JP2005314575A - Bleaching and washing agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching and washing agent composition that shows high bleaching and washing effect to textile products. <P>SOLUTION: This bleaching and washing agent composition comprises (a) 8 to 25 % mass of an inorganic peroxide as hydrogen peroxide, (b) 0.01 to 1 % mass of fluorescent brightening agent, and additionally (c) 5 to 20 % mass of a compound selected from alkanoyloxybenzene sulfonic acid bearing a 6-14C alkanoyloxy group and alkanoyloxybenzene carboxylic acid bearing a 6-14C alkanoyloxy group and their salts, where the content of the surfactant is less than 5 % mass in total. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a bleach cleaning composition and a bleach cleaning method for textiles such as clothing.

  Bleaching detergents can be divided into chlorine and oxygen types. Chlorine bleaching detergents are limited in the fibers that can be used, and furthermore, they cannot be used for color patterns and have a unique irritating odor. Recently, oxygen-based bleach cleaners that do not have these drawbacks have become extremely popular. As this oxygen bleaching detergent, sodium percarbonate and sodium perborate are widely used as bleaching bases in terms of bleaching performance and stability.

Oxygen bleach cleaners are used in combination with various bleach activators (organic peracid precursors) because they have less bleaching power than chlorine bleach cleaners. As typical bleach activators, tetraethylenediamine, alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid, tetraacetylglycolyluril, glucose pentaacetate and the like are known (Patent Documents 1 to 3). Moreover, although it is also known to mix | blend a fluorescent whitening agent with a bleaching agent or a cleaning agent (patent documents 4-5), there is no suggestion which improves the effect of a fluorescent whitening agent.
JP-A-11-217590 JP-A-10-95996 Japanese Patent No. 3320304 Japanese Patent Laid-Open No. 9-20899 JP 2001-254100 A

  An object of the present invention is to provide a bleaching detergent composition which has a higher bleaching cleaning effect and exhibits a high bleaching cleaning effect on hard-to-remove stains such as curry attached to textiles.

  In the present invention, (a) inorganic peroxide (hereinafter referred to as “component (a)”) is 8 to 25% by mass using hydrogen peroxide, (b) fluorescent whitening agent (hereinafter referred to as “component (b)”) is 0. The present invention relates to a bleaching detergent composition containing 01 to 1% by mass and having a surfactant content of 5% by mass or less.

  The present invention also relates to a method for bleaching a textile product, comprising bringing the textile product into contact with an aqueous medium containing the bleaching detergent composition of the present invention at a concentration of 0.1% by mass or more for 30 minutes or more.

  ADVANTAGE OF THE INVENTION According to this invention, the bleach cleaning composition excellent in the bleach cleaning effect and the bleach cleaning method of textiles are provided.

<(A) component>
Examples of the inorganic peroxide of the component (a) used in the present invention include inorganic peroxide salts such as percarbonate, perborate and perphosphate. Among these, percarbonate is used. preferable. The salt is preferably an alkali metal salt such as a sodium salt or a potassium salt.

  (A) The average particle diameter of a component becomes like this. Preferably it is 200-1000 micrometers, Most preferably, it is 250-400 micrometers. In order to prevent caking of the bleaching detergent composition, the content of fine powder that passes through a sieve having a pore size of 125 μm is preferably 50% by mass or less, and preferably 30% by mass or less. Particularly preferred is 20% by mass or less.

  The content of the component (a) in the bleaching detergent composition of the present invention is 8 to 25% by mass as hydrogen peroxide in consideration of blending with other components while giving sufficient bleaching detergency. Preferably it is 10-20 mass%, Most preferably, it is 13-18 mass%.

<(B) component>
Although it does not restrict | limit especially as a fluorescent whitening agent used as (b) component, A biphenyl type | mold fluorescent whitening agent is preferable and 4,4-bisphenyl salt is more preferable. Furthermore, it is preferable that it is a fluorescent whitening agent which improved the water solubility by containing a sulfonic acid group or its alkali metal salt. In view of the storage stability in a composition containing a dissolution rate and a bleaching component at a high concentration, it is preferable not to contain a stilbene type fluorescent whitening agent. Specifically, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 4,4′-bis- (2-sulfo-4-chlorostyryl) -biphenyl salt and the like. Commercial products such as Chino Pearl CBS and Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals) can also be used.

  In the present invention, in order to improve the dyeing property of the fluorescent brightening agent, the content of the surfactant in the composition is 5% by mass or less, more preferably 3% by mass or less. The surfactant here is an amphiphilic substance having hydrophilic and lipophilic atomic groups in the molecule, and in particular, an anionic surfactant, a cationic surfactant contained in the composition, The total amount of the nonionic surfactant and the amphoteric surfactant is taken as the content. Furthermore, the total amount of the anionic surfactant and / or the nonionic surfactant can be set as the surfactant content. In particular, considering the influence of the nonionic surfactant on the dyeing property of the optical brightener, the content of the nonionic surfactant in the composition is preferably 3% by mass or less.

  Among the above surfactants, the anionic surfactant includes a sulfate ester salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, and an ethoxylated product of an alcohol having 8 to 20 carbon atoms. One or more kinds selected from sulfate ester salts, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts and fatty acid salts are included. The counter ion of these anionic surfactants is preferably an alkali metal salt, and particularly sodium or potassium.

  In particular, the surfactant preferably contains one or more selected from linear alkylbenzene sulfonates having 12 to 14 carbon atoms in the alkyl chain and alkyl sulfates having 12 to 18 carbon atoms.

  Among the above surfactants, nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene. One or more types selected from block polymers are listed.

  In particular, the surfactant is a polyoxyalkylene alkyl ether, in particular, 4 to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide is added to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms. It is preferable to include a polyoxyalkylene alkyl ether having an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5.

  In the present invention, (1) linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain, (2) alkyl sulfate having 12 to 18 carbon atoms, and (3) linear or branched having 10 to 18 carbon atoms. At least a polyoxyalkylene alkyl ether having an HLB value (calculated by the Griffin method) of 10.5 to 15.0 obtained by adding 4 to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide to a primary or secondary alcohol of the chain The total content of any of the surfactants is preferably 5% by mass or less, and more preferably 3% by mass or less.

  The content of the component (b) in the bleaching detergent composition of the present invention is 0.01 to 1% by mass, preferably 0.1 to 0.5%, from the viewpoint of providing sufficient bleaching detergency. It is mass%, Most preferably, it is 0.1-0.3 mass%.

  The bleach detergent composition of the present invention further comprises (c) an alkanoyloxybenzenesulfonic acid having an alkanoyloxy group having 6 to 14 carbon atoms, an alkanoyloxybenzenecarboxylic acid having an alkanoyloxy group having 6 to 14 carbon atoms, and these 5 to 20% by mass of a compound selected from the following salts [hereinafter referred to as component (c)], 1 to 5% by mass of (d) dispersant (hereinafter referred to as component (d)), or (e) a chelating agent [ (Excluding component (d)) [hereinafter referred to as component (e)] is preferably contained in an amount of 1 to 5% by mass in order to obtain higher bleaching power.

<(C) component>
(C) Although it does not restrict | limit especially as a component, The compound represented by the following general formula (c1) can be mentioned.

[Wherein, R ¹ represents a linear alkyl group having 5 to 13 carbon atoms, and Y represents a sulfonic acid group or a carboxylic acid group, or an alkali metal salt, alkaline earth metal salt or ammonium salt thereof. ]

In the formula (c1), when R ¹ has 5 or more carbon atoms, the dirt has high adsorptivity and can exhibit sufficient bleach cleaning performance. If it is 13 or less, it is sufficient even under low temperature cleaning conditions. Since solubility can be provided, it is preferable.

  As a compound corresponding to the general formula (c1), for example, a compound represented by the following general formula (c2) or (c3) is preferable.

[Wherein, R ² represents a linear alkyl group having 5 to 13 carbon atoms, M ¹ represents a sodium atom, a potassium atom or an ammonium group, and R ³ represents a linear alkyl group having 5 to 13 carbon atoms. ]

  In order to increase the stability of the component (c), it can be mixed with a water-soluble binder and other components to form a granulated product. The description of paragraphs 0017 to 0022 of JP-A No. 11-217590 can be referred to for the granulated product of component (c).

  The content of the component (c) in the bleaching detergent composition of the present invention is preferably 5 to 20% by mass, more preferably 8 to 18% by mass in order to impart sufficient bleaching detergency and to prevent caking. %, Particularly preferably 10 to 15% by mass.

<(D) component>
The dispersant as the component (d) is not particularly limited. As the carboxylic acid polymer, (d1) polyacrylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, hydroxyacrylic acid heavy Acrylic polymers such as polymers, polysaccharide-acrylic acid copolymers, (d2) polyvalent carboxylic acids such as maleic acid, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid and aspartic acid An acid polymer is mentioned. In addition, polymer compounds such as (d3) glyoxylic acid polymer and (d4) polysaccharides (cellulose derivatives such as carboxymethyl cellulose) can be used.

  The component (d) is preferably a carboxylic acid polymer having a weight average molecular weight of several hundred to 100,000, particularly an acrylic acid polymer. Carboxylic acid polymers are preferred in terms of the effect of dispersing solid particle soil from the garment into the washing bath and the effect of preventing the particles from reattaching (recontamination) to the garment.

  Examples of the carboxylic acid polymer include those having a repeating unit represented by the following general formula. The copolymer is generally random polymerization.

[Wherein, X and P each represent a hydrogen atom, a hydroxyl group or —CH ₂ OH; Y represents a hydrogen atom, —COOM ′ or —CH ₂ COOM ′; Z represents —COOM ′ or —CH _2; COOM ′ is indicated. M ′ represents an inorganic or organic counter ion. ]

  Among these carboxylic acid polymers, salts of acrylic acid-maleic acid copolymers and polyacrylates are preferable, and those having a weight average molecular weight of 1,000 to 80,000 are preferable. Examples of these salts include alkali metal salts such as sodium salt and potassium salt, and ammonium salts. The carboxylic acid polymer is usually easily obtained by polymerizing an unsaturated organic carboxylic acid or organic polycarboxylic acid, but has a weight average molecular weight of 2,000 or more and a carboxyl group of 10 or more. If it is a thing, the unsaturated carboxylic acid monomer as the raw material will not be limited.

  The content of the component (d) in the bleaching detergent composition of the present invention is preferably 1 to 5% by mass, more preferably 2 to 4 in consideration of blending with other components while giving sufficient dispersibility. It is mass%, Most preferably, it is 3-4 mass%.

<(E) component>
(E) What can be used as a component is mentioned below. In the present invention, the polymer compound used as the component (d) is not included in the content of the component (e). (E1) Phosphoric acid compounds such as phytic acid or their salts, (e2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphone Acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, phosphonic acid such as methanehydroxyphosphonic acid or salts thereof, (e3) 2-phosphonobutane- 1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, phosphonocarboxylic acid such as α-methylphosphonosuccinic acid or a salt thereof, (e4) glycine or a derivative thereof, aspartic acid, glutamic acid (E5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyl Aminopolyacetic acid such as Louisinodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid or a salt thereof, (e6) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid Organic acids such as succinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid or salts thereof, (e7) aluminosilicates such as zeolite A, (e8) aminopoly (methylenephosphonic acid) or salts thereof, or Examples thereof include polyethylene polyamine poly (methylene phosphonic acid) or a salt thereof.

As the component (e), those satisfying the Ca chelate stability constant (pK _Ca ) at 20 ° C. and the organic peracid residual rate at 20 ° C., which are obtained by the following method, are preferable.

The Ca chelate stability constant can be determined by the following method. Buffer _{NH 4 Cl-NH 4 OH (} pH10.0) solution of 0.1 mol / L was prepared as to prepare all sample solution using the same. For measurement of the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ electrode are used. First, the relationship between the calcium chloride concentration and the electrode potential is determined, and a calibration curve is created. Next, a calcium chloride 5.36 × 10 ⁻² mol / L solution and a chelating agent sample 5.36 × 10 ⁻⁴ mol / L solution are prepared. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ electrode. Assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1, the Ca chelate stability constant is obtained from the following formula.

[Wherein [Ca] indicates the residual metal ion concentration (mol / L), [L] _Total indicates the initial chelating agent concentration (mol / L), and [Ca] _Total indicates the initial metal ion concentration (mol / L). )

The Ca chelate stability constant (pK _Ca ) of the component (e) is preferably 4.5 or more, more preferably 5 to 12, in order to capture hardness components such as Ca ²⁺ and increase the bleaching detergency. Especially preferably, it is 6-10.

  When the bleaching detergent composition of the present invention contains the component (c), the component (e) preferably has an organic peracid residual ratio of 80% or more as measured by the following method. An aqueous solution consisting of 100 ppm sodium percarbonate having an effective oxygen concentration of 12% by mass (mass ratio, the same applies hereinafter) and 35 ° C. ion-exchanged water is prepared in a 1 L beaker, and (c) component 0.1 mmol / L is added thereto. At this time, the concentration of component (c) is as follows:

Based on the compound represented by Next, after reacting for 20 minutes, an equimolar amount of a chelating agent is added to the organic peracid precursor, and the remaining amount of organic peracid when reacted for another 20 minutes is used. Rate (%) = obtained from the amount of organic peracid after reaction × 100 / initial amount of organic peracid. The amount of organic peracid is measured by titration with sodium thiosulfate.

  The organic peracid residual ratio at 20 ° C. of the component (e) is preferably 80% or more, more preferably 90% or more, particularly preferably in order to suppress the decomposition of the component (c) and increase the bleaching detergency. 95% or more.

  (E) As a component, what is represented by the following general formula (e1) can be mentioned.

[Wherein, W ¹ and X ¹ are each a hydrogen atom, —R, —R—OH, —COOM, —SO ₃ M or —PO ₃ M (where R is an alkyl group having 1 to 5 carbon atoms, , An alkenyl group or an alkylene group, M represents a hydrogen atom, an alkali metal salt, an alkaline earth metal salt or an ammonium group), and Y ¹ and Z ¹ are a hydrogen atom, —R, —R—OH, respectively. , -COOM, -SO ₃ M or -PO ₃ M or _{-R'-COOM, -R'-SO 3} M or -R'-PO ₃ M (wherein, M, R is as defined above, R ′ represents a C 1-5 alkyl group, alkenyl group or alkylene group). ]

  Examples of the chelating agent corresponding to the general formula (e1) include those represented by the following formula.

  The content of the component (e) in the bleaching detergent composition of the present invention is preferably 1 to 5% by mass, more preferably 1.5 to 4% by mass in order to impart sufficient bleaching detergency. Most preferably, it is 2-3 mass%.

  In the bleaching detergent composition of the present invention, the mass ratio of the component (b) to the surfactant is (b) component / surfactant = 1/50 to 10 / 1, more preferably 1/30 to 1/1, and particularly preferably 1/20 to 5/1.

  In the bleaching detergent composition of the present invention, the mass ratio of the component (a) to the component (c) is (a) / (c) = 30/1 to 1 / 1, more preferably 15/1 to 3/1, and particularly preferably 10/1 to 5/1.

<Enzyme>
The bleaching detergent composition of the present invention can contain enzymes such as amylase, protease, lipase and cellulase, more preferably contains amylase and / or protease, and particularly preferably contains amylase and protease. .

  Examples of amylase include α-amylase and β-amylase. The α-amylase is preferably an enzyme obtained from Bacillus licheniformis or Bacillus subtilis, and commercially available products include Termamyl (registered trademark, Novo Industry), Maxamil (registered trademark, Gist), and the like. Moreover, as β-amylase, enzymes obtained from bacteria such as Bacillus sp., Soybeans, and malt can be used, and commercially available products include Amano (registered trademark Amano Pharmaceutical Co., Ltd.), Multitome (registered trademark, Nagase Biochemicals). Industrial companies).

  As for amylase, it is desirable to mix starch debranching enzyme. Desirable starch debranching enzymes are obtained from a variety of sources, but are generally derived from fungi. For example, pullulanase, isopullulanase, isoamylase showing amylopectin-6-glucanohydrase activity obtained from bacteria belonging to the genus Klebsiella, bacteria belonging to the genus Bacillus, bacteria belonging to the genus Aspergillus, bacteria belonging to the genus Pseudomonas . The compounding amount of amylase is preferably 0.1 to 50 units, more preferably 0.2 to 25 units, and particularly preferably 0.5 to 20 units in 1 g of the composition as the amount of enzyme activity. Here, 1 unit / g is the amount of enzyme that produces 1 μmol of glucose per minute, and is measured by the DNS (3,5-dinitrosalicylic acid) method. If the amount of the enzyme is 0.1 unit or more, sufficient enzyme activity can be obtained. If it is 50 units or less, the bleaching performance is exhibited without causing the organic peracid generated from the bleach activator to be activated by the reducing sugar generated when amylase decomposes the starch.

In addition, the measuring method of the enzyme activity by DNS method is shown below.
(1) Substrate: 0.5% by mass potato-derived soluble starch (reagent, Sigma) solution
(2) Preparation of substrate solution Dissolve 1.0 g of potato-derived soluble starch in 100 ml of ion-exchanged water.
(3) Sample preparation Place 0.5 ml of the substrate solution in a test tube, add 0.4 ml of 100 mM Glycine-NaOH buffer (pH = 10.0), 0.1 ml of enzyme solution diluted appropriately, and place in a 50 ° C constant temperature bath. Incubate for 15 minutes. After completion of the reaction, 1 ml of DNS solution is added, and color is developed in boiling water for exactly 5 minutes. After color development, the solution is immediately placed in an ice-water bath and cooled. After cooling, add 4 ml of ion-exchanged water, mix well, and immediately measure the absorbance at 535 nm.
(4) Preparation of blank 0.5 ml of the substrate solution is put in a test tube, 0.4 ml of 100 mM Glycine-NaOH buffer (pH = 10.0) is added thereto, and 1 ml of the DNS solution is added thereto, and the color is accurately developed in boiling water for 5 minutes. Let the color develop and immediately cool in an ice-water bath. After cooling, add 4 ml of ion-exchanged water, mix well, and immediately measure the absorbance at 535 nm.
(5) Preparation of calibration curve Place 0.5 ml of the substrate solution in a test tube, add 0.4 ml of 100 mM Glycine-NaOH buffer (pH = 10.0), and adjust the glucose concentration to 250-1500 μmol / l. Add 0.1 ml of glucose solution for use. 1 ml of the DNS solution is added thereto, and the color is developed accurately in boiling water for 5 minutes. After the color development, it is immediately placed in an ice water bath and cooled. After cooling, add 4 ml of ion-exchanged water, mix well, and immediately measure the absorbance at 535 nm. Taking the glucose concentration on the horizontal axis and the absorbance on the vertical axis, the slope is obtained, and the conversion factor (F) is calculated as follows.
F-1 / (tilt) × 1/15 × 1 / 0.1
(6) Calculation of activity Calculate enzyme activity by the following formula.
Activity (U / L) = σ absorbance × F × dilution factor σ absorbance = (absorbance of sample) − (absorbance of blank)
(7) Preparation of DNS reagent (1L)
16 g of sodium hydroxide is dissolved in 200 ml of ion exchange water. To this, 5 g of DNS is gradually added and dissolved. After completely dissolving the DNS, add 300 g of sodium potassium tartrate. After completely dissolving, it is adjusted to 100 ml with ion exchange water.

  Examples of proteases include alcalase, sabinase (both Novo Nordic), API-21 (Showa Denko Co., Ltd.), Maxacal (Gist Procaides). Preferably, it is a product produced by a fungus derived from Bacillus sp. For example, alkaline protease K-14 (Bacillus. Protease K-16 (Bacillus.sp KSM-16 (Microtechnological Laboratories No. 11418)) The enzyme activity is preferably 0.1 to 1000 APU / L, more preferably 1 to 100 APU / L. The specific blending amount in the composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and particularly preferably 0.1 to 1% by mass. The enzyme activity of the protease is measured by an improved method of Anson-hemoglobin method [Anson. MLJ Gen. Physiol., Vol. 22, p79 (1938)], that is, urea used as a substrate. Modified hemog In a solution prepared so that the final concentration of the bottle is 14.7 mg / ml, after reacting at a temperature of 25 ° C. and a pH of 10.5 for 10 minutes, trichloroacetic acid is added to the reaction solution to a final concentration of 31.25 mg / ml. The trichloroacetic acid soluble component is colored with a phenol reagent, and the activity per 10 minutes of reaction is obtained from a calibration curve with the coloration degree of 1 mmol of tyrosine as 1 APU. Therefore, in the present invention, 1 APU is the amount of alkaline protease that gives a soluble amount of trichloroacetic acid in 1 minute with the same coloration as 1 mmol of tyrosine is colored by a phenol reagent. It shows that.

  In addition to the above, the bleaching detergent composition of the present invention can be blended with known components blended in the detergent or bleaching agent. An example is shown below.

(1) Acid agent An acid agent can be mix | blended so that pH of a washing | cleaning liquid (composition solution) may not become high too much. Examples of the acid agent include polycarboxylic acids such as lactic acid, succinic acid, malic acid, and gluconic acid in addition to the organic sequestering agent.

(2) Bulking agent As a bulking agent (neutral salt), sodium sulfate generally called mirabilite can be blended. Sodium sulfate is effective in forming the skeleton of the detergent particles after drying, like the inorganic alkaline agent. Other preferable neutral salts include sodium chloride and potassium chloride.

(3) Polymers [other than the component (d)]
Polyethylene glycol, polyvinyl alcohol, or the like can be blended as a binder or powder physical agent for densifying the composition. These polymers also have an effect of preventing recontamination on hydrophobic fine particles, and those having a weight average molecular weight of 200 to 200,000 can be used. Further, polyvinyl pyrrolidone can be blended in order to impart an effect of preventing color transfer.

(4) Enzyme stabilizer As the enzyme stabilizer, a calcium salt or magnesium salt of a reducing agent (sodium sulfite, sodium hydrogen sulfite), a polyol, a boron compound, or the like can be blended. The reducing agent stabilizes the enzyme by removing chlorine in tap water. Furthermore, sodium sulfite has an effect as an antioxidant in addition to the above effect.

(5) Blue tinting agent Examples of the blue tinting agent include those described in JP-B-49-8005, JP-B-49-26286, and JP-B-53-45808.

(6) Anti-caking agent Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like. Clay (smectite clay) is also effective as a softening agent.

(7) Fragrance As the fragrance, a fragrance conventionally blended in a detergent, for example, a fragrance described in JP-A No. 63-101696, dimethylbenzylcarbinyl acetate, tricyclo [5.2.1.0 ^2,6 ] -dece-3 -En-8-yl acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-ene-8-isopropionate, 3-amyl-4-acetoxytetrahydropyran, 4-tert-butylcyclohexyl acetate, 2 -Tert-butylcyclohexyl acetate, p-tert-butyl-α-methylhydrocinnamic aldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, Examples include α-amylcinnamic aldehyde, α, α'-dimethyl-p-ethylhydrocinnamic aldehyde, etc. be able to. Of course, in order not to cause deterioration due to other detergent components, the type and the blending ratio and blending amount of each fragrance component to be blended are considered.

(8) Antifoaming agent Examples of the antifoaming agent include conventionally known antifoaming agents such as silicone / silica. This antifoaming agent may be a defoaming agent granulated product produced by using the method described in JP-A-3-186307, page 4, left lower column. An example of a method for producing a defoamer granulated product is as follows. First, 20 g of silicone (compound type, PS antifoam) manufactured by Dow Corning Co., Ltd. as a defoaming component is added to 100 g of maltodextrin (enzyme modified dextrin) manufactured by Nissho Chemical Co., Ltd. Add and mix 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 anhydrous nitric acid at 70 to 80 ° C. were then manufactured. Granulate with an extrusion granulator (model EXKS-1) to obtain a granulated product.

  The bleaching detergent composition of the present invention contains the above components (a) and (b), more preferably components (c) to (e), an enzyme, and other components. It is granular. The composition of the present invention is suitable for bleach washing of textile products such as clothing and bedding.

<Washing method>

  In particular, the bleaching detergent composition of the present invention is used as an aqueous medium obtained by dissolving in a liquid component containing water. The density | concentration of the bleaching detergent composition in the said aqueous medium is 0.1 mass% or more, Preferably it is 0.2-5 mass%, More preferably, it is 0.3-2 mass%. The fiber product is brought into contact with the aqueous medium having such a concentration for 30 minutes or more, preferably 30 to 120 minutes. The temperature of the aqueous medium is preferably 5 to 50 ° C, more preferably 20 to 40 ° C. The aqueous medium preferably has a pH of 8 to 12 and more preferably 10 to 11 at the temperature during use.

  In addition, such an aqueous medium is applied to textile products by a method of directly applying or dripping it on a soiled part, and a method of filling and spraying a container with a spray such as a trigger type sprayer. You can also.

  An aqueous solution containing the granular bleaching detergent composition shown in Table 1 at a concentration of 0.5% by mass is prepared. 4 pieces of each of the curry-stained cloths prepared below are put into this aqueous solution and immersed for 2 hours. Thereafter, the contaminated cloth was taken out, put into a commercially available aqueous detergent solution having a concentration of 0.0667% by mass, and washed normally with a tartometer (80 rpm × 10 minutes). After rinsing with tap water and drying, the bleaching rate was calculated according to the following formula.

  The reflectance was measured with ND-300A manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

<Preparation of curry-contaminated cloth>
After removing the solid content of the retort curry made of house food (curry Marche: manufactured in December 2003) with a mesh, the obtained liquid was heated until it was boiled. Cotton gold cloth # 2003 was immersed in this solution and boiled for about 15 minutes. After removing from the fire as it was and leaving it to stand for about 2 hours, the cloth was taken out and the curry liquid adhering to the excess was removed with a spatula and allowed to dry naturally. Thereafter, it was pressed and subjected to an experiment as a 10 cm × 10 cm test piece.

1) Sodium percarbonate used contained 20% by mass as the hydrogen peroxide concentration.
2) Trade name “Tinopearl CBS-X”, manufactured by Ciba Specialty Chemicals 3) Sodium lauroyloxybenzenesulfonate 4) Acrylic acid-maleic acid copolymer, average molecular weight 70000 (trade name “Socaran CP-5”, BASF Made)
5) Trade name “Trilon M”, manufactured by BASF 6) Trade name “Termamyl”, activity 7000 U / g, Novo Industry 7) Trade name “alkaline protease K-16”, Bacillus sp. KSM-K16 (Microtechnological Laboratories No. 11418), activity 1.87 PU / mg, purified according to the reference example of JP-A-5-255492.
8) Linear alkyl (carbon number 12) sodium benzenesulfonate 9) Polyoxyethylene (ethylene oxide average addition mole number 10) alkyl (carbon number 12-14) ether

Claims (7)

(A) Bleaching containing 8 to 25% by mass of inorganic peroxide as hydrogen peroxide, (b) 0.01 to 1% by mass of optical brightener, and a surfactant content of 5% by mass or less Cleaning composition. The bleaching detergent composition according to claim 1, wherein (b) is a biphenyl type optical brightener. Further, (c) an alkanoyloxybenzenesulfonic acid having an alkanoyloxy group having 6 to 14 carbon atoms, an alkanoyloxybenzenecarboxylic acid having an alkanoyloxy group having 6 to 14 carbon atoms, and a compound selected from these salts are used in an amount of 5-20. The bleaching-cleaner composition of Claim 1 or 2 containing the mass%. The bleaching detergent composition according to any one of claims 1 to 3, further comprising (d) 1 to 5% by mass of a dispersant. The bleaching detergent composition according to any one of claims 1 to 4, further comprising 1 to 5% by mass of (e) a chelating agent [excluding (d)]. The bleaching detergent composition according to any one of claims 1 to 5, further comprising amylase and / or protease. A method for bleaching a textile product, comprising the step of bringing the textile product into contact with an aqueous medium containing the bleaching detergent composition according to any one of claims 1 to 6 at a concentration of 0.1% by mass or more for 30 minutes or more.