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy One or more selected from ethylene alkyl ether, polyoxyethylene dialkyl ether, polyoxyethylene glycol, polyoxyethyleneoxypropylene glycol, and polyoxypropyleneoxyethyleneoxypropylene glycol can be used. It is preferable to use one or more selected from polyoxyethylene alkyl ether, polyoxyethylene dialkyl ether, polyoxyethylene glycol, polyoxyethylene oxypropylene glycol, and polyoxypropylene oxyethylene oxypropylene glycol.

Component (D) is selected from nonionic surfactants represented by the following general formula (d-1) and nonionic surfactants represented by the following general formula (d-2) from the viewpoint of finish. One or more nonionic surfactants are preferred. Further, one or more nonionic surfactants selected from nonionic surfactants represented by general formula (d-2) are preferred, and nonionic surfactants represented by general formula (d-2 ′) are preferred. One or more nonionic surfactants selected from are more preferable.
R ^1d —O— (EO) _p — (PO) _q — (EO) _r —H (d−1)
[Wherein R ^1d represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, or a hydrocarbon group having 8 to 18 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q and r each represent an average number of added moles, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, r is 1 or more and 10 or less, and p = 1 to 10, q = 0.5 to 5 and r = 1 to 10. “— (EO) _p — (PO) _q — (EO) _r —” ”is a block bond. ]
R ^2d —O— (EO) _s — (AO) _t —H (d-2)
[Wherein R ^2d represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, or a hydrocarbon group having 8 to 18 carbon atoms, EO represents an oxyethylene group, and AO represents an oxypropylene group or an oxybutylene group. . s and t each represent an average added mole number, s is 1 or more and 20 or less, and t is 0.5 or more and 20 or less. “— (EO) _s — (AO) _t —” is a block bond. ]

In general formula (d-1), q is 0.5 or more, preferably 1 or more, and 5 or less, 4.5 or less, further 3 or less, and further preferably 2 or less. p + r is 2 or more, preferably 3 or more, more preferably 4 or more, and 20 or less, preferably 18 or less, and more preferably 16 or less.

In the general formula (d-1), R ^1d is preferably a hydrocarbon group having 10 to 14 carbon atoms, more preferably a linear alkyl group having 10 to 14 carbon atoms, preferably p = 2 to 8, and q = 0.5 -4.5, further 1-3, and more preferably 1-2, r = 2-8 is preferable, p + r = 4-16 is preferable, and 4-15 is more preferable. Specific examples of the nonionic surfactant of the general formula (d-1) include polyoxyethylene (3) polyoxypropylene (1.5) polyoxyethylene (3) lauryl ether, polyoxyethylene (5) polyoxypropylene. Examples thereof include one or more selected from (1.5) polyoxyethylene (5) lauryl ether and polyoxyethylene (5) polyoxypropylene (4.5) polyoxyethylene (5) lauryl ether. Here, regarding the said compound, the inside of () is the average addition mole number of ethylene oxide or propylene oxide (the same applies hereafter).

In the general formula (d-2), R ^2d is a linear or branched alkyl group having 8 to 18 carbon atoms, more preferably a linear or branched alkyl group having 8 to 16 carbon atoms, particularly, A linear or branched alkyl group having 8 to 14 carbon atoms is preferred.

In the general formula (d-2), s is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and m is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, particularly The number is preferably 14 or less.

In general formula (d-2), t is preferably 0.5 or more, more preferably 1 or more, still more preferably 2 or more, and n is preferably 20 or less, more preferably 18 or less, still more preferably 15 or less. Particularly preferably, the number is 10 or less.

The nonionic surfactant represented by the general formula (d-2) is preferable from the viewpoint of detergency as well as finish.

The compound of the general formula (d-2) can be synthesized by adding EO to an alcohol having a hydrocarbon group of R ^2d and then adding PO.

As the nonionic surfactant represented by the general formula (d-2), a nonionic surfactant represented by the following general formula (d-2 ′) is more preferable.
R ^2′d —O— (EO) _s1 — (PO) _t1 —H (d-2 ′)
[ ^Wherein R ^2'd represents a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms, or a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms. EO represents an oxyethylene group and PO represents an oxypropylene group. s1 and t1 each represent an average added mole number, s1 is 4 or more and 10 or less, t1 is 2 or more and 10 or less, t1 / s1 is 0.3 or more and 1.5 or less, and s1 = 4˜ 10, t1 = 2 to 10, and 0.3 ≦ (t1 / s1) ≦ 1.5. “— (EO) _s1 — (PO) _t1 —” is a block bond. ]

In the general formula (d-2 ′), R ^2′d is preferably a branched alkyl group having 10 to 14 carbon atoms or a branched alkenyl group, and more preferably a branched alkyl group having 10 to 14 carbon atoms. Further, ^among the branched alkyl groups or branched alkenyl groups having 10 to 14 carbon atoms of R ^2′d , secondary alkyl groups or alkenyl groups having 10 to 14 carbon atoms are preferable. In the general formula (d-2 ′), s1 = 5 to 9 is preferable, and t1 = 5 to 9 is preferable. Specific examples of the nonionic surfactant represented by the general formula (d-2 ′) include polyoxyethylene (7) polyoxypropylene (8.5) -sec-dodecyl ether, polyoxyethylene (7) polyoxypropylene (8 And 5) -sec-tridecyl ether, and polyoxyethylene (7) polyoxypropylene (8.5) -sec-tetradecyl ether.

In addition, the compound of the general formula (d-2 ′) is ^obtained by adding PO after adding EO to a branched chain (preferably secondary) alcohol having a branched chain (preferably secondary) hydrocarbon group of R ^2′d. It can be synthesized by adding.

Component (D) is made from the nonionic surfactant represented by the general formula (d-1) and the nonionic surfactant represented by the general formula (d-2 ′) from the viewpoint of finish. One or more selected nonionic surfactants are preferred.

Further, as the component (D), from the viewpoint of detergency, non-foaming property and low foaming property, a nonionic surfactant represented by the following general formula (d-3) and a general formula (d-4) One or more nonionic surfactants selected from the nonionic surfactants to be used are preferred.
HO- (EO) _a- (PO) _b- (EO) _c -H (d-3)
HO- (PO) _d- (EO) _e- (PO) _f -H (d-4)
[Wherein, EO represents an oxyethylene group, and PO represents an oxypropylene group. a, b, c, d, e and f are average added mole numbers, each independently, a number of 1 or more, further 2 or more, further 3 or more, and 350 or less, further 200 or less, further 100 or less, Further, the number is 1 to 350, 2 to 200, and 3 to 100. ]

In the general formulas (d-3) and (d-4), EO is preferably contained in an amount of 10 mol% or more in the total of EO and PO, and a, b, c, d, e, and f are included so as to satisfy this. It is preferable to select.
Further, from the viewpoint of low foaming property, a nonionic surfactant represented by the general formula (d-4) is more preferable.

When the component (D) is a nonionic surfactant represented by the general formulas (d-1) and (d-2), the weight average molecular weight of the component (D) is preferably 200 or more, and 5 2,000 or less, more preferably 2,000 or less. The weight average molecular weight of the component (D) is preferably 200 to 5,000, more preferably 200 to 2,000.

When the component (D) is a nonionic surfactant represented by the general formulas (d-3) and (d-4), the weight average molecular weight of the component (D) is 1,000 to 15,000. It is preferably 1,500 to 6,000.

Among the components (D), the compound of the general formula (d-1) is available from Nippon Shokubai Co., Ltd. under the trade name “Softanol”. The compound of the general formula (d-2 ') is available from Kao Corporation under the trade name “Emulgen”. The compound of the general formula (d-3) is available from ADEKA Corporation under the trade name “Pluronic”. The compound of the general formula (d-4) is available from BASF under the trade name “Pluronic R”.

<Solid bleach composition>
The blending amount of the component (A) in the solid bleaching agent composition of the present invention (ratio in all blending components, hereinafter the same) is 1.5% by mass or more, and further 2% by mass or more from the viewpoint of bleaching properties. Furthermore, 3 mass% or more is preferable, and it is 5 mass% or less, Furthermore, 4.5 mass% or less, Furthermore, 4 mass% or less is preferable. Further, the blending amount of the component (A) in the solid bleaching agent composition of the present invention (ratio in all blending components, hereinafter the same) is 1.5 to 5% by mass, preferably 2 from the viewpoint of bleaching properties. To 5% by mass, and more preferably 3 to 5% by mass.

The blending amount of the component (B) in the solid bleaching composition of the present invention is preferably 1% by mass or more from the viewpoint of storage stability, and is 10% by mass or less, further 5% by mass or less, and further 3% by mass or less. Is preferred. In addition, the blending amount of the component (B) in the solid bleaching composition of the present invention is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and still more preferably 1 to 5% by mass from the viewpoint of storage stability. 3% by mass.

The blending amount of the component (C) in the solid bleaching agent composition of the present invention, preferably the total blending amount of the alkali metal silicate anhydride salt and the alkali carbonate alkali metal salt, is from the viewpoint of detergency and storage stability. Therefore, 20 mass% or more, further 40 mass% or more is preferable, and 60 mass% or less is preferable. The blending amount of the component (C) in the solid bleaching agent composition of the present invention, preferably the total blending amount of the alkali metal silicate anhydride salt and the alkali metal carbonate carbonate anhydride salt, is detergency and storage stability. In view of the above, 20 to 60% by mass is preferable, and 40 to 60% by mass is more preferable.

The blending amount of the component (D) in the solid bleaching composition of the present invention is 0.5% by mass or more, 1.0% by mass or more, and further 1.5% by mass from the viewpoint of detergency and storage stability. The above is preferable, and it is 2.5% by mass or less. In addition, the blending amount of the component (D) in the solid bleaching composition of the present invention is 0.5 to 2.5% by mass and 1.0 to 2.5% by mass from the viewpoint of detergency and storage stability. % Is more preferable, and 1.5 to 2.5% by mass is even more preferable.

The mass ratios described below are based on the amount of each component unless otherwise specified. Moreover, the mass ratio described below can be based on the content.

The mass ratio of (A) / (B) is preferably 0.3 or more, more preferably 0.5 or more, and further preferably 1 or more, and 5 or less, and further 4 from the viewpoints of bleachability, storage stability, and chlorine residual ratio. Hereinafter, 2 or less is more preferable. The mass ratio of (A) / (B) is preferably 0.5 to 5, more preferably 1 to 4, and further preferably 1 to 2, from the viewpoints of bleachability, storage stability, and chlorine residual ratio.

The mass ratio of (A) / (C) is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more, from the viewpoints of bleachability, storage stability, and effective chlorine residual ratio. 15 or less, more preferably 0.1 or less. The mass ratio of (A) / (C) is preferably from 0.01 to 0.15, more preferably from 0.03 to 0.1, and still more preferably from the viewpoints of bleachability, storage stability, and effective chlorine residual ratio. 0.05 to 0.1 is preferable.

The mass ratio of (A) / (D) is preferably 0.6 or more, more preferably 0.8 or more, and further preferably 1 or more, and 5 or less, further 4 or less, and further 2 or less from the viewpoints of bleachability and detergency. Is preferred. Further, the mass ratio of (A) / (D) is preferably from 0.6 to 5, more preferably from 0.8 to 4, and further preferably from 1 to 2, from the viewpoints of bleachability and detergency.

The mass ratio of (B) / (C) is preferably 0.01 or more, from the viewpoint of storage stability, effective chlorine residual rate, and detergency, and is 0.1 or less, further 0.07 or less, and further preferably 0.00. 05 or less is preferable. The mass ratio of (B) / (C) is preferably 0.01 to 0.1, more preferably 0.01 to 0.07, and still more preferably 0.01 to 0.07, from the viewpoints of storage stability, effective chlorine residual rate, and detergency. 0.01 to 0.05 is preferable.

The mass ratio of (B) / (D) is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more, and 3 or less from the viewpoints of storage stability, effective chlorine residual rate, and detergency. Further, it is preferably 2 or less, more preferably 1.5 or less. In addition, the mass ratio of (B) / (D) is preferably 0.1 to 3, more preferably 0.3 to 2, and even more preferably 0.5 to 0.5 from the viewpoints of storage stability, effective chlorine residual ratio, and detergency. 1.5 is preferable.

The mass ratio of (C) / (D) is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more, and preferably 60 or less, further 50 or less, and further 30 or less from the viewpoints of detergency and storage stability. The mass ratio of (C) / (D) is preferably 5 to 60, more preferably 10 to 50, and further preferably 20 to 30 from the viewpoints of detergency and storage stability.

From the viewpoint of formulation, the content of sodium tripolyphosphate in the solid bleaching composition of the present invention is preferably less than 20% by mass, further 18% by mass or less, further 16% by mass or less, and further 14% by mass or less. Is preferred. The lower limit of the content of sodium tripolyphosphate is 0% by mass. The content of sodium tripolyphosphate in the solid bleaching composition of the present invention may be 0% by mass. Such a content is suitable for a composition in which a phosphorus-containing compound is reduced or a so-called phosphorus-free composition.

The water content in the solid bleaching agent composition of the present invention is 5% by mass or more and 10% by mass or less, preferably 8% by mass or less from the viewpoints of bleachability, storage stability, and effective chlorine residual ratio. . The water content in the solid bleaching agent composition of the present invention is 5 to 10% by mass, preferably 5 to 8% by mass, from the viewpoints of bleachability, storage stability and effective chlorine residual ratio.

The amount of water in the composition in the present invention means the total amount of crystal water and adhering water. The amount of adhering water in the composition can be measured by the Karl Fischer method (JIS K 0068). The amount of water of crystallization in the composition is determined by differential scanning calorimetry (DSC) method (manufactured by Seiko Denshi: Model DSC6200 temperature range reference: alumina. Sample amount: about 10 mg. Temperature rate: 5 ° C./min, measurement temperature range: 30 ° C. to 350 ° C., N ₂ flow rate: 100 ml / min) The total amount of adhering water and crystal water in the composition measured by such a method can be used as the water content in the composition.

Also, the amount of water in the composition can be determined by calculation based on the amount taken from the blended components. For example, for the raw materials used for blending, for each of the crystal water, the adhering water, and the water in the aqueous solution (which becomes crystal water or adhering water in the composition), the respective analytical values or calculated values are used, and the blending amount of each component From this, the amount of water derived from each component can be determined, and the water content of the solid bleaching agent composition of the present invention can be calculated as the sum of them.

Describing in more detail based on examples and comparative examples, among the ingredients used in the examples and comparative examples, the components containing crystal water include sodium dichloroisocyanurate dihydrate, sodium citrate 3Na and 2 water. Salt, sodium silicate, pentahydrate. The amount of water of crystallization of sodium dichloroisocyanurate dihydrate was 13.0% by mass, as determined from JIS K 0068-7. In addition, the amount of water of crystallization of sodium citrate 3Na · 2 hydrate is determined by the “Shipping Additive” “Sodium citrate” method, that is, the test method for weight loss on drying described in the “Food Additives Official Document (7th edition)” The loss on drying was determined under the conditions described in the section “Trisodium citrate” and found to be 12.3% by mass. The amount of crystallization water of sodium silicate pentahydrate was calculated from the molecular structure and was 42.5% by mass.

In addition, among the blending components used in Examples and Comparative Examples, examples of the component containing adhering water include polyacrylic acid and acrylic acid-maleic acid copolymer. The difference in mass% of solid content “ISO3251 (5 g / 150 ° C./16 h)” was determined as adhering water. As a result, 8.0% by mass of polyacrylic acid and 8.0% by mass of acrylic acid-maleic acid copolymer were obtained. %Met.

Further, among the blending components used in Examples and Comparative Examples, the components used in the aqueous solution were the polymer compounds (1) and (2), and the measurement was performed by the Karl Fischer method. For the measurement, Hiranuma trace moisture measuring device AQ7 was used, and Coulomat AK (Hayashi Junyaku Kogyo Co., Ltd.) was used as the generation solution, and Coulomat CGK (Hayashi Junyaku Kogyo Co., Ltd.) was used as the counter electrode solution. As a result, the water content of the aqueous solution of the polymer compound (1) was 65.0% by mass, and the effective content was 35.0% by mass. The water content of the aqueous solution of the polymer compound (2) was 60.0% by mass, and the effective content was 40.0% by mass.

<(E) component>
The solid bleaching agent composition of the present invention preferably contains a polymer compound as the component (E). From the viewpoint of preventing dye stain adhesion, as a component (E), a polymer compound having a monomer unit (e1) derived from one or more monomers selected from a monomer having a quaternary ammonium group and a monomer having an amino group It is preferable to mix. The polymer compound (E) preferably has a monomer unit (e1) and a monomer unit (e2) represented by —SO ₂ — from the viewpoint of finish.

When the component (E) has a monomer unit (e1) and a monomer unit (e2), from the viewpoint of finish, the molar ratio of the monomer unit (e2) / monomer unit (e1) is 0.01 or more, and further 0.03 As described above, 0.05 or more is preferable, and 1 or less, further 0.75 or less, and further 0.5 or less is preferable. When the component (E) includes the monomer unit (e1) and the monomer unit (e2), the molar ratio of the monomer unit (e2) / monomer unit (e1) is preferably 0.01 to 1 from the viewpoint of finish. More preferably, it is 0.03 to 0.75, and still more preferably 0.05 to 0.5.

As the component (E), the monomer unit (e1) is 10 mol% or more, further 30 mol% or more, further 50 mol% or more, further 60 mol% or more, and 99 mol% or less, based on all monomer units, A polymer compound containing 90 mol% or less, and further 80 mol% or less, having a monomer unit (e1) and a monomer unit (e2), and the monomer unit (e2) / monomer unit (e1) molar ratio is 0.00. The polymer compound is preferably 01 or more, further 0.03 or more, further 0.05 or more, and 1 or less, further 0.75 or less, and further 0.5 or less. Further, as the component (E), the monomer unit (e1) is contained in an amount of 10 to 99 mol% based on the total monomer units, and the molar ratio of the monomer unit (e2) / monomer unit (e1) is 0.01 to 1. Certain polymer compounds are preferred.

As the monomer used for constituting the monomer unit (e1), one or more selected from the compounds represented by the following general formula (e1-1) and the compounds represented by the general formula (e1-2) are preferable.

[Wherein, R ^1e , R ^2e , R ^3e , R ^7e , R ^8e , R ^9e are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. X and Y are each independently an alkylene group having 1 to 12 carbon atoms, — (CO) OR ^12e —, — (CO) (NH) R ^12e —, ^—O (CO) R ^12e —, and — A group selected from R ^13e —O (CO) —R ^12e —. Here, R ^12e and R ^13e are each independently an alkylene group having 1 to 5 carbon atoms. R ^4e is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^1e R ^2e C═C (R ^3e ) —X—. R ^5e is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^6e is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group and R ^6e is an alkyl group, a hydroxyalkyl group, or a benzyl group, Z ⁻ represents an anion. When R ^6e contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ^6e become anions.
Examples of the anion of Z ⁻ include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. Can be mentioned. R ^10e is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^7e R ^8e C═C (R ^9e ) —Y—. R ^11e is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]

Specifically preferred as the compound of the general formula (e1-1) is acryloyl (or methacryloyl) aminoalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium. Salt, acryloyl (or methacryloyl) oxyalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, N- (ω-alkenyl (2 to 10 carbon atoms) ) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt and N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (1 carbon atom) -3) One or two or more types selected from quaternary ammonium salts are included, and diallyldimethylammonium salt is more preferable.

Specifically preferred as the compound of the general formula (e1-2) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N-dialkyl (C1-3) amine, acryloyl (or methacryloyl). ) Oxyalkyl (C1-5) -N, N-dialkyl (C1-3) amine, N- (ω-alkenyl (C2-10))-N, N-dialkyl (C1 3) One or two selected from amine, N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine, and diallylamine And allylamine, diallylmethylamine, diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, and And one or more selected from acryloyl (or methacryloyl) oxyethyl-N, N-dimethylamine are preferred.

From the viewpoint of surface adsorption power, the component (E) preferably contains the monomer unit (e1) in an amount of 10 mol% or more, further 30 mol% or more, further 50 mol% or more, and further 60 mol% or more based on the total monomer units, And preferably it contains 99 mol% or less, further 90 mol% or less, and also 80 mol% or less. From the viewpoint of surface adsorption power, the component (E) is preferably 10 to 99 mol%, more preferably 30 to 90 mol%, still more preferably 50 to 90 mol% of the monomer unit (e1) with respect to the total monomer units. %, More preferably 60 to 80 mol%. This mol% is calculated by [number of moles of monomer unit (e1) / number of moles of all monomer units] × 100.

The preferred monomer unit (e2) possessed by the polymer compound (E) is —SO ₂ —. As a method for introducing such a monomer unit into the polymer compound, a predetermined amount of SO ₂ gas is used in the general formula. Blowing into a solution containing one or more compounds selected from the compound of (e1-1) and the compound of general formula (e1-2), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di Lauroyl peroxide, azobisisobutyronitrile, azobisisobarrel nitrilo, 2,2'-azobis (2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxy Heavy selected from acetic acid, perbenzoic acid, persulfate, and hydrogen peroxide Obtained by polymerizing using an initiator. A solvent can be used at the time of polymerization. Specifically, alcohols selected from water, methanol, ethanol and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazo Lydinone, acetonitrile, propionitrile, toluene, xylene and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably −20 to 200 ° C., preferably −10 to 100 ° C. In the present invention, polymerization can also be performed by light or radiation, and the polymerization can be efficiently performed by irradiating light with a wavelength of 300 to 450 nm.

The component (E) of the present invention can contain a structural unit derived from a monomer having an anionic group (hereinafter referred to as monomer unit (e3)). In that case, the molar ratio of the monomer unit (e1) to the monomer unit (e3) is preferably monomer unit (e1) / monomer unit (e3) = 10/90 or more, more preferably 30/70 or more, and more preferably 50/50 or more. And 90/10 or less, Furthermore 85/15 or less, Furthermore 80/20 or less are preferable. The molar ratio of the monomer unit (e1) to the monomer unit (e3) is such that the monomer unit (e1) / monomer unit (e3) = 10/90 to 90/10, more preferably 30/70 to 85/15, particularly 50 / It is preferably 50 to 80/20. Examples of the monomer having an anionic group include the following (e3-1).

(E3-1) Acrylic acid and its salt, methacrylic acid and its salt, maleic acid and its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl Compounds selected from sulfonates, methallylsulfonates, sulfopropyl methacrylates, and mono-ω-methacryloyloxyalkyl phosphates (having 1 to 12 carbon atoms)

From the viewpoint of finish, the monomer unit (e3) is an anion derived from a monomer having an anionic group selected from acrylic acid and its salt, methacrylic acid and its salt, maleic acid and its salt, and maleic anhydride. Ionic monomer units are preferred.

The monomer unit (e3) is preferably acrylic acid or a sodium salt or potassium salt thereof, methacrylic acid or a sodium salt or potassium salt thereof, maleic acid or a sodium salt or potassium salt thereof from the viewpoint of finish.

The counter ion of the anionic group of the monomer unit (e3) may be a cationic group (cation group selected from a quaternary ammonium group and an amino group) of the monomer unit (e1).

The component (E) of the present invention can also have a structural unit derived from a nonionic monomer (hereinafter referred to as monomer unit (e4)). Examples of the nonionic monomer include monomers selected from the following (e4-1) to (e4-3).

(E4-1) Acrylic (or methacrylic) amide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid ( Or methacrylic acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone-containing compound

(E4-2) Acrylic acid (or methacrylic acid) alkyl (carbon number 1 to 5), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (carbon 1-5) and an ester group-containing compound selected from vinyl acetate

(E4-3) Ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4 Olefin compounds selected from methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene

The monomer unit (e4) is preferably a monomer unit derived from the monomer (e4-1) from the viewpoint of finish.

When the component (E) has a monomer unit (e4), the molar ratio of the monomer unit (e4) / monomer unit (e1) is 0.05 or more, further 0.1 or more, and further preferably 0.00 from the viewpoint of finish. 2 or more are preferable, and 1 or less, further 0.75 or less, and further 0.5 or less are preferable. When the component (E) has a monomer unit (e4), the molar ratio of the monomer unit (e4) / monomer unit (e1) is 0.05 to 1, more preferably 0.1 to It is preferably 0.75, and more preferably 0.2 to 0.5.

The polymer compound of the component (E) of the present invention has a weight average molecular weight of preferably 1,000 or more, more preferably 5,000, and preferably 6,000,000 or less, further 500,000 or less, and further 100 , 000 or less, and further 60,000 or less. The polymer compound of component (E) of the present invention preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 1,000 to 500,000, and still more preferably 1,000 to 100. 5,000, more preferably 5,000 to 60,000. This weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.

The polymer compound of the component (E) used in the present invention is composed of the monomer unit (e1), the monomer unit (e2), and preferably the monomer units (e3) and (e4) of the main chain or side chain in the polymer compound. It doesn't matter if it exists. These may be randomly polymerized, block polymerized, or graft polymerized. In the present invention, it is more preferable to use a polymer compound composed only of the monomer unit (e1), the monomer unit (e2) and the monomer unit (e3).

The component (E) is preferably used as an aqueous solution having a concentration of 25 to 40% by mass from the viewpoint of handling properties.

As the radical initiator of the polymer compound (E) used in the present invention, a water-soluble radical initiator or a persulfate radical initiator having an azo group in the molecule can be preferably used. A persulfate radical initiator is preferred as the radical initiator.

Examples of persulfate-based radical initiators include ammonium persulfate, sodium persulfate, and potassium persulfate, and these may be used alone or in combination of two or more. In particular, sodium persulfate is preferable.

The blending amount of the component (E) in the solid bleaching composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further 0.5% by mass or more from the viewpoint of finish. And, it is preferably 5% by mass or less, further 4.5% by mass or less, further 3% by mass or less, and further 2% by mass or less. Further, the blending amount of the component (E) in the solid bleaching composition of the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 4.5% by mass from the viewpoint of finish. The amount is preferably 0.5 to 3% by mass, and more preferably 0.5 to 2% by mass.

The total amount of component (D) and component (E) in the solid bleaching composition of the present invention is preferably 0.6% by mass or more, more preferably 0, from the viewpoint of detergency or finish. 0.8 mass% or more, more preferably 1 mass% or more, and from the viewpoint of storage stability, it is preferably 3 mass% or less, more preferably 2.5 mass% or less, and even more preferably 2 mass% or less. is there.

The mass ratio of (A) / (E) is preferably 1 or more, more preferably 1.4 or more, and further preferably 2 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less, from the viewpoints of bleachability and finish. . The mass ratio of (A) / (E) is preferably 1 to 10, more preferably 1.4 to 8, and still more preferably 2 to 7, from the viewpoints of bleachability and finish.

The mass ratio of (B) / (E) is preferably 0.5 or more, more preferably 0.8 or more, and further preferably 1.4 or more, and 15 or less, from the viewpoints of storage stability, effective chlorine residual rate, and finish. Further, it is preferably 12 or less, more preferably 10 or less. The mass ratio of (B) / (E) is preferably from 0.5 to 15, more preferably from 0.8 to 12, and even more preferably from 1.4 to 1.4, from the viewpoints of storage stability, effective chlorine residual rate, and finish. 10 is preferred.

From the viewpoint of detergency, the mass ratio of (C) / (E) is preferably 15 or more, more preferably 30 or more, and is preferably 100 or less, more preferably 80 or less, and further preferably 60 or less. The mass ratio of (C) / (E) is preferably from 15 to 100, more preferably from 30 to 80, and even more preferably from 30 to 60, from the viewpoint of detergency.

From the viewpoint of detergency, the mass ratio of (D) / (E) is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.4 or more, and 8 or less, further 6 or less, and further 4 or less. preferable. The mass ratio of (D) / (E) is preferably from 0.1 to 8, more preferably from 0.3 to 6, and further preferably from 0.4 to 4, from the viewpoint of detergency.

<Other ingredients>
The solid bleaching agent composition of the present invention can contain a polymer compound selected from polyacrylic acid, acrylic acid-maleic acid copolymer, and salts thereof. Moreover, the solid bleaching agent composition of the present invention can contain a compound called a builder, particularly an organic compound.

In the solid bleaching agent composition of the present invention, a polymer compound selected from polyacrylic acid, acrylic acid-maleic acid copolymer, and salts thereof can be blended. The weight average molecular weight of the polyacrylic acid or a salt thereof is preferably 1000 or more, more preferably 2000 or more, and more preferably 3000 or more, and 20000 or less, further 15000 or less, further 10,000 or less, and further 5000 or less, from the viewpoint of preventing staining of dye stains. Is preferred. In addition, the weight average molecular weight of the acrylic acid-maleic acid copolymer or salt thereof is preferably 2000 or more, more preferably 10,000 or more, and more preferably 60000 or more, and more preferably 100,000 or less, further 90,000 or less, from the viewpoint of preventing staining of the dye stain. Furthermore, 80,000 or less is preferable. This weight average molecular weight can be determined by using gel / permeation chromatography with polyacrylic acid as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent. The salt is preferably an alkali metal salt such as a sodium salt or a potassium salt.

In the acrylic acid-maleic acid copolymer or salt thereof, the molar ratio of acrylic acid / maleic acid is preferably 90/10 or more, more preferably 75/25, and preferably 50/50 or less, more preferably 65/35 or less. . The salt is preferably an alkali metal such as sodium salt or potassium salt. The molar ratio of acrylic acid / maleic acid can be determined by detecting the pyrolyzate of the copolymer by pyrolysis gas chromatography (PGC).

The blending amount of the polymer compound selected from polyacrylic acid, acrylic acid-maleic acid copolymer and salts thereof in the solid bleaching composition of the present invention is preferably 8% by mass from the viewpoint of preventing staining of dye stains. In addition, the content is further 8.5% by mass or more, further 9% by mass or more, and preferably 20% by mass or less, further 15% by mass or less, and further 10% by mass or less.

In the present invention, it is preferable to blend both polyacrylic acid or a salt thereof and an acrylic acid-maleic acid copolymer or a salt thereof. Mass ratio of blending amount of polyacrylic acid or salt thereof and blending amount of acrylic acid-maleic acid copolymer or salt thereof (polyacrylic acid or salt thereof) / (acrylic acid-maleic acid copolymer or salt thereof) Is preferably 3 or more, more preferably 3.5 or more, and still more preferably 4 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less from the viewpoint of preventing dye stain adhesion.

As an action mechanism of the builder, a metal chelate action, an alkali buffer action, and a solid particle dispersion action are important. Especially, it is preferable to mix | blend a chelating agent. In addition, a polymer compound selected from polyacrylic acid, acrylic acid-maleic acid copolymer, and salts thereof may have a function as a builder.

Examples of organic acids of builder component organic acid alkali metal salts include dicarboxylic acids and tricarboxylic acids. Moreover, as a kind of organic acid, an amino acid and hydroxycarboxylic acid are mentioned, Hydroxycarboxylic acid is preferable. The molecular weight of the builder component is preferably less than 1000.

Among the organic acids of the builder component, dicarboxylic acids include succinic acid, fumaric acid, maleic acid, tartaric acid, malic acid, aspartic acid, glutaric acid, glutamic acid, adipic acid, peric acid, itaconic acid, terephthalic acid, and the like. Examples of the acid include citric acid, and examples of the amino acid include phenylalanine, tryptophan, asparagine, glutamine, valine, isoleucine, leucine, histidine, methionine, and tyrosine.

Examples of the alkali metal salt include sodium salt and potassium salt, preferably sodium salt.

The builder component is preferably an alkali metal salt of hydroxycarboxylic acid, more preferably an alkali metal salt of hydroxycarboxylic acid selected from tartaric acid, malic acid, and citric acid, and more preferably an alkali metal salt of citric acid. From the viewpoint of metal ion scavenging ability, sodium citrate is more preferable.

In the solid bleaching composition of the present invention, the blending amount when blending the chelating agent is preferably 20% by mass or more, more preferably 25% by mass or more, and 60% by mass or less, and further preferably 40% by mass or less. Further, the blending amount when the chelating agent is blended is preferably 20 to 60% by mass, more preferably 25 to 40% by mass in the solid bleaching composition of the present invention.

In the composition of the present invention, a powdery organic polymer compound having water absorption by hydrogen bonding can be further blended. Specifically, dextrin, carrageenan, xanthan gum, guar gum, pectin, locust bin gum, or derivatives thereof, polysaccharides such as modified starch, methylcellulose, carboxymethylcellulose, synthetic polymer compounds such as polyvinyl alcohol, polyacrylamide, polyethylene oxide, etc. Is mentioned. The blending amount of the organic polymer compound in the powder having water absorption is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the solid bleaching composition of the present invention from the viewpoint of storage stability. Further, it is 1% by mass or more, and preferably 20% by mass or less, further 15% by mass or less, and further 10% by mass or less. Further, the blending amount of the organic polymer compound in the powder having water absorbability is preferably 0.1 to 20% by mass, more preferably 0 in the solid bleaching agent composition of the present invention from the viewpoint of storage stability. 0.5 to 15% by mass, particularly preferably 1 to 10% by mass.

The solid bleaching composition of the present invention comprises an anionic surfactant (for example, an anionic surfactant described in WO99 / 58633 pamphlet), an amphoteric surfactant, an enzyme, a bleaching agent [(A ) Other than the component], an antifoaming agent, an antirust agent, a hydrotrope agent, a surface modifier, a fragrance and the like can be blended.

The solid bleaching composition of the present invention is in the form of powder, granules, pellets, tablets or the like.

The solid bleaching agent composition of the present invention can be used as a cleaning solution diluted to an appropriate concentration with water or the like when used, and in that case, diluted to 0.05 to 0.5% by mass. it can.

The solid bleaching composition of the present invention can be used for commercial and household dishwashers, but is particularly suitable for commercial use that is washed in large quantities at once and many times a day.

When washing with a commercial dishwasher, for example, set a plastic hopper filled with a solid bleaching agent composition for a dishwasher in a hopper dedicated to a commercial dishwasher in a predetermined direction, or Transfer the solid bleach composition filled in a pouch container etc. to a hopper for a commercial dishwasher. And the spray or shower etc. are sprayed with water or warm water with respect to the set composition, and the melt | dissolved washing | cleaning liquid is supplied to the inside of a commercial dishwasher, and is used for washing | cleaning of tableware.

In commercial dishwashers, when washing dishes continuously, the cleaning liquid is circulated with a pump and used repeatedly. Since the cleaning liquid prepared from the composition of the present invention is excellent in storage stability and has little decrease in effective chlorine concentration, an excellent cleaning effect can be obtained even in such a usage mode of continuous circulation.

In the solid bleaching agent composition of the present invention, the water content in the final composition is 5 to 10% by mass of the blending component including the component (A), the component (B), the component (C) and the component (D). Can be used to manufacture. In this case, the amount of water taken in from each component can be confirmed by the above method, and the amount of water in the final composition can be determined by calculation. In addition, mixing of the said mixing | blending component can be performed in arbitrary orders.

The solid bleaching composition of the present invention contains (A) component 1.5 to 5% by mass, (B) component, and (C) component, and has a water content of 5 to 10% by mass. It may be a thing. Further, the solid bleaching agent composition of the present invention has a component (A) of 1.5 to 5% by mass, a component (B), a component (C), and a component (D) of 0.5% by mass or more. It may be a solid bleach composition containing 5% by mass or less and having a water content of 5% by mass or more and 10% by mass or less. Further, the solid bleaching agent composition of the present invention has a component (A) of 1.5 to 5% by mass, a component (B), a component (C), and a component (D) of 0.5% by mass or more. It may be a solid bleaching composition containing 5% by mass or less, having a sodium tripolyphosphate content of 0% by mass or more and less than 20% by mass, and having a moisture content of 5% by mass or more and 10% by mass or less. . With respect to these compositions, the above-mentioned preferred embodiments such as the components (A) to (D), the water content, and optional components can be employed. At that time, the blending amount may be read as the content.

Embodiments of the present invention are shown below.
<Section 1>
(A) Sodium dichloroisocyanurate dihydrate (hereinafter referred to as “component (A)”) is selected from 1.5% by mass to 5% by mass, (B) amorphous silica, and crystalline calcium silicate. One or more kinds of liquid-supporting powder [hereinafter referred to as component (B)], (C) an inorganic alkali metal salt anhydride (hereinafter referred to as component (C)), and (D) nonionic surface activity A solid bleaching composition comprising 0.5% by mass or more and 2.5% by mass or less of an agent [hereinafter referred to as component (D)], and having a water content of 5% by mass or more and 10% by mass or less.

<Section 2>
The component (B) has an oil absorption capacity of 120 ml / 100 g or more and 1000 ml / 100 g or less, more preferably 600 ml / 100 g or less, or 120 to 1000 ml / 100 g, or 120 to 1000 ml / 100 g, according to the method described in JIS K6220 (−1995). The solid bleaching agent composition according to <Item 1>, which is a 600 ml / 100 g powder.

<Section 3>
The component (B) has a specific surface area of 30 (m ² / g) or more, further 50 (m ² / g) or more, 600 (m ² / g) or less, further 400 (m ² / g) or less, Or 30-600 (m ² / g)
Further, the solid bleaching composition according to <Item 1> or <Item 2>, which is a powder of 50 to 400 (m ² / g).

<Section 4>
(B) The solid bleaching composition according to any one of <Item 1> to <Item 3>, wherein the component is amorphous silica.

<Section 5>
Any one of <Claim 1> to <Claim 4>, wherein the component (C) is at least one selected from (C1) an anhydride of an alkali metal silicate and (C2) an anhydride of an alkali metal carbonate. A solid bleach composition as described.

<Section 6>
The component (C) is one or more selected from (C1) an anhydride of an alkali metal silicate and (C2) one or more selected from an anhydride of an alkali metal carbonate, The mass ratio (C1) / (C2) of the blending amount of C2) is 10/90 or more, further 20/80 or more, 50/50 or less, and further 40/60 or less, <Item 1> to <Item 5 > The solid bleaching agent composition in any one of>.

<Section 7>
The solid bleaching composition according to <5> or <6>, wherein (C1) is anhydrous sodium silicate and (C2) is anhydrous sodium carbonate.

<Section 8>
(C) The solid bleaching composition according to any one of <1> to <4>, wherein the component is one or more selected from anhydrous sodium carbonate, anhydrous potassium carbonate, and anhydrous sodium silicate. object.

<Section 9>
The component (D) is at least one nonionic surfactant selected from a nonionic surfactant represented by the following general formula (d-1) and a nonionic surfactant represented by the general formula (d-2 ′) The solid bleaching agent composition according to any one of <Item 1> to <Item 8>, which is a surfactant.
R ^1d —O— (EO) _p — (PO) _q — (EO) _r —H (d−1)
[Wherein R ^1d represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, or a hydrocarbon group having 8 to 18 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q and r each represent an average number of added moles, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, r is 1 or more and 10 or less, and p = 1 to 10, q = 0.5 to 5 and r = 1 to 10. “— (EO) _p — (PO) _q — (EO) _r —” ”is a block bond. ]
R ^2′d —O— (EO) _s1 — (PO) _t1 —H (d-2 ′)
[ ^Wherein R ^2'd represents a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms, or a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms. EO represents an oxyethylene group and PO represents an oxypropylene group. s1 and t1 each represent an average added mole number, s1 is 4 or more and 10 or less, t1 is 2 or more and 10 or less, t1 / s1 is 0.3 or more and 1.5 or less, and s1 = 4˜ 10, t1 = 2 to 10, and 0.3 ≦ (t1 / s1) ≦ 1.5. “— (EO) _s1 — (PO) _t1 —” is a block bond. ]

<Section 10>
The component (D) is one or more nonionic surfactants selected from nonionic surfactants represented by the following general formula (d-3) and nonionic surfactants represented by the general formula (d-4) The solid bleaching composition according to any one of <Item 1> to <Item 8>, which is a surfactant.
HO- (EO) _a- (PO) _b- (EO) _c -H (d-3)
HO- (PO) _d- (EO) _e- (PO) _f -H (d-4)
[Wherein, EO represents an oxyethylene group, and PO represents an oxypropylene group. a, b, c, d, e and f are average added mole numbers, and are each independently a number of 1 or more, 2 or more, 3 or more, 350 or less, 200 or less, or 100 or less. is there. ]

<Section 11>
The blending amount of component (A) (ratio in all blending components, hereinafter the same) is 1.5% by mass or more, further 2% by mass or more, further 3% by mass or more, and 5% by mass or less, and further 4.5%. <5% by mass or less, further 4% by mass or less, or the blending amount of the component (A) is 1.5 to 5% by mass, further 2 to 5% by mass, and further 3 to 5% by mass. The solid bleaching composition according to any one of> to <10>.

<Section 12>
The blending amount of the component (B) is 1% by mass or more and 10% by mass or less, further 5% by mass or less, further 3% by mass or less, or 1 to 10% by mass, further 1 to 5% by mass, The solid bleaching composition according to any one of <Item 1> to <Item 11>, further comprising 1 to 3% by mass.

<Section 13>
The blending amount of the component (C), and further the total blending amount of the alkali metal silicate anhydride salt and the alkali carbonate carbonate anhydrous salt is 20% by mass or more, further 40% by mass or more, and 60% by mass or less. The solid bleaching agent composition according to any one of <Item 1> to <Item 12>, which is or is 20 to 60% by mass and 40 to 60% by mass.

<Section 14>
The blending amount of the component (D) is 0.5% by mass or more, 1.0% by mass or more, further 1.5% by mass or more, and 2.5% by mass or less, or 0.5-2. The solid bleaching agent composition according to any one of <Item 1> to <Item 13>, which is 5% by mass, further 1.0 to 2.5% by mass, and further 1.5 to 2.5%.

<Section 15>
The mass ratio (A) / (B) of the blending amount of the component (A) and the blending component (B) is 0.3 or more, further 0.5 or more, further 1 or more, 5 or less, further 4 or less, The solid bleaching composition according to any one of <Item 1> to <Item 14>, further 2 or less, or 0.5 to 5, further 1 to 4, and further 1 to 2.

<Section 16>
The mass ratio (A) / (C) of the blending amount of the component (A) and the blending component (C) is 0.01 or more, further 0.03 or more, further 0.05 or more, and 0.15 or less, <Claim 1> to <Claim 15> which is 0.1 or less, or 0.01 to 0.15, further 0.03 to 0.1, and further 0.05 to 0.1. The solid bleaching composition according to claim 1.

<Section 17>
The mass ratio (A) / (D) of the blending amount of the component (A) and the blending component (D) is 0.6 or more, further 0.8 or more, further 1 or more, 5 or less, further 4 or less, The solid bleaching composition according to any one of <Item 1> to <Item 16>, further 2 or less, or 0.1 to 5, further 0.5 to 4, and further 1 to 2.

<Section 18>
The mass ratio (B) / (D) of the blending amount of the component (B) and the blending component (D) is 0.1 or more, further 0.3 or more, further 0.5 or more, 3 or less, and further 2 Any one of <Item 1> to <Item 17>, which is 1.5 or less, or 0.1 to 3, further 0.3 to 2, and further 0.5 to 1.5. A solid bleach composition as described.

<Section 19>
The mass ratio (C) / (D) of the blending amount of the component (C) and the blending component (D) is 5 or more, further 10 or more, further 20 or more, 60 or less, further 50 or less, and further 30 or less. The solid bleaching agent composition according to any one of <Item 1> to <Item 18>, which is, or 5 to 60, further 10 to 50, and further 20 to 30.

<Section 20>
Further, (E) a polymer compound having a monomer unit (e1) derived from one or more monomers selected from a monomer having a quaternary ammonium group and a monomer having an amino group (hereinafter referred to as “component (E)”) The solid bleaching agent composition according to any one of <Item 1> to <Item 19>.

<Section 21>
The solid bleaching agent composition according to <20>, wherein the component (E) has a monomer unit (e2) represented by —SO ₂ —.

<Section 22>
Component (E) is a monomer unit (e1) of 10 mol% or more, further 30 mol% or more, further 50 mol% or more, further 60 mol% or more, and 99 mol% or less, and further 90 mol%, based on all monomer units. It is a polymer compound containing not more than mol%, further not more than 80 mol%, having a monomer unit (e1) and a monomer unit (e2), and the monomer unit (e2) / monomer unit (e1) molar ratio is 0.01. The solid bleaching agent composition according to <21>, which is a polymer compound of 0.03 or more, 0.05 or more, 1 or less, further 0.75 or less, and further 0.5 or less.

<Section 23>
<Item 20> to <Item 22>, wherein the monomer unit (e1) is composed of one or more monomers selected from a compound of the following general formula (e1-1) and a compound of the general formula (e1-2) The solid bleaching composition of any one of Claims.

<Section 24>
The solid bleaching according to any one of <20> to <23>, wherein the component (E) includes a structural unit derived from a monomer having an anionic group (hereinafter referred to as a monomer unit (e3)). Agent composition.

<Section 25>
The molar ratio of the monomer unit (e1) to the monomer unit (e3) is such that the monomer unit (e1) / monomer unit (e3) = 10/90 or more, further 30/70 or more, further 50/50 or more, and 90/10. Hereinafter, 85/15 or less, further 80/20 or less, or 10/90 to 90/10, further 30/70 to 85/15, further 50/50 to 80/20, <Item 24> Solid bleach composition.

<Section 26>
The solid bleaching agent composition according to <Item 24> or <Item 25>, wherein the monomer unit (e3) is composed of one or more monomers selected from the following compounds (e3-1):
(E3-1) Acrylic acid and its salt, methacrylic acid and its salt, maleic acid and its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl Compounds selected from sulfonates, methallylsulfonates, sulfopropyl methacrylates, and mono-ω-methacryloyloxyalkyl phosphates (having 1 to 12 carbon atoms)

<Section 27>
The weight average molecular weight of the component (E) is 1,000 or more, further 5,000, and 6,000,000 or less, further 500,000 or less, further 100,000 or less, and further 60,000 or less. Or 1,000 to 6,000,000, 1,000 to 500,000, 1,000 to 100,000, 5,000 to 60,000, <Item 20> to <Item 26 > The solid bleaching agent composition in any one of>.

<Section 28>
The amount of component (E) is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and 5% by mass or less, preferably 4.5% by mass or less. More preferably 3% by mass or less, still more preferably 2% by mass or less, or 0.1 to 5% by mass, preferably 0.3 to 4.5% by mass, more preferably 0.5 to 3% by mass. %, More preferably 0.5 to 2% by mass, The solid bleaching composition according to any one of <Item 20> to <Item 27>.

<Section 29>
The total amount of component (D) and component (E) is 0.6% by mass or more, preferably 0.8% by mass or more, more preferably 1% by mass or more, and 3% by mass. The solid bleaching agent composition according to any one of <Item 20> to <Item 28>, which is preferably 2.5% by mass or less, more preferably 2% by mass or less.

<Section 30>
The mass ratio (A) / (E) between the blending amount of (A) and the blending amount of (E) is 1 or more, further 1.4 or more, further 2 or more, 10 or less, further 8 or less, and further 7 or less. The solid bleaching composition according to any one of <Item 20> to <Item 29>, which is, or 1 to 10, further 1.4 to 8, and further 2 to 7.

<Section 31>
The mass ratio (B) / (E) of the blending amount of (B) and the blending amount of (E) is 0.5 or more, further 0.8 or more, further 1.4 or more, and 15 or less, further 12 or less, The solid bleaching agent composition according to any one of <Item 20> to <Item 30>, further 10 or less, or 0.5 to 15, further 0.8 to 12, and further 1.4 to 10. object.

<Section 32>
The mass ratio (C) / (E) between the blending amount of (C) and the blending amount of (E) is 15 or more, further 30 or more, and 100 or less, further 80 or less, further 60 or less, or 15 to The solid bleaching agent composition according to any one of <Item 20> to <Item 31>, which is 100, further 30 to 80, and further 30 to 60.

<Section 33>
The mass ratio (D) / (E) of the blending amount of (D) and the blending amount of (E) is 0.1 or more, further 0.3 or more, further 0.4 or more, and 8 or less, further 6 or less, The solid bleaching agent composition according to any one of <Item 1> to Item 32, which is 4 or less, or 0.1 to 8, further 0.3 to 6, and further 0.4 to 4. object.

<Section 34>
Further, <Claim 1> to <Claim 33> formed by blending a polymer compound selected from polyacrylic acid, an acrylic acid-maleic acid copolymer, and salts thereof (hereinafter referred to as an acrylic acid polymer compound). The solid bleaching agent composition of any one of these.

<Section 35>
The blending amount of the acrylic polymer compound is 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass or more, and 20% by mass or less, preferably 15% by mass or less, more preferably The solid bleaching agent composition according to <Item 34>, which is 10% by mass or less.

<Section 36>
The solid bleaching composition according to <Item 34> or <Item 35>, wherein polyacrylic acid or a salt thereof and an acrylic acid-maleic acid copolymer or a salt thereof are blended as an acrylic acid polymer compound. .

<Section 37>
Mass ratio of blending amount of polyacrylic acid or salt thereof and blending amount of acrylic acid-maleic acid copolymer or salt thereof (polyacrylic acid or salt thereof) / (acrylic acid-maleic acid copolymer or salt thereof) The solid bleaching composition according to <Item 36>, wherein is 3 or more, preferably 3.5 or more, more preferably 4 or more, and 20 or less, preferably 15 or less, more preferably 10 or less.

<Section 38>
The solid bleaching agent composition according to any one of <Item 1> to <Item 37>, further comprising an organic acid alkali metal salt.

<Section 39>
The organic acid alkali metal salt is an alkali metal salt of hydroxycarboxylic acid, and further is an alkali metal salt of hydroxycarboxylic acid selected from tartaric acid, malic acid, and citric acid, and further an alkali metal salt of citric acid. <Item 38> The solid bleaching agent composition.

<Section 40>
The blending amount of the organic acid alkali metal salt is 20% by mass or more, further 25% by mass or more, and 60% by mass or less, further 40% by mass or less, or 20 to 60% by mass, further 25 to 40% by mass. The solid bleaching agent composition according to <Item 38> or <Item 39>.

<Section 41>
(A) 1.5 mass% or more and 5 mass% or less of sodium dichloroisocyanurate dihydrate, (B) It has 1 or more types of liquid support ability chosen from amorphous silica and crystalline calcium silicate. Powder, (C) an inorganic alkali metal salt anhydride, and (D) a nonionic surfactant in an amount of 0.5% by mass to 2.5% by mass and a water content of 5% by mass to 10%. The solid bleaching composition which is the mass% or less.

<Section 42>
The solid according to <Item 41>, further comprising (E) a polymer compound having a monomer unit (e1) derived from one or more monomers selected from a monomer having a quaternary ammonium group and a monomer having an amino group. Bleach composition.

<Section 43>
The content of sodium tripolyphosphate is 0% by mass or more and less than 20% by mass, further 18% by mass or less, further 16% by mass or less, and further 14% by mass or less, according to <Item 1> to <Item 42>. The solid bleaching composition of any one of Claims.

<Item 44>
The solid bleaching composition according to any one of <Item 1> to <Item 43>, wherein the water content is 8% by mass or less, or 5 to 8% by mass.

<Section 45>
Use of the composition according to any one of <Item 1> to <Item 44> as a solid bleaching agent, preferably for washing dishes.
Examples Examples and comparative examples are shown below. The examples are illustrative of the invention and are not intended to limit the invention.

<Preparation of solid bleach composition>
The solid bleaching compositions in Tables 1 and 2 are powders prepared by the following method (total blending amount: 10 kg). The solid bleaching compositions shown in Tables 1 and 2 were both powdery and had a bulk density of 0.7 to 1.0 (g / ml). Moreover, the moisture content in the composition of Tables 1 and 2 was calculated | required from calculation based on the quantity taken in from a compounding component.

(D) component is dripped and mixed in the state which mixed sodium citrate 3Na * 2 hydrate, anhydrous sodium sulfate, and (B) component. (C) component is mixed there, (E) component is dripped, Then, polyacrylic acid and an acrylic acid-maleic acid copolymer are thrown in, and it stirs and mixes. After confirming uniform mixing, the component (A) was added and stirred and mixed. Compositions having different blending components in Examples and Comparative Examples were blended at appropriate locations in accordance with this to prepare compositions.

Examples of the apparatus for stirring and mixing each component include a Nauter mixer and a Henschel mixer. In addition, when the components (D) and (E), which are liquid components, are dropped and mixed, the dropping rate is preferably 2 to 5 minutes, and divided addition (intermittent addition) is preferred. The solid bleaching compositions shown in Tables 1 and 2 were dropped when the Nauter mixer “Hosokawa Micron Co., Ltd. Model: DBY-10R” was used as an apparatus and the liquid components (D) and (E) were mixed dropwise. The speed was adjusted for 3 minutes and the addition method was divided addition (intermittent addition).

In the blending method, the mixing temperature from the start of stirring at least one of sodium citrate 3Na · dihydrate, anhydrous sodium sulfate and component (B) to the final mixture is 20-50 ° C. Is preferred. The stirring time required for each step is preferably 3 to 7 minutes. In the preparation of the solid bleaching compositions of Tables 1 and 2, among the sodium citrate 3Na · 2 hydrate, anhydrous sodium sulfate and the component (B), stirring of the sodium citrate 3Na · 2 hydrate was started. The mixing temperature until the final mixture was obtained was 25-40 ° C. The stirring time required for each step was 5 minutes.

<Evaluation>
Detergency, storage stability, and anti-dyeing property (finishing property) were evaluated by the following methods. The results are shown in Tables 1 and 2.

[1] Evaluation of detergency Four magnetic dishes were prepared by uniformly applying 2 g of egg yolk to a 7 cm radius of the central part on a magnetic dish (diameter 200 mm × height 30 mm) and then drying at 80 ° C. for 30 minutes. They are set in a one-door type commercial dishwasher (SANYO DW-230L type), solid bleach composition concentration 0.1% by mass, washing temperature 50 ° C., washing time 40 seconds, rinsing temperature 80 ° C. The rinsing time was 10 seconds. After taking out and drying at room temperature, the area of the model soil remaining on the magnetic dish was determined, and the ratio of the area before the test and the area after the test [[(area before test−area after test) / (area before test)] × 100] was used as the cleaning rate (%).

[2] Storage stability evaluation (2-1) Method 1
2kg of the solid bleaching agent composition is filled into a bag-like container (material: nylon / PET laminate film) and shape (flat bag, approx. 3L capacity), sealed and stored in a dryer adjusted to 50 ° C for 30 days. After that, the solid bleaching agent composition was diluted to 0.1% by mass, the effective chlorine concentration was measured, and the effective chlorine residual rate after storage was determined from the effective chlorine concentration before and after storage. This evaluation is an evaluation of storage stability assuming storage in the form of a pouched product. The effective chlorine concentration was determined by the following method.

100 ml of cleaning solution (composition concentration 0.1% by mass) is accurately weighed into 200 ml of beaker. Potassium iodide (10 mass% solution) and sulfuric acid (10 mass% solution) are added and mixed, and then titrated with a sodium thiosulfate 0.01 (mol / L) solution (0.049 g / drop). The point where the blue color disappeared was taken as the end point. From the obtained titer (ml), the effective chlorine concentration was determined by the following formula.
Effective chlorine concentration (ppm) = sodium thiosulfate 0.01 (mol / L) titration (ml) × 3.546

(2-2) Method 2
As in Method 1, except that a sodium thiosulfate 0.01 (mol / L) solution was titrated at 0.03 g / drop, the effective chlorine concentration was determined.

[3] Evaluation of prevention of pigment stain adhesion Poured tea “Assam 2.5 g / hot water (90 ° C. or higher): 110 g” was poured into two tempered glass cups (diameter 84 mm) and left for 10 seconds, and then the tea was discarded. The glass is the object to be cleaned.

Using a door-type commercial dishwasher (Sanyo Electric DW-230L type), the solid bleach composition concentration was 0.1% by weight, stored at 50 ° C for 30 days, cleaning temperature 50 ° C, cleaning time 40 seconds, rinsing Washing operation conditions were set at a temperature of 80 ° C. and a rinsing time of 10 seconds.

After repeating a series of operations of black tea immersion, black tea disposal, and washing 20 times, the tea astringent stain adhering to the tempered glass cup was visually judged in the following four stages to evaluate the pigment stain adhesion prevention property.

* Criteria 4 for preventing dye stain adhesion; no colored marks are observed.
3; Slight coloring marks are observed.
2; Clearly colored marks are observed.
1; Colored marks are observed inside the cup, and more adherent.

(Note) The components in the table are as follows.
・ Sodium dichloroisocyanurate dihydrate: Neochlor 55G [Shikoku Chemicals Co., Ltd.]
・ Sodium dichloroisocyanurate ・ Anhydride: Neochlor 60MG [Shikoku Kasei Kogyo Co., Ltd.]
Amorphous silica (1): Tocsil NR [Tokuyama Corporation, oil absorption capacity 250 ml / 100 g, average particle size 130 μm, specific surface area 195 (m ² / g)]
Amorphous silica (2) Fine seal F80 [Tokuyama Corporation, oil absorption capacity 275 ml / 100 g, average particle size 1.5 μm, specific surface area 295 (m ² / g)]
-Crystalline calcium silicate: Florite R [Tokuyama Corporation, oil absorption capacity 450 ml / 100 g, average particle size 25 μm, specific surface area 115 (m ² / g)]
・ Anhydrous sodium silicate: Musuimetakeisaw D [Guangei Chemical Industry Co., Ltd.]
・ Anhydrous sodium carbonate: Soda ash (light ash) [Central Glass Co., Ltd.]
・ Anhydrous potassium carbonate: Potassium carbonate [Asahi Glass Co., Ltd.]
・ Sodium silicate, pentahydrate: Dry metacaustic 5 aq [Guangei Chemical Industry Co., Ltd.]
Nonionic surfactant (1): R ^2d in the general formula (d-1) is a secondary alkyl group having 12 to 14 carbon atoms, s = 7.0, t = 8.5 nonionic surfactant [Product name: Softanol EP7085, Nippon Shokubai Co., Ltd.]
Nonionic surfactant (2): ethylene oxide adduct of nonylphenol (average number of moles added 5)
Nonionic surfactant (3): EO, PO, EO block polymer [trade name: Pluronic L-44 ADEKA Corporation]
Nonionic surfactant (4): PO / EO / PO block polymer [trade name: Pluronic RPE2520 (manufactured by BASF)]
-Aqueous solution of polymer compound (1): aqueous solution of a copolymer (weight average molecular weight 23000) of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 70/25/5) (aqueous solution having an effective content of 35% by mass, The amount of the aqueous solution is shown in the table.)
-Aqueous solution of high molecular compound (2): aqueous solution of a copolymer of diallyldimethylammonium chloride and acrylic acid (molar ratio 64/36) (weight average molecular weight 450,000, Merquat 280, manufactured by Calgon Corp.) (aqueous solution having an effective content of 40% by mass) In the table, the amount of the aqueous solution is shown.) ・ Citrate 3Na · Dihydrate: Purified sodium citrate M [Fuso Chemical Co., Ltd.]
・ Sodium tripolyphosphate: Sodium polyphosphate [Shimonoseki Mitsui Co., Ltd.]
・ Polyacrylic acid: Sokalan PA25CL Granules (manufactured by BASF) ・ Acrylic acid-maleic acid copolymer: Sokalan CP5 Granules (manufactured by BASF)
・ Anhydrous sodium sulfate: Neutral anhydrous bow glass [Shikoku Kasei Kogyo Co., Ltd.]

Claims

(A) 1.5 mass% or more and 5 mass% or less of sodium dichloroisocyanurate dihydrate, (B) It has 1 or more types of liquid support ability chosen from amorphous silica and crystalline calcium silicate. Powder, (C) anhydride of inorganic alkali metal salt, and (D) nonionic surfactant are blended in an amount of 0.5% by mass or more and 2.5% by mass or less, and the water content is 5% by mass or more. Solid bleach composition which is 10 mass% or less.
The solid bleaching composition according to claim 1, wherein (C) is at least one selected from (C1) an anhydride of an alkali metal silicate and (C2) an anhydride of an alkali metal carbonate.
(C) is one or more selected from (C1) an anhydride of an alkali metal silicate and (C2) one or more selected from an anhydride of an alkali metal carbonate, and the amount of (C1) and (C2 The mass ratio (C1) / (C2) of the blending amount is 10/90 or more and 50/50 or less.
The solid bleaching composition according to claim 2 or 3, wherein (C1) is anhydrous sodium silicate and (C2) is anhydrous sodium carbonate.
Further, (E) a polymer compound having a monomer unit (e1) derived from one or more monomers selected from a monomer having a quaternary ammonium group and a monomer having an amino group is blended. The solid bleaching agent composition of any one of these.
The component (D) is at least one nonionic surfactant selected from a nonionic surfactant represented by the following general formula (d-1) and a nonionic surfactant represented by the general formula (d-2 ′) The solid bleaching composition according to any one of claims 1 to 5, which is a surfactant.
R 1d —O— (EO) p — (PO) q — (EO) r —H (d−1)
[Wherein R 1d represents a hydrocarbon group having 8 to 18 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q, and r each represent an average added mole number, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, and r is 1 or more and 10 or less. “— (EO) p — (PO) q — (EO) r —” ”is a block bond. ]
R 2′d —O— (EO) s1 — (PO) t1 —H (d-2 ′)
[ Wherein R 2'd represents a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms, or a branched alkyl group or branched alkenyl group having 8 to 18 carbon atoms. EO represents an oxyethylene group and PO represents an oxypropylene group. s1 and t1 each represent an average added mole number, s1 is 4 or more and 10 or less, t1 is 2 or more and 10 or less, t1 / s1 is 0.3 or more and 1.5 or less, and s1 = 4˜ 10, t1 = 2 to 10, and 0.3 ≦ (t1 / s1) ≦ 1.5. “— (EO) s1 — (PO) t1 —” is a block bond. ]
The solid bleaching composition according to any one of claims 1 to 6, wherein a mass ratio (A) / (D) of the blending amount of (A) and the blending amount of (D) is 0.6 or more and 5 or less. .
The solid bleaching composition according to any one of claims 1 to 7, wherein a mass ratio (A) / (B) of the blending amount of (A) to the blending amount of (B) is 0.3 or more and 5 or less. .
The solid bleaching composition according to any one of claims 1 to 10, wherein a mass ratio (C) / (D) of the blending amount of (C) and the blending amount of (D) is 5 or more and 60 or less.
The solid bleaching composition according to any one of claims 5 to 9, wherein (E) has a monomer unit (e2) represented by -SO 2- .
The solid bleaching composition according to claim 10, wherein the molar ratio of monomer unit (e2) / monomer unit (e1) is 0.01 or more and 1 or less.
The solid bleaching composition according to any one of claims 5 to 11, wherein a mass ratio (A) / (E) of the blending amount of (A) and the blending amount of (E) is 1 or more and 10 or less.
The solid bleaching composition according to any one of claims 5 to 12, wherein the sum of the blending amount of (D) and the blending amount of (E) is 0.6 mass% or more and 3 mass% or less.
(A) 1.5 mass% or more and 5 mass% or less of sodium dichloroisocyanurate dihydrate, (B) It has 1 or more types of liquid support ability chosen from amorphous silica and crystalline calcium silicate. Powder, (C) an inorganic alkali metal salt anhydride, and (D) a nonionic surfactant in an amount of 0.5% by mass to 2.5% by mass and a water content of 5% by mass to 10%. The solid bleaching composition which is the mass% or less.
The solid bleaching composition according to any one of claims 1 to 14, wherein the content of sodium tripolyphosphate is 0% by mass or more and less than 20% by mass.
Use for using the solid bleaching composition according to any one of claims 1 to 15 for washing dishes. *