JP5783760B2 - Bleaching composition - Google Patents

Description

  The present invention relates to a bleaching composition.

In general, bleaching compositions (bleaching detergents, bleaching agents, etc.) in which substances having a bleaching effect (bleaching components) are blended are used for washing and bleaching of textile products such as clothing. The bleaching effect of the bleaching composition is exerted by the oxidation reaction of the bleaching component. As the bleaching component, a hydrogen peroxide-based compound (hydrogen peroxide, peroxide that dissolves in water to generate hydrogen peroxide, etc.) In addition, chlorinated compounds (such as sodium hypochlorite) are used. Among them, since the handling is easy, those using a hydrogen peroxide compound as a bleaching component have attracted attention.
Hydrogen peroxide compounds have a feature that they can be used for colored products, but have a problem that they are inferior to chlorine compounds in terms of bleaching power.

In order to solve these problems, organic peracid precursors and metal complexes that enhance the bleaching power of hydrogen peroxide compounds have been studied.
For example, a chelating agent having a coordination site of 5 or less and / or an anion generated from the chelating agent and a bleaching oxidation assistant containing a copper and / or manganese compound have been proposed (for example, Patent Document 1). . According to the invention of Patent Document 1, bleaching power is improved by promoting oxidation by a hydrogen peroxide-based compound.

WO09 / 0748459 pamphlet

However, the bleaching composition is required to further improve the bleaching effect, and in particular, it is desired to finish white fiber products whiter (whiteness improving effect).
Then, this invention aims at the bleaching composition which can finish textiles whiter.

As a result of intensive studies, the inventors have found that by combining a specific fluorescent agent, a specific long-chain alkylamine, and a specific surfactant, the whiteness of the fiber product can be dramatically improved. The present invention has been reached.

That is, the bleaching composition of the present invention is selected from the group consisting of component (A): a water-soluble salt of a transition element, a water-soluble salt of zinc, or a water-soluble salt of silver in the fourth period of the periodic table. More than one kind of water-soluble metal salt, component (B): a compound represented by formula (I) or (II) described later, and component (C): hydrogen peroxide or peroxidation that generates hydrogen peroxide in water And (D) component: non-soap anionic surfactant and (E) component: biphenyl type fluorescent agent, and the mass ratio represented by (B) component / (E) component is 1. It is characterized by being 2 or more.
Furthermore, it is preferable to contain (F) component: carboxymethylcellulose or its salt.

  According to the bleaching composition of the present invention, the textile product can be made whiter.

(Bleachable composition)
The bleaching composition of the present invention is one or more selected from the group consisting of component (A): a water-soluble salt of a transition element in the fourth period of the periodic table, a water-soluble salt of zinc, or a water-soluble salt of silver. (B) component: long-chain alkylamine compound, (C) component: hydrogen peroxide or a peroxide that generates hydrogen peroxide in water, and (D) component: non-soap anion interface It contains an activator and (E) component: biphenyl type fluorescent agent.
In this article, the bleaching composition includes a bleaching detergent and a bleaching agent. A bleaching agent is a composition that mainly focuses on the bleaching of textile products (laundry) to be treated and emphasizes bleaching power. A bleaching detergent is mainly intended for washing laundry. However, the bleaching power is inferior to that of the bleaching agent, but the composition emphasizes detergency.

 The dosage form of a bleaching composition is not specifically limited, For example, solids, such as a granular form, a tablet, a briquette, a sheet | seat, a bar, etc. may be sufficient.

 When the bleaching composition is solid, the moisture content is preferably 8% by mass or less. If it is 8 mass% or less, the stability of (C) component mentioned later will increase.

 When making a bleaching composition into a granular form, it is preferable that the average particle diameter of a granular material is 200-1500 micrometers, for example, and it is more preferable that it is 250-1000 micrometers. If the average particle diameter is 200 μm or more, powdering during use is suppressed. On the other hand, if it is 1500 micrometers or less, the solubility to water will improve.

The average particle size in this article is a value determined by the following measurement method.
The average particle diameter can be measured by a classification operation using a 9-stage sieve having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked in order on a tray, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, a lid is put on, and a low-tap sieve shaker (stock) (Made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute) and vibrating for 10 minutes. Thereafter, the sample remaining on each sieve and the tray is collected for each sieve, and the mass of the sample is measured. Then, the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “b μm”. To do. In addition, the integrated value of the mass frequency from the tray to the a μm sieve is “c%”, and the mass frequency on the a μm sieve is “d%”. And an average particle diameter (50 mass% particle diameter) is calculated | required by following (1) Formula, and let this be an average particle diameter of a sample.

The pH of the solid bleaching composition is not particularly limited, but from the viewpoint of washing performance, the pH in a 1% by weight aqueous solution of the bleaching composition is preferably 8 or more, and the 1% by weight The pH in the aqueous solution is more preferably 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
In addition, pH (25 degreeC) of a bleaching composition shows the value measured with a pH meter (HM-30G, Toa DKK Corporation) etc.

When making a bleaching composition into a liquid, it is preferable that a viscosity (25 degreeC) is 10-300 mPa * s. When the viscosity is within the above range, the handling when measuring the bleaching composition is good.
The viscosity of the bleaching composition indicates a value (measurement condition: rotor No. 2, rotation speed 30 rpm, viscosity after 10 rotations) measured by a B-type viscometer (manufactured by TOKIMEC).

  The pH of the liquid bleaching composition is preferably 2-7. If pH is in the said range, the storage stability of a bleaching composition can be maintained favorable. When pH exceeds 7, decomposition | disassembly of each component (especially (C) component) may occur, and it may become difficult to fully obtain the effect of the present invention.

<(A) component: water-soluble metal salt>
The component (A) is at least one water-soluble metal salt selected from the group consisting of a water-soluble salt of a transition element, a water-soluble zinc salt, or a water-soluble silver salt in the fourth period of the periodic table. By containing (A) component, the bleaching composition accelerates | stimulates the oxidation reaction by (C) component mentioned later, and the improvement of a whiteness improvement effect is aimed at.

 (A) Although the metal which comprises a component will not be specifically limited if it is any of the transition elements in the 4th period of a periodic table, zinc, and silver, While increasing the whiteness of a textile product and raising a cleaning power, Copper, zinc and silver are preferred.

 Examples of the water-soluble salt constituting the component (A) include sulfate, nitrate, chloride, acetate, perchlorate, cyanide, ammonium salt, gluconate, tartrate, citrate and the like. In view of particularly good solubility in a solvent such as water, sulfates and chlorides are preferable, and sulfates are more preferable.

Examples of such component (A) include water-soluble substances such as copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper chloride ammonium, copper gluconate, copper tartrate, copper perchlorate and the like. Copper salts, zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc chloride ammonium, zinc gluconate, zinc tartrate, zinc perchlorate, and other water-soluble zinc salts, silver sulfate, silver nitrate, acetic acid Examples thereof include water-soluble silver salts such as silver, silver fluoride, and silver perchlorate.
These (A) components can be used individually by 1 type or in combination of 2 or more types.

 Although the particle diameter of (A) component is not specifically limited, When a bleaching composition is a granular material, it is preferable that it is 300 micrometers or less in particle diameter.

 The content of the component (A) in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, the type of the component (A), etc., for example, as a metal ion in the bleaching composition. 0.001-0.5 mass% is preferable, 0.01-0.3 mass% is more preferable, and 0.02-0.1 mass% is further more preferable. Further, when a water-soluble zinc salt is used as the component (A), the content of the water-soluble zinc salt in the bleaching composition is preferably 0.002 to 2% by mass, preferably 0.02 to 1% by mass as zinc ions. Is more preferable, and 0.05-0.5 mass% is preferable. If the content of the component (A) in the bleaching composition is less than the above lower limit value, it is difficult to obtain a sufficient whiteness improvement effect, and even if the content exceeds the upper limit value, further improvement in whiteness improvement effect is obtained. Hateful.

<(B) component>
The component (B) is a long chain alkylamine compound. The bleaching composition contains the component (B), thereby forming a complex of the component (A) and the component (B) during the washing process or the bleaching process. It remains in the product and exhibits a good whiteness improvement effect.
Examples of the component (B) include compounds represented by the following formula (I) or (II). Among these, from the viewpoint of further enhancing the whiteness improving effect, the compound represented by the formula (II) is preferable as the component (B).

(In the formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents a hydrogen atom or (CH ₂ ) _m1 -COOX ^2. X ¹ and X ² each represent 1 independently represents one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group, n1 is a number from 1 to 3, and m1 is any one of 1 to 3 Number.)

(In the above formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m2 ), and r is 1 or 0. When r is 0, A ² and A ³ are each independently selected from a hydrogen atom and a methyl group, and when r is 1, either A ² or A ³ One is a hydrogen atom and the other is either a hydrogen atom or CH ₂ COOX ^3. X ³ is selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. N2 is a number from 1 to 3, and m2 is a number from 1 to 3.

In the formula (I), the alkyl group represented by R ¹ has 8 to 22 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, and still more preferably 12 to 14 carbon atoms. If the number of carbon atoms is not less than the above lower limit value, dirt is easily adsorbed, and if it is not more than the above upper limit value, the component (B) can be easily dissolved in water and the whiteness improving effect can be sufficiently exhibited. In particular, when R ¹ is an alkyl group having 12 to 14 carbon atoms, the balance between hydrophobicity (that is, adsorption to dirt) and hydrophilicity (that is, solubility in water) is good, and whiteness is improved. The effect can be further enhanced.

In the formula (I), in X ¹ , examples of the alkali metal atom include sodium and potassium, examples of the alkaline earth metal atom include magnesium and calcium, and examples of the cationic ammonium group include trimethylammonium. And tetramethylammonium.

 In the formula (I), n1 is 1 to 3. When n is within the above range, the complex formed by the component (A) and the component (B) is stabilized and the whiteness improving effect can be further enhanced.

In the formula (I), ^{X 2} is the same as ^{X 1,} m1 is the same as n1.

  Examples of the compound represented by the formula (I) include compounds represented by the following formula (I-1) or (I-2).

(In the above (I-1) formula, ^{R 1} is the same as ^{R 1} of formula ^(I), X 1, ^{X 2} is the same as ^X 1, ^{X 2,} respectively formula (I), n1 is ( I) It is the same as n1 in the formula, and m1 is the same as m1 in the formula (I).)

(In the above (I-2) expression, ^{R 1} is the same as ^{R 1} of formula (I), ^{X 1} is the same as ^{X 1} in formula (I), n1 is the same as n1 of formula (I) .)

  Examples of the compound represented by the formula (I-1) include sodium octyliminodiacetate, sodium lauryliminodiacetate, sodium myristyliminodiacetate, sodium palmitateiminodiacetate and the like, octyliminodipropion Examples thereof include alkyliminodipropionates such as sodium acid, sodium lauryliminodipropionate, sodium myristyliminodipropionate, and sodium palmitate iminodipropionate.

  Examples of the compound represented by the formula (I-2) include sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate and the like. Can be mentioned. Of these, alkyliminodiacetate is preferred in view of the stability of the complex.

In the formula (II), R ² is any of an alkyl group having 8 to 22 carbon atoms and an acyl group having 8 to 22 carbon atoms. The carbon number of R ² is preferably 8 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, and still more preferably 12 to 14 carbon atoms. If the number of carbon atoms of the alkyl group or acyl group is not less than the above lower limit value, dirt is easily adsorbed, and if it is not more than the above upper limit value, the component (B) can be easily dissolved in water, and the whiteness improvement effect is sufficient. Can demonstrate. In particular, when R ² is an alkyl group or acyl group having 12 to 14 carbon atoms, the balance between hydrophobicity and hydrophilicity is good, and the whiteness improving effect can be further enhanced.
Q is (NH— (CH ₂ ) _m2 ), and r is 1 or 0 (single bond). If r is 1 or less, the complex of (A) component and (B) component will be stabilized in the washing | cleaning process or a bleaching process, and the whiteness improvement effect will be heightened more.
When r is 0 (single bond), A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group.
On the other hand, when r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . At this time, X ³ is the same as X ¹ in the formula (I).
n2 is the same as n1 in the formula (I), and m2 is the same as m1 in the formula (I).

  Examples of the compound represented by the formula (II) include compounds represented by the following formula (II-1) or (II-2).

(In the above (II-1) formula, ^{R 2} is the same as ^{R 2} of formula ^(II), A 2, ^{A 3} is the same as ^A 2, ^{A 3,} respectively formula (II), n2 is ( II) Same as n2 in formula.)

(In the formula (II-2), R ² is the same as R ^{2 in the} formula (I), A ² is the same as A ^{2 in the} formula (II), and n ² is the same as n ^{2 in the} formula (II). And m2 is the same as m2 in the formula (II).)

Examples of the compound represented by the formula (II-1) include cocoalkylpropylenediamine, beef tallow alkylpropylenediamine, laurylethylenediamine, myristylethylenediamine, palmitylethylenediamine, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid. Examples include dimethylaminopropylamide.
Examples of the compound represented by the formula (II-2) include lauryl diethylene triamine, myristyl diethylene triamine, palmityl diethylene triamine, lauryl dipropylene triamine, myristyl dipropylene triamine, palmityl dipropylene triamine, and alkyldiaminoethyl glycine.
Of these, alkyldiaminoethylglycine is preferred in view of the stability of the complex.
These (B) components can be used individually by 1 type or in combination of 2 or more types.

 The content of the component (B) in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, the type and amount of the component (A), for example, 0.01 to 1% by mass Is preferable, 0.05-0.8 mass% is more preferable, and 0.1-0.5 mass% is further more preferable. If the content of the component (B) is not less than the above lower limit value, it is easy to form a complex with the component (A), and if it is not more than the above upper limit value, it is difficult to damage the fiber product and is unique to the component (B). The odor of can be suppressed.

<(C) component>
Component (C) is hydrogen peroxide or a peroxide that generates hydrogen peroxide in water. A bleaching composition can exhibit the bleaching effect by containing (C) component.

Examples of the component (C) include peroxides such as sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, hydrogen peroxide, etc. Among them, as the peroxide, Sodium percarbonate is preferred from the standpoint of solubility during use and stability during storage.
These (C) components can be used singly or in appropriate combination of two or more.

 When the bleaching composition is solid, a peroxide is used as the component (C). In the bleaching composition, the peroxide may be blended as it is, or coated particles in which the peroxide particles are coated (for example, coated particles such as coated sodium percarbonate particles) may be blended. . By using the coated particles, stability during storage can be improved.

 As the coated particles, known particles can be used. For example, the coated sodium percarbonate particles are coated with silicic acid and / or silicate and boric acid and / or borate, or a combination of a surfactant such as LAS and an inorganic compound. Are preferred. Specifically, as described in Japanese Patent No. 2,189,991 and the like, it is coated by spraying silicic acid and / or alkali metal silicate aqueous solution and boric acid and / or alkali metal borate aqueous solution. And those coated with an aromatic hydrocarbon sulfonic acid and / or an alkali silicate alkali salt, carbonate, bicarbonate and sulfate having an average particle size of 10 to 500 μ, such as paraffin No. 2871298, paraffin, wax, etc. Examples thereof include those coated with a water-insoluble organic compound. For non-hazardous material, it may be used by powder blending with various inorganic materials such as sodium carbonate and sodium hydrogen carbonate.

 When the water content of the bleaching composition is high, coated peroxides coated with sodium percarbonate and silicic acid and sodium borate, aromatic hydrocarbon sulfonic acids and alkali silicates, carbonates, bicarbonates and sulfuric acids It is more preferable to use a salt-coated one.

 As coated sodium percarbonate particles, JP-A-59-196399, USP4526698 (both sodium percarbonate coated with borate), JP-A-4-31498, JP-A-6-40709 And those produced by the methods described in JP-A-7-118033 and Japanese Patent No. 2871298.

 (C) When mix | blending a component with a bleaching composition as particle | grains (peroxide particle | grains or covering particle | grains), 200-1000 micrometers is preferable and, as for the average particle diameter of this particle | grain, 500-1000 micrometers is more preferable. Moreover, in order to improve solubility and stability, it is preferable that the particles having a particle size of less than 125 μm and particles having a particle size of more than 1400 μm are 10% by mass or less in the component (C).

 When the bleaching composition is a liquid, either hydrogen peroxide or peroxide may be used as the component (C).

 Content of (C) component in a bleaching composition can be determined in consideration of the use and dosage form of a bleaching composition, and the kind of (C) component, for example, 1-30 mass is preferable, 2-20 The mass% is more preferable, and 3 to 15 mass% is further more preferable. When the content of the component (C) is less than the lower limit, the whiteness improvement effect may be insufficient, and even if the content exceeds the upper limit, a further whiteness improvement effect may not be obtained.

<(D) component>
Component (D) is a non-soap anionic surfactant, that is, an anionic surfactant not classified as soap. When the bleaching composition contains the component (D), the function of dissolving or dispersing the soil in the washing liquid is enhanced, the permeability to the textile is improved, and the whiteness improving effect is exhibited.

Examples of the component (D) include the following anionic surfactants.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(11) C14-18 fatty acid methyl ester sulfonate (MES).
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts.
These (D) components can be used singly or in appropriate combination of two or more.

  In addition, (D) is not limited to said anionic surfactant, In addition, a well-known non-soap anionic surfactant can be used suitably, and any one of these is independent, or 2 or more types Can be used in appropriate combination.

In a solid bleaching composition, particularly a granular bleaching composition, the component (D) is preferably blended as surfactant-containing particles.
Suitable surfactant-containing particles include surfactant-containing particles (anionic surfactant-containing particles) having an anionic surfactant as a main surfactant, and surfactants having a nonionic surfactant as a main surfactant. And contained particles (nonionic surfactant-containing particles). Any one of these surfactant-containing particles may be used, or they may be used in combination.

≪Anion-containing activator particles≫
Anionic surfactant-containing particles are particles in which an anionic surfactant is an essential component and the anionic surfactant content is the largest among the surfactants blended in the anionic surfactant-containing particles. Means.

 Examples of the anionic surfactant blended in the anionic surfactant-containing particles include the component (D) described above. The anionic surfactant blended in the anionic surfactant-containing particles may be one type or two or more types.

 The anionic surfactant-containing particles can contain other surfactants (nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.) other than anionic surfactants, although their contents are limited. is there.

 When the bleaching composition contains a surfactant other than the component (D), the total amount of the anionic surfactant and the nonionic surfactant in the bleaching composition is 50% by mass or more of the total surfactant. It is preferably 80% by mass or more, and more preferably 95% by mass or more. If it is less than the lower limit, the whiteness improving effect may be reduced.

The content of all the surfactants in the anionic surfactant-containing particles is determined in consideration of the cleaning performance desired for the bleaching composition, and is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, for example. %, More preferably 15 to 50% by mass. If it is the above-mentioned range, sufficient cleaning effect can be exhibited.
Further, in the anionic surfactant-containing particles, the mass ratio of the anionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 55/45, and 95/5 to 70. / 30 is more preferable.

The anion-containing surfactant particles may contain components other than the surfactant.
Examples of other components that may be contained in the anionic surfactant-containing particles include components described in <Optional Components> described below. Among these, an inorganic or organic detergency builder is preferable, and an inorganic builder is particularly preferable.

 As the inorganic builder, potassium salts such as potassium carbonate and potassium sulfate, and alkali metal chlorides such as potassium chloride and sodium chloride are preferable because they have the effect of improving solubility. Among them, potassium carbonate, alkali metal chlorides such as potassium chloride and sodium chloride are preferable from the viewpoint of the balance between the effect of improving solubility and cost.

 When potassium carbonate is blended, the content thereof is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 3 to 3% in the anionic surfactant-containing particles from the viewpoint of improving the solubility. 10% by mass.

 When blending an alkali metal chloride, the content is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, more preferably 2% by mass in the anion-containing surfactant-containing particles from the viewpoint of improving the solubility. It is 3-7 mass%.

The physical property value of the anionic surfactant-containing particles is not particularly limited, but for example, the bulk density is usually preferably 0.3 g / cm ³ or more, and preferably 0.5 to 1.2 g / cm ^3. More preferably, it is 0.6-1.1 g / cm < ³ >.
The bulk density is a value measured according to JIS-K3362.

 The average particle size (50% by mass particle size) of the anionic surfactant-containing particles is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. If the average particle size (50% by mass particle size) is less than 200 μm, dust may be easily generated, while if it exceeds 1500 μm, the solubility may be insufficient.

The fluidity of the anionic surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as the angle of repose. If the angle of repose exceeds 60 °, the handleability of the particles may deteriorate.
The angle of repose can be measured by a so-called angle-of-rest angle of repose measuring method that measures the angle formed by the horizontal surface of the slip surface formed when particles filled in the container flow out (the same applies hereinafter).

The anionic surfactant-containing particles can be obtained by a known method, for example, by the following method (1) or (2).
Method (1): A method of granulating a neutralized salt type anionic surfactant.
Method (2): A method in which an acid precursor of an anionic surfactant is dry neutralized and granulated.
Examples of the granulation method used in method (1) include the following methods (1-1) to (1-5).

(1-1) An extrusion granulation method in which a raw material powder of a surfactant and a binder compound (surfactant, water, polymers, etc.) are kneaded and kneaded, and then extruded and granulated.
(1-2) A kneading and crushing granulation method in which a raw material powder of a surfactant and a binder compound are kneaded and kneaded to obtain a solid detergent, and the resulting solid detergent is crushed and granulated.
(1-3) A stirring granulation method in which a binder compound is added to a raw material powder of a surfactant and stirred with a stirring blade for granulation.
(1-4) A rolling granulation method in which a binder compound is sprayed and granulated while rolling a raw material powder of a surfactant.
(1-5) A fluidized bed granulation method in which a raw material powder of a surfactant is fluidized and a liquid binder is sprayed and granulated.

In the method (2), the acid precursor of the anionic surfactant and the alkaline inorganic powder are neutralized while being contacted and mixed, and granulated. As the granulation method, the same granulation method as the granulation method mentioned in the method (1) can be used.
As the acid precursor of the anionic surfactant, any acid precursor can be suitably used as long as it is the acid precursor of the anionic surfactant described above.

Moreover, although it does not specifically limit as alkaline inorganic powder as a neutralizing agent, An alkali metal carbonate, an alkali metal silicate, an alkali metal phosphate, etc. are mentioned.
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate / potassium carbonate and the like. Examples of the alkali metal silicate include sodium silicate and layered sodium silicate. Examples of the alkali metal phosphate include sodium tripolyphosphate and sodium pyrophosphate. Among these, alkali metal carbonates are preferable, and sodium carbonate, potassium carbonate, and sodium carbonate / potassium are more preferable. These neutralizing agents can be used singly or in appropriate combination of two or more.

 The anion-containing surfactant particles granulated by the above-described method can be classified as necessary, and only the anion-containing surfactant-containing particles having a desired particle size can be used in products.

[Nonionic surfactant particles]
Nonionic surfactant particles include nonionic surfactant, which will be described later, as an essential component, and the content of nonionic surfactant is the largest among the surfactants blended in the nonionic surfactant particles. Means particles.

 The nonionic surfactant blended in the nonionic surfactant-containing particles is not particularly limited, and the above-described various nonionic surfactants can be used. The nonionic surfactant blended in the nonionic surfactant-containing particles may be one type or two or more types.

 Nonionic surfactant particles can contain other surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, etc.) other than nonionic surfactants, although their content is limited. is there.

The content of all the surfactants in the nonionic surfactant-containing particles can be determined in consideration of the cleaning performance desired for the composition. For example, the content is preferably 5 to 85% by mass, more preferably 10 to 10% by mass. 60% by mass. If it is the above-mentioned range, sufficient cleaning effect can be exhibited.
Further, in the nonionic surfactant particles, the mass ratio of nonionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 60/40, and 95/5 to 70. / 30 is more preferable.
In addition, when an anionic surfactant is not mix | blended in the nonionic surfactant particle | grains to contain, the anionic surfactant containing (D) component or (D) component will be mix | blended independently in a bleaching composition. .

The nonionic surfactant-containing particles may contain components other than the surfactant. The other components are not particularly limited, and for example, those mentioned as other components other than the surfactant in the description of the anionic surfactant-containing surfactant particles can be appropriately blended.
Among them, an inorganic or organic cleaning builder can be mentioned as a component that is suitably blended in the nonionic surfactant particles. As the cleaning builder, a cleaning builder that can be blended with the anionic surfactant-containing particles described above can be similarly used. The same applies to the content of suitable cleaning builder and cleaning builder.

Moreover, it is preferable to mix | blend the oil-absorbing support | carrier for carry | supporting a nonionic surfactant in nonionic surfactant particle | grains.
The oil-absorbing carriers, JIS-K5101 oil absorption is preferably represented by the Test Method 80 cm ^3/100 g or more, more preferably oil of 150~600cm ³ / 100g material is preferably used. Examples of such an oil-absorbing carrier include components described in JP-A-5-125400 and JP-A-5-209200. These oil-absorbing carriers can be used alone or in combination of two or more.

The oil-absorbing carrier is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass.
Moreover, it is preferable to mix | blend the clay mineral etc. as a granulation adjuvant in nonionic surfactant particle | grains.

As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are particularly preferable. Clay minerals that can be used as a detergent component of the present invention is preferably less than oil absorption of 80 cm ^3/100 g, more preferably at 30~70cm ³ / 100g, bulk density is preferably 0.1 g / cm ³ or more, more preferably 0.2 to 1.5 g / cm ³ . Specific examples of such clay minerals include components described in JP-A-9-87691.
The clay mineral is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass.

The physical property value of the nonionic surfactant-containing particles is not particularly limited. For example, the bulk density is usually preferably 0.3 g / cm ³ or more, and preferably 0.5 to 1.2 g / cm ^3. More preferably, it is 0.6-1.1 g / cm < ³ >. Moreover, the average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. If the average particle size is less than 200 μm, dust may be easily generated, while if it exceeds 1500 μm, the solubility may be insufficient.
Further, the fluidity of the nonionic surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

The nonionic surfactant-containing particles can be obtained by the same granulation method as the anionic surfactant-containing particles.
The obtained nonionic surfactant particles can be classified as necessary, and only nonionic surfactant-containing particles having a desired particle size can be used in products.

 The bleaching composition may contain only the anion-containing surfactant particles containing the component (D) or the nonionic surfactant particles containing the component (D), or the anion-containing product not containing the component (D). The surfactant particles and the nonionic surfactant particles containing the component (D) may be combined in combination, or the anionic surfactant particles containing the component (D) and the nonionic surfactant containing no component (D). You may mix | blend in combination with surfactant particle | grains.

The content of the component (D) in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition. 5-80 mass% is preferable, for example, content of (D) component in a solid bleaching composition is more preferable, 8-40 mass% is more preferable, and 10-30 mass% is further more preferable. If the content of the component (D) is less than the above lower limit, the whiteness improving effect may be insufficient, and if it exceeds the upper limit, the content of other components is relatively reduced, and the present invention. There is a possibility that the effect of is not sufficiently obtained.
The content of the component (D) in the liquid bleaching composition is, for example, preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and further preferably 3 to 7% by mass. If it is less than the lower limit, the whiteness improving effect may be insufficient, and if it exceeds the upper limit, stability at low temperatures may be reduced.

  The mass ratio (D / B ratio) represented by (D) component / (B) component is preferably 1 or more, and more preferably 5 or more. When the bleaching composition is in a granular form, if it is less than 1, the component (B) is relatively increased with respect to the component (D) and tends to solidify.

<(E) component>
The component (E) is a biphenyl type fluorescent agent. A bleaching composition can exhibit the high whiteness improvement effect by containing (E) component. Examples of the component (E) include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- ( And styrylphenyl) naphthothiazole derivatives. Examples of such component (E) include Chino Pearl CBS-X (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).
These (E) components can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (E) in the bleaching composition can be determined in consideration of the use of the bleaching composition, the type of the component (E), and the like. For example, 0.001% by mass to 1% by mass is preferable. . When the content of the component (E) is less than the lower limit, the whiteness improvement effect may be insufficient, and even if the content exceeds the upper limit, further improvement in whiteness may not be expected.

 The mass ratio (B / E ratio) represented by (B) component / (E) component is 1.2 or more, preferably 1.2 to 500, and more preferably 3 to 250. When the B / E ratio is less than the above lower limit, the component (B) is relatively reduced, and the composite of the component (A), the component (B), the component (D), and the component (E) The adsorbing rate is reduced, and the whiteness improvement effect cannot be sufficiently obtained. If it exceeds the above upper limit value, the (E) component is relatively decreased, and the adsorption rate of the composite of the (A) component, the (B) component, the (D) component, and the (E) component to clothing is reduced. However, the whiteness improvement effect cannot be obtained sufficiently. In addition, if it exceeds the above upper limit value, the bleaching composition may be easily solidified when it is powdered.

<(F) component>
The bleaching composition of the present invention can contain (F) component: carboxymethyl cellulose or a salt thereof in addition to the components (A) to (E). The bleaching composition can further enhance the whiteness improving effect by containing the component (F).

 As the component (F), for example, an anionic water-soluble / water-insoluble cellulose ether obtained by reacting monochloroacetic acid after treating pulp with caustic soda as cellulose as a raw material is preferably exemplified. Examples of the component (F) include compounds having a repeating unit represented by the following formula (i).

[(I) In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom, a carboxymethyl group (CH ₂ COOH) or a salt thereof (CH ₂ COOZ), Z represents a counter ion, and p represents a repeating group. Represents the number of repeating units. ]

(I) In the formula, in R ^{3 to} R ⁵ , Z is a counter ion, and examples of Z include metal ions and ammonium ions. Examples of metal ions include alkali metal ions such as sodium ions and potassium ions. Among these, as Z, a metal ion is preferable, an alkali metal ion is more preferable, and a sodium ion is more preferable. That is, the component (F) is preferably carboxymethylcellulose sodium salt. This is because carboxymethylcellulose sodium salt has better solubility in water.

  The weight average molecular weight of the component (F) is preferably 100,000 or more, more preferably 300,000 or more, further preferably 500,000 or more, particularly preferably 600,000 or more, and most preferably 800,000 or more. As an upper limit of the weight average molecular weight of (F) component, 1.2 million or less is preferable, for example, and 1 million or less is more preferable. If the weight average molecular weight of (F) component is more than the said lower limit, the recontamination prevention effect can be improved notably, and if it is below the said upper limit, solubility will become favorable.

In the present invention, the weight average molecular weight of the component (F) can be measured by gel filtration chromatography (GPC) -differential refractive index detector (RI) system. Eluent: 0.1 M NaNO ₃ , Flow rate: 1 cm ³ / min, sample: 0.02 to 0.3% by mass (solvent; 0.1 M NaNO ₃ ), injection amount: 200 mm ³ , the weight average molecular weight was calculated as a numerical value in terms of PEG. Mean value. For the measurement of the weight average molecular weight, for example, liquid feed pump: Shodex DS-4 (manufactured by Showa Denko KK), degasser: ERC3115 (manufactured by ERC), column: Shodex SB-806MHQ (manufactured by Showa Denko KK), differential Refractive index detector: Shodex RI-71 (manufactured by Showa Denko KK) and the like can be used.

The degree of etherification of the component (F) is preferably 0.2 to 1.3, more preferably 0.2 to 0.8. If the degree of etherification is within the above range, the effect of preventing recontamination can be improved.
In the present invention, the degree of etherification refers to the number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit constituting cellulose (of R ^{3 to} R ⁵ in the above (i), carboxy Mean number of methyl groups (CH ₂ COOH) or a salt thereof). That is, it indicates how many of the three hydroxyl groups of the glucose ring are substituted with a carboxymethyl group or a salt thereof, and is a maximum of three.

As the component (F), for example, 1110, 11, 20, 1130, 1140, 1160, 1170, 1180, 1190, 1220, 12, 40, sold under the trade name “CMC Daicel” from Daicel Chemical Industries, Ltd. 1260, 1280, 1290, 1380, 2200, 2260, 2280, 24, 50, 2340, etc. F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, sold under the trade name “Sunrose” from Nippon Paper Chemical Co., Ltd. F1400MC, F1400MG, etc., Sunrose F series, SLD-F1 (named above), F-BSH-6, F-6HS9, etc. sold under the trade name “Serogen” by Daiichi Kogyo Seiyaku Co., Ltd. . Among the above, CMC Daicel 1130, 1140, 1180, 1190, 1280, Sunrose F1400LC, F1400MC, Sunrose SLD-F1, and Serogen F-6HS9 are particularly preferable.
These (F) components can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the component (F) in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, and is preferably 0.1 to 5% by mass, for example, 0.2 to 5% by mass. % Is more preferable, and 0.3 to 3% by mass is more preferable. If it is less than the above lower limit value, the whiteness improving effect may not be further improved, and even if it exceeds the above upper limit value, the improvement in whiteness improving effect is saturated, which may cause an economic disadvantage.
Further, from the viewpoint of further enhancing the whiteness improving effect, the mass ratio (F / E ratio) represented by the (F) component / (E) component is preferably 10 or more, and more preferably 20 or more. Although the upper limit of F / E ratio is not specifically limited, 100 or less is preferable. Even if the F / E ratio exceeds 100, the improvement in whiteness improvement effect is saturated, which may cause an economic disadvantage.

<Optional component>
The bleaching composition of this invention may contain arbitrary components other than the said component (A)-(F) in the range which does not impair the effect of this invention. The optional component is not particularly limited, and various additives conventionally blended in bleaching agents, bleaching detergents, and the like can be blended. Examples of optional components include surfactants other than (D) component (optional surfactants), fluorescent agents other than (E) component (optional fluorescent agents), fragrances, organic peracid precursors, detergency builders, and dyes. , Enzymes, enzyme stabilizers, polymers other than the component (F) (arbitrary polymers), anti-caking agents, antifoaming agents, reducing agents, metal ion scavengers, pH adjusters and the like.

[Optional surfactant]
The bleaching composition can contain a surfactant (optional surfactant) other than the component (D) as necessary.

≪Nonionic surfactant≫
The nonionic surfactant is not particularly limited as long as it is conventionally used for a cleaning agent, and various nonionic surfactants can be used. A nonionic surfactant may be mix | blended independently in a bleaching composition, and may be mix | blended with the anionic surfactant-containing particle | grains or nonionic surfactant-containing particle | grains mentioned above.

Examples of nonionic surfactants include the following.
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, and more preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the following formula (31).
R ⁹ CO (OA) qOR ¹⁰ (31)
In the above formula (31), R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and ethylene oxide, propylene oxide and the like are preferable.
q shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is 5-20.
R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.

Among the above nonionic surfactants, the nonionic surfactant (1) is preferable, and in particular, polyoxyalkylene obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms. Alkyl ethers or polyoxyalkylene alkenyl ethers are particularly preferred.
Further, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB value of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester obtained by adding ethylene oxide to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
The HLB of the nonionic surfactant is a value obtained by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho, 1991, No. 234). Page).
The melting point is a value measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test methods”.
These nonionic surfactants may be used singly or in appropriate combination of two or more.

≪Cationic surfactant≫
The cationic surfactant is not particularly limited as long as it is conventionally used in a cleaning agent, and various cationic surfactants can be used.
Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
“Long chain alkyl” in (1) to (3) represents an alkyl group having 12 to 26 carbon atoms. The alkyl group preferably has 14 to 18 carbon atoms.

  “Short-chain alkyl” refers to an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkyl group preferably has 1 or 2 carbon atoms. Examples of the substituent that the alkyl group may have include a phenyl group, a benzyl group, a hydroxyl group, a hydroxyalkyl group, and a polyoxyalkylene group. 2-4 are preferable and, as for carbon number of a hydroxyalkyl group, 2 or 3 is more preferable. 2-4 are preferable and, as for carbon number of the alkylene group in a polyoxyalkylene group, 2 or 3 is more preferable.

≪Amphoteric surfactant≫
The amphoteric surfactant is not particularly limited as long as it is conventionally used in a cleaning agent, and various amphoteric surfactants can be used.
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

≪Soap anionic surfactant≫
The soap-based anionic surfactant is not particularly limited as long as it is conventionally used for a cleaning agent, and various soap-based anionic surfactants can be used.
Examples of the soap-based anionic surfactant include higher fatty acid salts (soaps) having 10 to 20 carbon atoms.
When the bleaching composition contains soap, the mass ratio represented by the soap / (D) component is preferably 0/100 to 80/100, more preferably 0/100 to 65/100, and still more preferably 0. / 100 to 50/100.
When soap is used in the absence of component (D), a sufficient whiteness improvement effect cannot be obtained. In addition, when there is too much soap content with respect to (D) component, the whiteness improvement effect will fall. This is considered because soap and (A) component form metal salt and precipitate.

[Optional fluorescent agent]
Examples of the fluorescent agent (optional fluorescent agent) other than the component (E) include stilbene types such as 4,4′-bis (triazol-2-yl) stilbene derivatives and bis- (triazinylaminostilbene) disulfonic acid derivatives. A fluorescent agent is mentioned. Examples of commercially available stilbene-type fluorescent agents include Whitetex SA, Whitetex SKC (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and Chino Pearl AMS-GX (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.). . Of these, Tinopearl AMS-GX is preferred.
These optional fluorescent agents can be used singly or in appropriate combination of two or more.
The content of the optional fluorescent agent in the bleaching composition can be determined in consideration of the type thereof, and is preferably 0.001 to 1% by mass, for example.
Since the stilbene type fluorescent agent is decomposed by ultraviolet rays, if it is too much for the component (E), the whiteness of the finished fiber product will be hindered. For this reason, when using a stilbene type fluorescent agent as an arbitrary fluorescent agent, the mass ratio represented by the stilbene type fluorescent agent / (E) component is preferably 0/100 to 80/100, and 0/100 to 60/100. More preferred is 0/100 to 40/100.

[Fragrance]
A fragrance | flavor is not specifically limited, It can determine suitably considering a fragrance | flavor etc. from well-known fragrance | flavors.
As a fragrance | flavor, a fragrance | flavor component, a fragrance | flavor composition, etc. are mentioned, for example. The fragrance composition is a mixture comprising a fragrance component and other components (solvent, fragrance stabilizer, etc.).
The perfume composition can be appropriately selected depending on the purpose, and examples thereof include a perfume composition containing one or more perfume ingredients generally used in cleaning agents, fiber finishing agents and the like.
Specific examples of the fragrance component include aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances, animal fragrances, and the like.
A fragrance | flavor composition may contain additives, such as antioxidant and antiseptic | preservative, as needed, unless the effect of this invention is prevented other than a fragrance | flavor component and a solvent.

<Organic peracid precursor>
The bleaching composition preferably contains an organic peracid precursor represented by the following formula (g1).

(In the formula (g1), R ¹¹ represents a linear aliphatic hydrocarbon group having 7 to 18 carbon atoms, X is a hydrogen atom, —COOM or —SO ₃ M (M is independently a hydrogen atom or Represents a salt-forming cation).)

The organic peracid precursor is a compound that reacts with the component (C) to generate an organic peracid.
In the formula (g1), the aliphatic hydrocarbon group for R ¹¹ may be a saturated aliphatic hydrocarbon group (alkyl group) or an aliphatic hydrocarbon group having an unsaturated bond. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 8 to 11 from the viewpoint of excellent bactericidal and sterilizing effects.

Examples of the salt-forming cation in —COOM or —SO ₃ M include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and cationic ammonium such as trimethylammonium and tetramethylammonium.
M is preferably a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium, more preferably a hydrogen atom or an alkali metal.

(G1) In the formula, the bonding position of X in the benzene ring is not particularly limited. From the viewpoint of the rate of generation of peracid and manufacturability, the para position (position 4) of the bonding position of R ¹¹ C (═O) O— is preferred.
Examples of the compound represented by the formula (g1) include decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, and the like. Decanoyloxybenzoic acid and sodium dodecanoyloxybenzenesulfonate are preferred. Among these, 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are preferable.

In the case of a solid bleaching composition, the organic peracid precursor is preferably formulated as a granulated product or a molded product from the viewpoint of storage stability during storage, and more preferably as a granulated product. preferable. Hereinafter, the granulated product or molded product containing the organic peracid precursor is referred to as an organic peracid-containing solid.
The content of the organic peracid precursor in the organic peracid-containing solid can be determined in consideration of the use or dosage form of the bleaching composition, and is preferably 30 to 95% by mass, for example, 50 to 90% by mass. More preferred. Outside the above range, it may be difficult to obtain a sufficient granulated effect.

The organic peracid precursor is preferably an organic peracid-containing solid using a binder compound.
A well-known thing can be utilized as a binder compound. Preferable binder compounds include polyethylene glycol, saturated fatty acids having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 and salts thereof.
As the polyethylene glycol, polyethylene glycol having an average molecular weight of 500 to 25000 is preferable. The average molecular weight is more preferably 1000 to 20000, further preferably 2600 to 9300, and particularly preferably 7300 to 9300.
As a saturated fatty acid having 12 to 20 carbon atoms, a saturated fatty acid having 14 to 20 carbon atoms is preferable, and a saturated fatty acid having 14 to 18 carbon atoms is more preferable.

 In addition, the average molecular weight of polyethyleneglycol shows the average molecular weight described in cosmetic raw material standards (the second edition comment). The weight average molecular weight of polyacrylic acid and its salt is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.

In the organic peracid-containing solid, the content of the binder compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 5 to 20% by mass.
The organic peracid-containing solid may further contain a surfactant in order to improve the solubility in water when performing a bleaching treatment or a washing treatment.

As the surfactant contained in the organic peracid-containing solid, known ones such as those mentioned in the component (D) and optional components can be used.
Preferred surfactants include polyoxyalkylene alkyl ethers, olefin sulfonates, alkylbenzene sulfonates, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, mixtures of any two or more thereof, and the like.

 The polyoxyalkylene alkyl ether preferably has 10 to 15 carbon atoms in the alkyl group, and the alkylene oxide is added with ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). Is particularly preferred. The average number of added moles of alkylene oxide in the polyoxyalkylene alkyl ether is preferably 4 to 30 in total, and 5 to 15 in any case of EO, PO, or a mixture of EO and PO. More preferred. The molar ratio of EO / PO is preferably 5/0 to 1/5, and more preferably 5/0 to 1/2.

 As the olefin sulfonate, a sodium salt or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms is preferable.

 As the alkylbenzene sulfonate, a sodium salt or potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms is preferable. The alkyl sulfate ester salt is preferably an alkyl sulfate ester salt having an alkyl group having 10 to 18 carbon atoms, more preferably an alkali metal salt such as a sodium salt, more preferably sodium lauryl sulfate or sodium myristyl sulfate.

 As a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is more preferable. 1-10 are preferable and, as for the average polymerization degree (henceforth, average polymerization degree is described as POE) of the oxyethylene group in polyoxyethylene alkyl ether sulfate ester salt, 1-5 are more preferable. As the polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene lauryl ether sulfate sodium salt (POE = 2 to 5) and polyoxyethylene myristyl ether sulfate sodium salt (POE = 2 to 5) are particularly preferable.

 The content of the surfactant in the organic peracid-containing solid is preferably 0% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and further preferably 3% by mass to 10% by mass.

 The organic peracid-containing solid may further contain a film-forming polymer, zeolite or the like. If the bleaching composition contains an alkaline component and water, the presence of these components may cause hydrolysis of the component during storage, which may impair the effect, but contains a film-forming polymer, zeolite, etc. By doing, the said hydrolysis can be suppressed.

[Detergency Builder]
Detergency builders are roughly classified into inorganic builders and organic builders.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered sodium silicate (for example, manufactured by Clariant Japan Co., Ltd.). Of crystalline alkali metal silicates such as [Na-SKS-6] (δ-Na ₂ O · 2SiO ₂ )), amorphous alkali metal silicates, sulfates such as sodium sulfate and potassium sulfate, sodium chloride , Alkali metal chlorides such as potassium chloride, aluminosilicates and the like.

 As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.

 As the crystalline aluminosilicate, zeolite can be suitably blended, and any of A type, X type, Y type, and P type can be used as the zeolite.

 Among the above inorganic builder, sodium carbonate, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, and aluminosilicate are preferred, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, crystalline Alkali metal chlorides are particularly preferred.

 When potassium carbonate is blended, the content of potassium carbonate in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, for example, when the bleaching composition is in a granular form, 1-15 mass% is preferable from the point of the effect of a solubility improvement, 2-12 mass% is more preferable, and 5-12 mass% is further more preferable.

 When blending the crystalline alkali metal silicate, the content of the crystalline alkali metal silicate in the bleaching composition is preferably 0.5 to 40% by mass, and 1 to 25% by mass from the viewpoint of detergency. More preferably, 3-20 mass% is further more preferable, and 5-15 mass% is especially preferable.

 When blending the alkali metal chloride, the content of the alkali metal chloride in the bleaching composition is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, from the viewpoint of improving the solubility. 3-7 mass% is further more preferable.

 When blending the crystalline aluminosilicate, the content of the crystalline aluminosilicate in the bleaching composition is preferably 1 to 40% by mass in terms of powder properties such as detergency and fluidity. 30% by mass is particularly preferred.

Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, And polysaccharide derivatives such as polysaccharide oxides such as cellulose, amylose and pectin.
Among the above-mentioned organic builder, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer salt, and polyacetal carboxylic acid salt are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A No. 54-52196) are suitable.
These detergency builders can be used singly or in appropriate combination of two or more. For the purpose of improving detergency and soil dispersibility in the washing liquid, it is preferable to use an organic builder such as polyacrylate and acrylic acid-maleic acid copolymer salt together with an inorganic builder such as zeolite.
The content of the detergency builder in the bleaching composition is preferably used within a range not impairing the effects of the present invention in order to impart sufficient detergency.

[Dye]
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, pigments are preferred, and compounds having oxidation resistance such as oxides are particularly preferred. Such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like.
These pigment | dyes can be used individually by 1 type or in combination of 2 or more types as appropriate.

[enzyme]
The enzymes are classified according to the reactivity of the enzymes, and include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.

 Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promerin, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. Commercially available proteases include sabinase, alcalase, cannase, everase, deozyme (above trade name, manufactured by Novozymes), API21 (trade name, made by Showa Denko KK), Maxacar, Maxapem (above trade name, manufactured by Genencor) , Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.

 Examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.

 Examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name, manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).

 As cellulase, cellzyme (trade name, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E-III (and above) And cellulase described in JP-A-63-264699).

Examples of amylases include commercially available stainzymes, termamyls, duramils (trade names, manufactured by Novozymes) and the like.
These enzymes can be used individually by 1 type or in combination of 2 or more types as appropriate.

In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).
The content of the enzyme in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, and is preferably 0.3 to 2% by mass, for example.

[Enzyme stabilizer]
Examples of the enzyme stabilizer include calcium salts, magnesium salts, polyols, formic acid, boron compounds, etc. Among them, sodium tetraborate, calcium chloride and the like are preferable.
These enzyme stabilizers can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the enzyme stabilizer in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, and is preferably 0.05 to 2% by mass, for example.

[Optional polymers]
The polymer (arbitrary polymers) other than the component (F) has an average molecular weight that functions as a binder for increasing the density of the surfactant-containing particles, a powder physical agent, or a recontamination inhibitor for hydrophobic fine particles. 200 to 200,000 polyethylene glycol, acrylic acid and / or maleic acid polymers having a weight average molecular weight of 1,000 to 100,000, polyvinyl alcohol, cellulose derivatives such as carboxymethyl cellulose excluding component (F), terephthalic acid and ethylene glycol as soil release agents And / or polyvinyl pyrrolidone that functions as a color transfer inhibitor, such as a copolymer or terpolymer with a propylene glycol unit, and the like. Among them, polyethylene glycol having an average molecular weight of 1500 to 7000 is preferable.
These arbitrary polymers can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the polymers in the bleaching composition can be determined in consideration of the use and dosage form of the bleaching composition, and is preferably 0.05 to 5% by mass, for example.

[Anti-caking agent]
The powdery bleaching composition can contain a caking agent. Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like.
These anti-caking agents can be used singly or in appropriate combination of two or more.

[Defoamer]
Examples of antifoaming agents include those conventionally known, for example, silicone / silica.
The antifoaming agent may be a defoaming agent granulated product produced using the method described in JP-A-3-186307, page 4, lower left column. Specifically, first, 20 g of Dow Corning silicone (compound type, PS antifoam) is added as a defoaming component to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nissho Chemical Co., Ltd., and mixed to obtain a homogeneous mixture. . Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of neutral anhydrous sodium sulfate were mixed at 70 to 80 ° C., and then extruded by Fuji Powder Co., Ltd. Granulate with a granulator (model EXKS-1) to obtain a granulated product.
These antifoaming agents can be used alone or in combination of two or more.

[Reducing agent]
Examples of the reducing agent include sodium sulfite and potassium sulfite.

[Metal ion scavenger]
The metal ion scavenger captures trace metal ions and the like in tap water, and has an effect of suppressing adsorption of metal ions to fibers (objects to be cleaned).
As metal ion scavengers, in addition to those included in the detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) -H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic Acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) ) Organic phosphonic acid Conductor or a salt thereof; diglycolic acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
These metal ion scavengers can be used singly or in appropriate combination of two or more.
It is necessary to consider that the content of the metal ion scavenger in the bleaching composition is used within a range that does not impair the performance.

[PH adjuster]
The bleaching composition can contain an alkali agent and an acid for adjusting pH.
Examples of the alkali agent include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide and the like in addition to the alkali agents described in the detergency builder. For example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, manufactured by Rhodia), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio), is preferable.
Examples of the acid include the metal ion scavenger, alkali metal dihydrogen salts such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, hydrochloric acid. Etc.
These pH adjusters can be used singly or in appropriate combination of two or more.
In the washing treatment, a buffering agent may be used in combination in order to prevent a decrease in pH due to an acid component derived from fiber dirt.

(Production method)
As the method for producing the bleaching composition of the present invention, known production methods may be mentioned depending on the dosage form of the bleaching composition.
For example, as a method for producing a solid bleaching composition, the components (A) to (E) and, if necessary, the component (F) and an optional component are mixed with powder to form a granular bleaching composition. The method of obtaining is mentioned. Or the method of obtaining surfactant-containing particle | grains containing (A) component, powder-mixing this and (B)-(E) component, and obtaining a granular bleaching composition is mentioned. Furthermore, the manufacturing method which shape | molds a granular bleaching composition in a tablet, a briquette, a sheet | seat, a bar, etc. is mentioned.
In addition, for example, a manufacturing method or a component obtained by kneading the components (A) to (E), the component (F) and an optional component as necessary, and molding the resultant into a tablet, briquette, sheet, bar or the like. The kneaded granulation and extrusion granulation are given to the kneaded product, and the manufacturing method made into a powder form is mentioned.
Among these production methods, a production method having a step of kneading the component (B) with the component (A) is preferred, and a production having a step of kneading the component (B) with the components (A) and (E). The method is more preferred. By kneading the component (B) together with the component (A), the whiteness improving effect can be further enhanced, and solidification of the obtained granular bleaching composition can be suppressed.

  As a manufacturing method of a liquid bleaching composition, the method of disperse | distributing or melt | dissolving a (A)-(E) component and the (F) component and arbitrary component as needed in a dispersion medium is mentioned. Examples of the dispersion medium include water, a mixed liquid of water and alcohol, and the like.

(how to use)
The method of using the bleaching composition of the present invention is not particularly limited, and if the bleaching composition is a bleaching agent, the washing liquid has a bleaching composition concentration of 0.02 to 0.5% by mass together with the cleaning agent. Is prepared in a washing machine, and the textile product is washed (stir washing) in this washing liquid, or the textile product is immersed in a washing liquid having a bleaching composition concentration of 0.02 to 2% by mass (soaking) A method such as washing is preferred. Especially, it is suitable for performing immersion washing for 15 minutes-12 hours.
If the bleaching composition is a bleaching detergent, a washing liquid having a bleaching composition concentration of 0.02 to 0.2% by mass is prepared in a washing machine, and a textile product is stirred and washed with this washing liquid. For example, a method of immersing and washing fiber products with a washing liquid having a bleaching composition concentration of 0.02 to 2 mass% can be used. Especially, it is suitable for performing stirring washing for 5 to 20 minutes.
The fiber product may be anything that is generally regarded as a laundry, and examples thereof include clothing, cloths, sheets, and curtains.

As above-mentioned, the bleaching composition of this invention can finish a textile more white (whiteness improvement effect) by containing (A)-(E) component (whiteness improvement effect). The mechanism for obtaining the whiteness improvement effect is not clear, but can be estimated as follows.
A bleaching composition disperses the dirt which adhered to the textile product by (D) component in a washing | cleaning liquid.
In addition, when the bleaching composition is poured into water, the component (A) and the component (B) form a complex. This complex accelerates the oxidation reaction of the component (C) and satisfactorily decomposes the dirt adhering to the fiber product. In this way, the dirt adhering to the textile product is removed.
Furthermore, the complex of the component (A) and the component (B) tends to form a complex with the anionic component (D) and component (E). Therefore, in the bleaching composition, the bleaching composition is a complex of the component (A) and the component (B), the component (D), and the component (E) (hereinafter referred to as a fluorescent agent complex). Form). This fluorescent agent complex is considered to be cationic due to the presence of the component (B) and exhibit a high adsorbing power to the fiber product. As a result, the bleaching composition increases the adhesion amount of the component (E) to the fiber product and can exhibit a high whiteness improving effect.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. The composition in a table | surface is a pure part conversion amount of each component.

(Raw materials used)
The raw materials used in the following examples are shown below.
<(A) component: water-soluble metal salt>
A-1: CuSO ₄ .5H ₂ O (copper sulfate (II) pentahydrate), manufactured by Kanto Chemical Co., Ltd.
A-2: AgSO ₄ , special grade, manufactured by Wako Pure Chemical Industries, Ltd. A-3: ZnSO ₄ · 7H ₂ O (zinc sulfate (II) heptahydrate), manufactured by Kanto Chemical Co., Inc.

<(B) component: long chain alkylamine compound>
B-1: Octylamine which is an alkylamine (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 2.5 g (19.5 mmol), monochloroacetic acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 5.0 g (52.9 mmol) ) Was added to a mixed solution of 5 mL of water and 32 cm ³ of ethanol (special grade, manufactured by Kanto Chemical Co., Ltd.), and stirred at reflux for 6 hours. During this reflux and stirring, a sodium hydroxide aqueous solution (5.0 mol / dm ³ ) 7.8 cm ³ prepared from sodium hydroxide (special grade, manufactured by Kanto Chemical Co., Inc.) was added to adjust the pH. Thereafter, the solution was cooled to 4 ° C. to form a precipitate. The produced precipitate was washed with ethanol, filtered, dried under reduced pressure to recover the solid, and sodium octyliminodiacetate represented by the following formula (I-3) (in the formula (I-3) above) The carbon number of the alkyl group (R ²⁰ ) was 8).

B-2: The same operation as in B-1 was carried out except that 3.6 g (19.5 mmol) of laurylamine (primary, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alkylamine, and the above (I- 3) Sodium lauryliminodiacetate represented by the formula (in the formula (I-3), carbon number of alkyl group (R ²⁰ ) = 12) was obtained.

B-3: The same operation as in B-1 was performed except that 4.2 g (19.5 mmol) of myristylamine (special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine, and the above (I-3 ) Sodium myristyliminodiacetate represented by the formula (in the formula (I-3), carbon number of alkyl group (R ²⁰ ) = 14).

B-4: The same operation as in B-1 was performed except that 4.7 g (19.5 mmol) of palmitylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine, and the above (I-3) Sodium palmiticyliminodiacetate represented by the formula (in the above formula (I-3), carbon number of alkyl group (R ²⁰ ) = 16) was obtained.

B-5: Except that 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine, the same operation as in B-1 was performed, and the above formula (I-3) In the above formula (I-3), the number of carbon atoms of the alkyl group (R ²⁰ ) = 18.

B-6: Eicosylamine as an alkylamine (synthetic product; based on Langmuir, 1994, No. 10, page 1226, arachidic acid is reacted with thionyl chloride to form carboxylic acid chloride, to which ammonia is added. After obtaining the sunamide, it was reduced with lithium aluminum hydride to synthesize eicosylamine). The operation was performed in the same manner as compound (B-1) except that 5.8 g (19.5 mmol) was used. This gave sodium eicosyliminodiacetate represented by the above formula (I-3) (in the formula (I-3), the number of carbon atoms of the alkyl group (R ²⁰ ) = 20).

B-7: Sodium monochloroacetate in which 55.5 g (0.3 mol) of laurylamine (primary, manufactured by Wako Pure Chemical Industries, Ltd.), which is an alkylamine, was dissolved in 100 cm ³ of ethanol and dissolved in 50 cm ³ of water. 4 g (0.33 mol) was added to prepare a mixed solution. The mixture was heated to 60 ° C., and an aqueous sodium hydroxide solution (12.5 mol / dm ³ ) was added dropwise while adjusting the pH so as not to be 9 or less. After the dropwise addition, the reaction was allowed to proceed for 5 hours, and the precipitated salt was filtered and removed by washing. The resulting filtrate was distilled off under reduced pressure, and sodium laurylaminoacetate (of the alkyl group) represented by the following formula (I-4): Carbon number = 12) was obtained.

B-8: Cocoalkylpropylenediamine (duomine, manufactured by Lion Akzo Co., Ltd.) represented by the following formula (I-5) (in the formula (I-5) below, the alkyl group (R ²¹ ) has 12 carbon atoms and 14 centered).

B-9: 224 g (1.1 mol) of lauric acid (special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a four-necked flask, and nitrogen substitution was performed twice at 80 ° C. Thereafter, the temperature was raised to 170 ° C., and 173 g (1.7 mol) of dimethylaminopropylamine (Kana Special Grade, Kanto Chemical Co., Ltd.) was added dropwise over 2 hours while distilling off the replicating water. Furthermore, it was kept at 170 ° C. to 180 ° C. and aged for 7 hours.
After aging, the pressure was reduced and unreacted amine and water were distilled off to obtain lauric acid dimethylaminopropylamide (acyl group carbon number = 12) represented by the following formula (I-6).

B-10: Diethylenetriamine (Tokyo Chemical Industry Co., Ltd.) 10.3 g (100 mmol) and 1-iodododecane (Wako Pure Chemical Industries, Ltd.) 3.0 g (10 mmol) were stirred at 40 ° C. for 5 hours. Thereafter, 2.4 cm ³ of an aqueous sodium hydroxide solution (5.0 mol / dm ³ ) was added and further stirred for a while. After allowing to cool, extraction was performed 5 times with diethyl ether / water using a separatory funnel, and the organic layer was distilled off under reduced pressure. The obtained organic layer was column (Nacalai Tesque, silica gel 60, spherical, neutral), eluent: chloroform (special grade, manufactured by Kanto Chemical Co., Inc.) / Methanol (special grade, manufactured by Kanto Chemical Co., Ltd.) = 1/1. After purification by column chromatography under the above conditions, the solid was recovered by drying under reduced pressure to obtain lauryl diethylenetriamine (carbon number of alkyl group = 12) represented by the following formula (I-7).

<(B ′) component: Comparative product of component (B)>
B′-1: Iminodiacetic acid (special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (I′-1) was used.

 B′-2: Lauroyllysine (Amihope, Ajinomoto Co., Inc.) represented by the following formula (I′-2) (carbon number of acyl group = 12) was used.

 B′-3: Lauroylaspartic acid represented by the following formula (I′-3) (aminoformer, manufactured by Asahi Kasei Chemicals Corporation) (carbon number of acyl group = 12) was used.

 B′-4: Lauroyl sarcosine represented by the following formula (I′-4) (Soibon, manufactured by Kawaken Fine Chemical Co., Ltd.) (acyl group carbon number = 12) was used.

<Component (C): Hydrogen peroxide or a peroxide that generates hydrogen peroxide in water>
C-1: sodium percarbonate (PC), SPCC (trade name), effective oxygen amount 13.8% by mass, average particle size 870 μm, manufactured by Zhejiang JINKE CHEMICALS C-2: hydrogen peroxide, hydrogen peroxide (35% (Product name), manufactured by Mitsubishi Gas Chemical Co., Ltd.

<(D) component>
D-1: LAS-Na, linear alkyl (10 to 14 carbon atoms) sodium benzenesulfonate (Laipon LH-200 (LAS-H pure content 96% by mass, manufactured by Lion Corporation) at the time of preparing the surfactant composition Neutralize with 48% by weight aqueous sodium hydroxide). The compounding quantity in a table | surface shows the mass% as LAS-Na.

 D-2: LAS-K, straight chain alkyl (carbon number 10-14) potassium benzenesulfonate (Laipon LH-200 (LAS-H pure content 96% by mass, manufactured by Lion Corporation) at the time of preparing the surfactant composition Neutralize with 48% by weight aqueous potassium hydroxide). The compounding quantity in a table | surface shows the mass% as LAS-K.

 D-3: MES, carbon number 16: carbon number 18 = 80: 20 (mass ratio) fatty acid methyl ester sulfonate sodium salt (manufactured by Lion Corporation, AI = 70% by mass, balance is unreacted fatty acid methyl ester) Sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).

<(E) component: biphenyl type fluorescent agent>
E-1: Biphenyl type fluorescent agent, Chino Pearl CBS-X (trade name), manufactured by Ciba Specialty Chemicals Co., Ltd.

<(E ') component: Comparative product of (E) component>
E'-1: Stilbene type fluorescent agent, Chino Pearl AMS-GX (trade name), manufactured by Ciba Specialty Chemicals Co., Ltd.

<(F) component: carboxymethylcellulose or a salt thereof>
F-1: Sodium carboxymethyl cellulose, CMC Daicel 1170 (trade name), manufactured by Daicel Chemical Industries, Ltd.

[Optional ingredients]
<(D ′) component: soap anionic surfactant>
D′-1: soap, fatty acid sodium having 12 to 18 carbon atoms (pure content; 67% by mass, titer; 40 to 45 ° C., fatty acid composition; C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 mass%, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight; 289, Lion Corporation Made).

<Others>
Nonionic surfactant: Leox CC-150-90 (trade name), an alcohol having an alkyl group having 12 to 14 carbon atoms, an average of 15 moles of ethylene oxide adduct, manufactured by Lion Co., Ltd. Zeolite: A-type zeolite, Mizusawa・ Sodium sulfate: anhydrous sodium sulfate, neutral anhydrous sodium sulfate (trade name), manufactured by Shikoku Kasei Kogyo Co., Ltd. ・ Sodium carbonate: heavy sodium carbonate (soda ash), manufactured by Asahi Glass Co., Ltd. ・ potassium carbonate: potassium carbonate・ Asahi Glass Co., Ltd. ・ MA agent: acrylic acid / maleic anhydride copolymer sodium salt, Socaran CP7 (trade name), manufactured by BASF ・ MGDA: trisodium methylglycine diacetate, manufactured by BASF ・ Organic peracid precursor (OBS12): Sodium 4-dodecanoyloxybenzenesulfonate (produced in Production Example 1 below) The thing)
-Sodium benzoate: Sodium benzoate, manufactured by Toa Gosei Co., Ltd.-Trisodium citrate: Sodium citrate, manufactured by Miles (USA)-95% ethanol: Synthetic alcohol 95 ° C, Nippon Alcohol Sales Co., Ltd.-Paratoluene Sulfonic acid: PTS acid, manufactured by Kyowa Hakko Chemical Co., Ltd. Polyethylene glycol: PEG # 1000, manufactured by Lion Co., Ltd. Isothiazolone solution: Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl -4-isothiazolin-3-one / magnesium salt / water mixture), manufactured by Rohm and Haas,
Fragrance composition A: Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399
Fragrance composition B: Fragrance composition B described in Tables 11 to 18 of JP-A-2002-146399
-Dye A: Green No. 3, manufactured by Sakai Kasei Co., Ltd.-Dye B: Ultramarine, Dainichi Seika Kogyo Co., Ltd.-Sodium hydroxide: Tsurumi Soda Co., Ltd.-Sulfuric acid: Toho Zinc Co., Ltd.-Enzyme: Evalase 8T / Mixture of LIPEX50T / Termamyl 60T / Celzyme 0.7T = 5/2/1/2 (mass ratio), manufactured by Novozymes ・ Baking soda: sodium bicarbonate, special grade reagent, manufactured by Kanto Chemical Co., Inc.

<< Production Example 1 >> Production of OBS12 Sodium p-phenolsulfonate (reagent, manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent, manufactured by Kanto Chemical Co., Ltd.), and lauric acid chloride (reagent, OSB12 was produced by the following method using Tokyo Chemical Industry Co., Ltd.) and acetone (reagent, produced by Kanto Chemical Co., Inc.).
100 g (0.51 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of N, N-dimethylformamide, and 111 g (0.51 mol) of lauric acid chloride was stirred at 50 ° C. for 30 with stirring with a magnetic stirrer. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was carried out for 3 hours, and N, N-dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then in a water / acetone (= 1/1 mol) solvent. And recrystallized to obtain sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90%.
70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate thus obtained, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M, manufactured by Lion Corporation), and sodium alkyl sulfate having 14 to 18 carbon atoms (trade name) : Sandet LNM, manufactured by Sanyo Chemical Industries, Ltd.) was mixed by a continuous pro-shear mixer (WA type, manufactured by Taiheiyo Kiko Co., Ltd.) so as to have a ratio of 5 parts by mass to obtain a mixed powder. The mixed powder was put into a continuous kneader (KRS-S1 type, manufactured by Kurimoto Iron Works Co., Ltd.), kneaded at 60 ° C., and then extruded through a 0.8 mm porous screen to obtain a noodle-like mixture. The resulting mixture was pulverized using a pulverizer (NEW SPEED MILL, manufactured by Okada Seiko Co., Ltd.) while mixing the mixture so that the amount of A-type zeolite was 5 parts by mass as a pulverization aid. The pulverized product was sieved to obtain granules (particle size: 70% by mass of OBS12) having a particle size of 300 to 700 μm.

(Examples 1-2)
According to the composition of Table 1, the bleaching composition of each example was manufactured by the following series of processes. In the table, the production method of this example was described as “1”.
<Spray drying process>
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. The component (D) excluding the nonionic surfactant and MES and the optional surfactant were added to this and stirred for 10 minutes. Subsequently, after adding the MA agent and stirring for another 10 minutes, a part of the A-type zeolite (from the amount described in the composition in the table, 1.0% by mass for addition at the time of kneading, 5.0% by mass For the pulverization aid and 1.5 mass% of the surface modification excluding A-type zeolite), sodium carbonate, potassium carbonate, and sodium sulfate. After further stirring for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass, the slurry is spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size (50% by mass particle size). Spray-dried particles having a thickness of 320 μm, a bulk density of 0.30 g / cm ³ and a water content of 5% by mass were obtained.

<Kiwa kneading process A>
Part of the nonionic surfactant (with a water concentration of 25% by mass) prepared in the MES-Na (D-3) aqueous slurry (prepared to a moisture concentration of 25% by mass) obtained by sulfonating and neutralizing the fatty acid ester of the raw material 25% by mass with respect to MES-Na), and concentrated under reduced pressure with a thin-film dryer until the water concentration becomes 11% by mass to obtain a mixed concentrate of MES-Na and nonionic surfactant. It was.
The spray-dried particles obtained in the above <spray-drying step>, the above-mentioned mixed concentrate, 1.0% by mass of A-type zeolite, 0.5% by mass of the nonionic surfactant for spray addition, the nonion in the above-mentioned mixed concentrate The remaining nonionic surfactant excluding the surfactant, (A) component, (E) component and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Works), and the kneading capacity was 120 kg / hr. The mixture was kneaded under conditions of a temperature of 60 ° C. to obtain a surfactant-containing kneaded material containing 6% by mass of water containing the surfactant. Cutting the surfactant-containing kneaded material with a cutter while using a pelleter double (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed is 5 m / s) To obtain a pellet-shaped activator molded product having a length of about 5 to 30 mm.

<Crushing process>
An amount equivalent to 5.0% by mass of A-type zeolite as a grinding aid was added to the obtained pellet-shaped activator molded product, and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). Crushing using a Fitzmill (DKA-3, manufactured by Hosokawa Micron Corporation) to obtain a pulverized product containing an active agent (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm).

<Surface coating process>
The above pulverized activator-containing pulverized product, component (F), component (C), organic peracid precursor and sodium hydrogen carbonate as necessary, are added to a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm). , Having a baffle plate with a clearance of 20 mm and a height of 45 mm with respect to the inner wall surface of the drum of the container 131.7 dm ³ , under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. ) Component and 1.5% by mass of surface modifying A-type zeolite, while spraying 0.5% by mass of nonionic surfactant and fragrance, roll for 1 minute to produce surfactant-containing particles. Obtained.

<Powder mixing process>
While transferring the obtained surfactant-containing particles at a speed of 0.5 m / s by a belt conveyor (surfactant-containing particle layer height 30 mm, layer width 300 mm), the amounts of enzymes and dyes listed in the table Was quantitatively fed to obtain a powdery bleaching composition (average particle size 530 μm, bulk density 0.84 g / cm ³ , angle of repose 45 °).
About the obtained bleaching composition, the whiteness improvement effect and solidification property were evaluated, and the results are shown in the table.

(Examples 3-35, Comparative Examples 1-11)
According to the compositions in Tables 1 to 10, the same procedure as in Example 1 was conducted except that (B) component was not added in <Surface coating step> and <Kiwa kneading step A> was changed to <Kiwa kneading step B> below. Thus, a granular bleaching composition (average particle size 510 μm, bulk density 0.86 g / cm ³ , angle of repose 45 °) was obtained. About the obtained bleaching composition, the whiteness improvement effect and solidification property were evaluated, and the results are shown in the table.
In the table, the production method of this example was described as “2”.

<Kiwa kneading process B>
Spray-dried particles obtained in <spray-drying step> of Example 1, the above-mentioned mixed concentrate, 1.0% by mass of A-type zeolite, 0.5% by mass of nonionic surfactant for spray addition, the above-mentioned mixed concentration The remaining nonionic surfactant excluding the nonionic surfactant in the product, (A) component, (B) component, (E) component, MGDA and water continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Co., Ltd.) ) And kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded material containing 6% by mass of a surfactant. Cutting the surfactant-containing kneaded material with a cutter while using a pelleter double (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed is 5 m / s) To obtain a pellet-shaped activator molded product having a length of about 5 to 30 mm.

(Examples 36 to 38)
According to the composition of Table 11, (D) component, nonionic surfactant, 95% ethanol, polyethylene glycol, and paratoluenesulfonic acid were put into a beaker and stirred with a magnetic stirrer (MITAMURA KOGYO INC.).
Next, water heated to 40 ° C. is added, sodium benzoate, citric acid, isothiazolone solution, fragrance, and pigment are added and stirred to dissolve these components, and then component (B) is added. In addition, the mixture was further stirred.
Next, a 10% by mass aqueous solution of component (A) is added, and after adding component (B), component (C) and component (E), sodium hydroxide and / or sulfuric acid is used so that the pH of the solution becomes 7. A liquid bleaching composition was prepared. About the obtained bleaching composition, the whiteness improvement effect was evaluated and the result is shown in a table | surface.
In the table, the production method of this example was described as “3”. The balance amount of water in the table refers to water whose blending amount is adjusted so that the total amount of the bleaching composition is 100% by mass in the liquid which is the final composition.

(Evaluation method)
<Whiteness improvement effect>
To a washing tester (Terg-O-Tometer), tap water (15 ° C.) 900 cm ³ and a cloth with a size of 30 cm square (65% polyester / 35% cotton, broad, manufactured by Tanigami Shoten Co., Ltd.) 2 A piece and 0.6 g of powder detergent for clothing (trade name; Top, manufactured by Lion Corporation) were added and washed at 120 rpm for 10 minutes. Subsequently, after dewatering until the mass of the washing liquid contained in the cloth became the same mass as the cloth, the process of rinsing with 900 cm ³ of tap water (15 ° C.) for 3 minutes was repeated twice, and then dewatered. Subsequently, the dehydrated cloth was dried with an iron to obtain a treated cloth.

Natto beef stew (trade name, lot (08.1.24A), manufactured by SBI Foods Co., Ltd.) was adjusted to 50 ° C. and filtered with gauze. One treated cloth was immersed in the filtrate placed in a 40 cm × 50 cm vat and left for 30 minutes.
Next, the treated cloth was taken out, air-dried by hanging and drying, and cut into 2 cm square. The cut piece was dried at 105 ° C. for 2 hours. The reflectance was measured with a colorimetric color difference meter (SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and a fabric with a Z value of 30 to 40 was used as a contaminated cloth.

To a washing tester (Terg-O-Tometer), 900 cm ^{3 of} tap water (15 ° C.), 10 sheets of contaminated cloth, 0.6 g of the bleaching composition of each example, and a skin shirt (100% cotton, The product No. G0134TS) was cut into 3 cm × 3 cm and 25 g, and washed at 120 rpm for 10 minutes. Next, after dewatering until the mass of the washing liquid contained in the contaminated cloth became the same mass as the contaminated cloth, the process of rinsing with 900 cm ³ of tap water (15 ° C.) for 3 minutes was repeated twice, and then dehydrated. The dehydrated soiled fabric was then air-dried for 3 hours during the day and dried with an iron.
The reflectivity was measured with a colorimetric color difference meter (SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) for each of the five contaminated cloths after washing, and the Z value was measured. The average value of the Z values of the five contaminated cloths was classified into the following evaluation criteria, and “◎◎”, “◎”, and “◯” were accepted.

≪Evaluation criteria≫
◎: 85 or more ◎: 80 or more and less than 85 ○: 75 or more and less than 80 Δ: 70 or more and less than 75 ×: less than 70

<Solidability A>
The bleaching composition of each example is housed in a commercially available powder detergent container for clothing (room-dried top (lot. 100714C7A, manufactured by Lion Corporation) with the contents removed) to close the opening of the container body. The glassine paper was adhered as described above, and the lid was closed to obtain a container containing the composition. About this container containing the composition, after repeating the operation of dropping from the height of 10 cm to the floor 5 times, 40 ° C. storage (90% RH, 16 hours) and 30 ° C. storage (60% RH, 8 hours) are defined as one cycle. Stored for 10 cycles. The bleaching composition was discharged from a container containing the composition after the completion of 10 cycles onto a wire mesh (6 mesh openings), and the mass of the material that passed through the wire mesh was measured (= A (g)). In addition, the mass of the bleaching composition remaining on the wire mesh was measured (= B (g)), and the solidification rate was determined by the following formula (2). The obtained solidification rate was classified into the following evaluation criteria, and “「 ”or“ ◯ ”was regarded as acceptable.

 Solidification rate (mass%) = B ÷ (A + B) × 100 (2)

≪Evaluation criteria≫
A: 0% by mass or more and less than 5% by mass O: 5% by mass or more and less than 10% by mass X: 10% by mass or more

<Solidification B>
The solidification rate was determined in the same manner as the solidification property A except that the storage period was 30 cycles, and the solidification property was evaluated.

As shown in Tables 1 to 8, in Examples 1 to 35 in which the present invention was applied to a granular bleaching composition, the whiteness evaluation was “◯” or “◎”, and solidification A and solidification B were All the results were “◯” or “◎”.
In addition, in Example 2 containing the component (F), the Z value increased by 5 points compared to Example 1 not containing the component (F). In Example 4 in which the component (B) was kneaded with the component (A), the Z value increased by 6 points compared to Example 2 in which the component (B) was used for coating the pulverized product containing the active agent, and the solidification property was increased. B was rising.
Further, Examples 4, 12, and 13 having a B / E ratio of 3 or more had an improved Z value as compared with Example 11 having a B / E ratio of 1.4. From this result, it was found that the whiteness improvement effect is enhanced as the B / E ratio is higher.
In Examples 36 to 38 in which the present invention was applied to a liquid bleaching composition, the whiteness evaluation was “◯”.

On the other hand, in Comparative Example 1 in which the B / E ratio was 1, and in Comparative Example 11 containing the component (E ′) instead of the component (E), the whiteness evaluation was “Δ”.
In Comparative Example 3 not containing (B) and Comparative Examples 7 to 10 containing the component (B ′) instead of the component (B), the whiteness evaluation was “x”.
In Comparative Example 4 containing no component (C), the whiteness evaluation was “Δ”.
In Comparative Example 2 containing no component (D), the whiteness evaluation was “x”. In Comparative Example 5 containing the component (D ′) instead of the component (D), the whiteness improvement effect was “x”. This is presumably because the component (D ′) was soap, and thus formed and formed a metal complex with the component (A). In addition, since the comparative example 5 did not have fluidity, the solidification property of the comparative example 5 was not evaluated.

  From these results, it was found that the bleaching composition to which the present invention is applied can finish the textile product whiter.

Claims (2)

(A) component: one or more water-soluble metal salts selected from the group consisting of water-soluble salts of transition elements, water-soluble salts of zinc or water-soluble salts of silver in the fourth period of the periodic table;
(B) component: a compound represented by the following formula (I) or (II) :
(C) component: hydrogen peroxide or a peroxide that generates hydrogen peroxide in water;
Component (D): a non-soap anionic surfactant;
(E) component: biphenyl type fluorescent agent,
Containing
(B) The bleaching composition characterized by mass ratio represented by a component / (E) component being 1.2 or more.

(In the above formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents a hydrogen atom or (CH ₂ ) _m1 -COOX ^2. X ¹ and X ² each represent 1 type independently selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group, n1 is a number from 1 to 3, and m1 is a number from 1 to 3. .)

(In the above formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m2 ), and r is 1 or 0. When r is 0, A ² and A ³ are each independently selected from a hydrogen atom and a methyl group, and when r is 1, either A ² or A ³ One is a hydrogen atom and the other is either a hydrogen atom or CH ₂ COOX ^3. X ³ is selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. N2 is a number from 1 to 3, and m2 is a number from 1 to 3.   (F) Component: Carboxymethylcellulose or its salt is contained, The bleaching composition of Claim 1 characterized by the above-mentioned.