JP4498813B2 - Granules for cleaning agents - Google Patents

Description

  The present invention relates to a granulated product for detergent, a bleaching detergent composition suitable for textiles such as clothing containing the granulated product, and a method for bleaching and washing textile products using the granulated product for detergent. About.

  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. Powdered, granular bleaching agents and cleaning agents are added to laundry washing media, or concentrated aqueous media are prepared and applied to textile stains.

  In general, oxygen bleaching detergents are used in combination with various bleach activators (organic peracid precursors) because they have weaker bleaching power than chlorine bleaching detergents. As typical bleach activators, tetraethylenediamine, alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid, tetraacetylglycolyluril, glucose pentaacetate and the like are known (Patent Documents 1 to 3).

A powder or granular oxygen-based bleaching detergent is required to have excellent solubility and that the powder component is stable in the composition. Patent Documents 4 to 7 disclose a technique in which components blended in a bleaching agent and a cleaning agent are used as a powder or a granulated product.
JP-A-11-217590 JP-A-10-95996 Japanese Patent No. 3320304 Japanese Patent Laid-Open No. 9-157597 JP 2001-152195 A JP-A-10-237498 Japanese Patent Laid-Open No. 9-20899

  The object of the present invention is excellent for various stains such as stain stains (stains derived from pigments such as foods and cosmetics), Eli stains (stains derived from sebum, etc.), and socks stains (composite stains such as sebum and mud). It is to provide a technique capable of imparting a bleaching effect, a cleaning effect, and excellent solubility to a powdered or granular oxygen-based bleaching agent or bleaching detergent.

  The present invention comprises (a) a compound selected from sodium carbonate and potassium carbonate (hereinafter referred to as component (a)) 40 to 90% by mass, (b) oleic acid, stearic acid, linoleic acid, palmitic acid and alkali metals thereof. 3 to 20% by mass of a compound selected from a salt or an alkaline earth metal salt (hereinafter referred to as component (b)), and (c) a polyhydric group having 10 to 18 carbon atoms and an average addition mole number of 2 to 5 Preparation for detergent containing polyoxyalkylene alkyl ether sulfate having an oxyalkylene group (oxyalkylene group has 2 to 4 carbon atoms) [hereinafter referred to as component (c)] in an amount of 3 to 20% by mass. Concerning grain.

  Moreover, this invention relates to the bleaching detergent composition containing the granulated material for detergents of the said invention, and an inorganic peroxide.

  Further, the present invention was prepared from a bleaching detergent composition containing 5% by mass or more of the above granulated product for detergent of the present invention, and 2 to 50 times the amount of water on a mass basis with respect to the composition. The present invention relates to a method for cleaning a textile product, which comprises a step of bringing an aqueous medium into contact with the textile product.

  According to the present invention, the bleaching detergent composition is imparted with excellent bleaching effect, cleaning effect and excellent solubility for various types of dirt such as sebum dirt, pigment dirt, inorganic dirt, and composite dirt of these. A granulated product is obtained.

<Granulated material>
[(A) component]
The component (a) is a compound selected from sodium carbonate and potassium carbonate, and is contained in the granulated product in an amount of 40 to 90% by mass, preferably 60 to 90% by mass, and more preferably 75 to 85% by mass. The component (a) is preferably sodium carbonate.

[Component (b)]
The component (b) is a compound selected from oleic acid, stearic acid, linoleic acid, palmitic acid, and alkali metal salts or alkaline earth metal salts thereof, preferably oleic acid, linoleic acid, and alkali metal thereof Compounds selected from salts or alkaline earth metal salts, oleic acid, linoleic acid, and alkali metal salts thereof are preferable, and oleic acid, linoleic acid, and sodium salts thereof are particularly preferable. Of these, an alkali metal salt (sodium salt) of oleic acid is preferable.

  The content of the component (b) in the granulated product of the present invention is 3 to 20% by mass, preferably 3 to 15% by mass, particularly from the viewpoint of imparting sufficient bleaching power and detergency. Preferably it is 4-7 mass%.

  In the granulated product of the present invention, the mass ratio of the component (a) and the component (b) is (b) / (a) = 1/50 to 1/5 in consideration of the combination of the dissolution rate and other components. More preferably, it is 1/30 to 1/6, and particularly preferably 1/20 to 1/8.

  In addition, the granulated product of the present invention may contain a compound selected from fatty acids and fatty acid alkali metal salts or alkaline earth metal salts other than the component (b), but is included in the granulated product. In the total amount of the compound selected from fatty acid and fatty acid alkali metal salt or alkaline earth metal salt, the ratio of (b) is 50% by mass or more, more preferably 60 to 100% by mass, and particularly 75 to 100% by mass, It is more preferable in terms of bleaching power and cleaning power of a bleaching agent and a cleaning agent using the granulated product.

[Component (c)]
The component (c) is a polyoxyalkylene having a hydrocarbon group having 10 to 18 carbon atoms, preferably an alkyl group and a polyoxyalkylene group having an average addition mole number of 2 to 5 (the oxyalkylene group has 2 to 4 carbon atoms). An alkylene alkyl ether sulfate (hereinafter referred to as component (c)). The polyoxyalkylene group is preferably a polyoxyethylene group. The component (c) is preferably a sodium salt.

  In the granulated product of the present invention, the mass ratio of the component (b) and the component (c) is (b) / (c) = 0.3-5, considering the improvement in solubility and the blending with other components. More preferably, it is 0.5-3, Most preferably, it is 0.7-1.5.

  The granulated product of the present invention preferably contains a surfactant other than the component (b) and the component (c) [hereinafter referred to as the component (d)]. As the surfactant of the component (d), an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be blended. Among these, an anionic surfactant, Nonionic surfactants are preferred.

  Examples of the anionic surfactant include sulfuric acid ester salt of linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α- A sulfo fatty acid salt, an α-sulfo fatty acid alkyl ester salt or a fatty acid salt [other than the component (b)] is preferred. As a counter ion, alkali metal salts are preferable, and sodium or potassium is particularly preferable. As the anionic surfactant, linear alkylbenzene sulfonates having 12 to 14 carbon atoms in the alkyl chain and alkyl sulfates having 12 to 18 carbon atoms are preferable.

  As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, as the nonionic surfactant, an HLB value obtained by adding 4 to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms (Griffin method) Of the polyoxyalkylene alkyl ether is 10.5 to 15.0, preferably 11.0 to 14.5.

  The content of the component (d) in the granulated product of the present invention is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, considering the improvement in solubility and the blending with other components. %, Particularly preferably 0.1 to 1% by mass.

  The granulated product of the present invention is produced by drying an aqueous solution or water slurry obtained by adding and mixing the component (a), the component (c) and other components to the aqueous solution containing the component (b). be able to. The drying is preferably spray drying. If necessary, the particle size may be adjusted by sieving.

  In the granulated product of the present invention, it is preferable from the viewpoint of improving solubility that 50% by mass or more, further 70% by mass or more, particularly 90% by mass or more of the particles are particles having a particle diameter of 125 μm to 500 μm. The average particle size of the granulated product of the present invention is preferably 125 to 400 μm, more preferably 200 to 350 μm.

<Bleaching detergent composition>
The bleaching detergent composition of the present invention contains 5% by mass or more, preferably 5 to 70% by mass, more preferably 20 to 70% by mass, and particularly preferably 40 to 60% by mass of the granulated product of the present invention. .

  In addition, the bleaching detergent composition of the present invention preferably contains 1 to 25% by mass, more preferably 8 to 25% by mass, of hydrogen peroxide as an inorganic peroxide for imparting sufficient bleaching power and detergency. More preferably, it contains 10 to 25% by mass. Examples of the inorganic peroxide include inorganic peroxide salts such as percarbonate, perborate and perphosphate, and among these, percarbonate is preferable. The salt is preferably an alkali metal salt such as a sodium salt or a potassium salt.

  The average particle size of the inorganic peroxide is preferably 200 to 1000 μm, particularly preferably 250 to 400 μm. 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.

  Further, the bleaching detergent composition of the present invention preferably contains a surfactant as described in the granulated product, and preferably contains an anionic surfactant and a nonionic surfactant. The content of the surfactant in the bleaching detergent composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass from the viewpoint of imparting sufficient bleaching power and detergency. Especially preferably, it is 5-10 mass%.

  The bleaching detergent composition of the present invention preferably contains an organic peracid precursor that reacts with hydrogen peroxide in water to generate an organic peracid. The organic peracid precursor is selected from alkanoyloxybenzenesulfonic acid having an alkanoyloxy group having 6 to 14 carbon atoms, alkanoyloxybenzenecarboxylic acid having an alkanoyloxy group having 6 to 14 carbon atoms, and salts thereof. Compounds are preferred.

  Examples of the organic peracid precursor include a compound represented by the following general formula (1).

[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 (1), when R ¹ has 5 or more carbon atoms, it has a high adsorptivity to dirt and can exhibit sufficient bleaching and washing performance. If it is 13 or less, it is sufficient even under low temperature washing conditions. It is preferable because it can provide high solubility.

  As the compound corresponding to the general formula (1), those represented by the following general formula (2) or (3) are 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 improve the stability of the organic peracid precursor, it can be mixed with a water-soluble binder and other components to form a granulated product. For the granulated product of the organic peracid precursor component, the description in paragraphs 0017 to 0022 of JP-A No. 11-217590 can be referred to.

  The content of the organic peracid precursor in the bleaching detergent composition of the present invention is preferably 0.5 to 20% by mass, more preferably imparting sufficient bleaching power and detergency, and preventing caking. Is 2 to 15% by mass, particularly preferably 3 to 10% by mass.

  The bleaching detergent composition of the present invention preferably contains a dispersant. Examples of the dispersant include a carboxylic acid polymer (1) polyacrylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer. Examples thereof include acrylic acid polymers such as coalescence, and (2) polyvalent carboxylic acid polymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, and aspartic acid. Moreover, high molecular compounds, such as (3) glyoxylic acid type polymer and (4) polysaccharide (cellulose derivatives, such as carboxymethylcellulose), are mentioned.

  As the dispersant, a carboxylic acid polymer having a weight average molecular weight of several hundred to 100,000, particularly an acrylic acid polymer is preferable. 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 dispersant in the bleaching detergent composition of the present invention is preferably 1 to 5% by mass, more preferably 2 to 4% by mass in consideration of blending with other components while giving sufficient dispersibility. And particularly preferably 3 to 4% by mass.

  The bleaching detergent composition of the present invention preferably contains a chelating agent (except for the above dispersant). Examples of the chelating agent include (1) phosphoric acid compounds such as phytic acid or their salts, (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy- Phosphonic acids such as 1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid or salts thereof (3 ) Phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid or their salts; (4) glycine or derivatives thereof. Amino acids such as aspartic acid and glutamic acid or salts thereof, (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydride Roxyethyliminodiacetic acid, triethylenetetraamine hexaacetic acid, aminopolyacetic acid such as diencoric acid or their salts, (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, Organic acids such as malic acid, succinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid or their salts, (7) aluminosilicates such as zeolite A, (8) aminopoly (methylenephosphonic acid) or their salts Or polyethylene polyamine poly (methylene phosphonic acid) or a salt thereof.

As the chelating agent, those satisfying the Ca che stability 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 chelating agent is preferably 4.5 or more, more preferably 5 to 12, in order to capture hardness components such as Ca ²⁺ and increase bleaching power and detergency. Especially preferably, it is 6-10.

  Further, when the bleaching detergent composition of the present invention contains an organic peracid precursor, the chelating agent preferably has an organic peracid residual ratio of 80% or more 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 ion exchange water at 35 ° C. is prepared in a 1 L beaker, and 0.1 mmol / L of organic peracid precursor is added thereto. . The addition concentration of the organic peracid precursor at this time is expressed by the following formula:

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 rate at 20 ° C. of the chelating agent is preferably 80% or more, more preferably 90% or more, particularly preferably, in order to suppress the decomposition of the organic peracid precursor and increase the bleaching power and detergency. Is 95% or more.

  As a chelating agent, what is represented by following General formula (4) 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). ]

  As a chelating agent applicable to General formula (4), what is represented by a following formula can be mentioned.

  The content of the chelating agent 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 power and detergency. Most preferably, it is 2-3 mass%.

  In the bleaching detergent composition of the present invention, the mass ratio of the component (a) to the component (d) is (a) / (d) = 30/1 to 1/1 in terms of the production efficiency of organic peracid. Further, 15/1 to 3/1, particularly 10/1 to 5/1 is preferable.

<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 Put 0.5 ml of substrate solution into a test tube, add 0.4 ml of 100 mM Glycine-NaOH buffer (pH = 10.0), and add 1 ml of DNS solution there, and develop color accurately 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 to 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.sp KSM-14 (No. 12587) by Kojiken Bacteria) and alkali described in JP-A-5-25492 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 the 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 to be blended with the detergent or the 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 an organic sequestering agent and polycarboxylic acids such as lactic acid, succinic acid, malic acid, and gluconic acid.

(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 (e)]
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. are then mixed. Granulate with an extrusion granulator (model EXKS-1) to obtain a granulated product.

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

  The bleaching detergent composition of the present invention may contain components (a) to (c) in addition to those in the granulated product of the present invention, but all (a) in the composition In the component, the component (a) in the granulated product is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and the component (b) in the granulated product in all the components (b) in the composition. The component is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and the total (c) component in the composition, the (c) component in the granulated product is 60 to 100% by mass, and further 80 to 80%. It is preferable that it is 100 mass%.

<Washing method>
The method for washing a textile product of the present invention comprises a bleaching detergent composition containing 5% by mass or more of the granulated product for detergent of the present invention, preferably the bleaching detergent composition of the present invention and the composition. A step of contacting a textile product with a concentrated aqueous medium prepared from 2 to 50 times the amount of water on a mass basis.

  In the present invention, the component (b) in the granulated product improves the cleaning power and bleaching power of the cleaning composition and the bleaching cleaning composition containing an inorganic peroxide. In order to improve the dissolution and dispersion rate of the component (b), in the present invention, the (a) component and the (c) component are used in combination in the granulated product. Such a granulated product can improve the detergency and bleaching power of the composition when blended with a bleaching detergent composition containing 1 to 20% by mass of inorganic peroxide as hydrogen peroxide. The bleaching detergent composition of the present invention is preferably brought into contact with the article to be cleaned by setting the aqueous solution containing the component (b) and hydrogen peroxide to 9 or more by a method of adding water to the composition and dissolving it. Since the powder bleach detergent composition containing the granulated product of the present invention is excellent in solubility, a bleach washing method for clothing in which a concentrated aqueous medium is prepared and brought into contact with the article to be cleaned can be easily implemented. .

  Therefore, the bleaching detergent composition of the present invention may be diluted with a weak alkaline detergent in a washing bath and washed in a washing machine or the like, but an aqueous medium containing the composition and water may be used. In order to obtain a high effect, a method of cleaning by directly contacting with dirt attached to clothing or the like is preferable. As a method of contact, a method of immersing the aqueous medium in a textile product, a method of directly applying or dripping on a soiled portion, and a method of spraying by filling a sprayed container such as a trigger sprayer. From the viewpoint of simplicity, a method of directly applying or dripping and adhering to a portion where dirt is attached is preferable. The contact time is preferably 5 to 480 minutes, more preferably 5 to 300 minutes, particularly preferably 10 to 300 minutes, and particularly preferably 30 to 200 minutes from the viewpoint of the cleaning effect. Moreover, as temperature to contact, Preferably it is 2-50 degreeC, More preferably, it is 5-40 degreeC.

  Washing clothes after contact washing with tap water or laundering with a weak alkaline detergent and rinsing is suitable, and washing with a weak alkaline detergent in particular removes the washing effect more efficiently. Preferred above. After rinsing, dehydrated and dried by natural drying or dryer.

  In particular, in the bleaching and cleaning method of the present invention, the bleaching detergent composition of the present invention is 0.1 to 10% by mass, preferably 1 to 8% by mass, more preferably 3 as component (a) hydrogen peroxide. -7% by mass, component (b) is contained in an amount of 0.1-10% by mass, preferably 1-8% by mass, more preferably 2-5% by mass, and the pH is 9 or more, preferably 9. It is preferable to contact the fiber product with an aqueous medium of 5-11. This pH is the pH at the time of washing. The contact time is preferably 5 minutes or longer, and more preferably 30 to 120 minutes. Moreover, the temperature of an aqueous medium is 5-50 degreeC, Furthermore, 20-40 degreeC is preferable.

  As a method for preparing and applying the aqueous medium used in the cleaning method of the present invention, for example, a cap having a coating means and a container to which the cap can be attached are prepared, and the composition and water are mixed at a predetermined ratio in the container. And then applying the aqueous medium to an object to be cleaned such as clothing. In this case, all or part of the aqueous medium is applied. The remainder of the aqueous medium can be used by mixing with a washing medium for washing. The article to be cleaned thus treated can be subjected to normal washing, or can be rinsed as it is to finish washing. In any case, after applying the aqueous medium, it is preferable to leave it for a certain time (for example, 1 to 2 hours). This aqueous medium is suitable as a bleaching detergent composition for coating and washing, and the composition comprises a step of directly contacting (coating, dipping, etc., preferably coating) dirt adhering to clothing without dilution. It can use for the washing | cleaning method of the clothing which has.

Examples 1-3 and Comparative Examples 1-4
<Method for producing granulated product>
In Table 1, the other components shown in Table 1 were mixed with the 10% by mass aqueous solution of component (b) at the ratio shown in Table 1, and spray-dried at a hot air temperature of 180 ° C. to obtain a dried product. The dried product was sieved, and a granulated product having a particle size of 125 to 500 μm was obtained.

<Method for evaluating dissolution rate>
To a 100 ml glass container, add 2.5 g of the granulated product and 50 ml of ion exchange water at 20 ° C., and use TAIYO RECIPRO SHAKER SR-2 as a shaker. The number of shakings was visually observed. Dissolution was confirmed by the colorless and transparent mixture. The results are shown in Table 1.

* 1: Sodium polyoxyethylene lauryl ether sulfate ester (average number of moles of ethylene oxide added 3)
* 2: Linear alkyl (carbon number 12) sodium benzenesulfonate * 3: Polyoxyethylene (ethylene oxide average addition mole number 10) alkyl (carbon number 12-14) ether * 4: Alkyl (carbon number 12-14) sulfuric acid sodium

Examples 4-6 and Comparative Examples 5-9
The granulated product of Table 1 and the other components shown in Table 2 were mixed at the ratio shown in Table 2 to obtain a bleaching detergent composition. About the obtained bleaching detergent composition, dissolution rate was evaluated like Example 1 etc. (however, it replaces with 2.5 g of granulated materials and uses 2.5 g of bleaching detergent composition). The results are shown in Table 2.

In Table 2, (c-1) and the anionic surfactant (1) are the same as those in Table 1. The other components are as follows.
* 5: Sodium percarbonate having a hydrogen peroxide concentration of 20% by mass was used.
* 6: Sodium lauroyloxybenzenesulfonate * 7: Acrylic acid-maleic acid copolymer, average molecular weight 70000 (trade name “Socaran CP-5”, manufactured by BASF)
* 8: Trade name "Trillon M", manufactured by BASF * 9: Trade name "Termamyl", active 7000 U / g, manufactured by Novo Industry

Claims (6)

(A) Compound 40 to 90% by mass selected from sodium carbonate and potassium carbonate, (b) Compound 3 selected from oleic acid, stearic acid, linoleic acid, palmitic acid and alkali metal salts or alkaline earth metal salts thereof. 20% by mass, and (c) a polyoxyalkylene alkyl ether having a hydrocarbon group having 10 to 18 carbon atoms and a polyoxyalkylene group having an average addition mole number of 2 to 5 (the oxyalkylene group has 2 to 4 carbon atoms) A granulated product for detergent containing 3 to 20% by mass of sulfate in the same particle. (B) / (c) The mass ratio is 0.5 to 3, (b) / (a) the mass ratio is 1/50 to 1/5, and 50% by mass or more of the particles have a particle diameter of 125 μm to 500 μm. The granulated product for a cleaning agent according to claim 1, wherein A bleaching detergent composition comprising the detergent granule according to claim 1 or 2 and an inorganic peroxide. An aqueous medium prepared from a bleaching detergent composition containing 5% by mass or more of the granulated product for detergent according to claim 1 or 2, and 2 to 50 times the amount of water on a mass basis with respect to the composition. A method for bleaching and washing textile products, comprising the step of contacting the textile products. The cleaning method according to claim 4, wherein the pH of the aqueous medium is 9 or more. The method according to claim 4 or 5, wherein the aqueous medium contains 0.2 to 10% by mass of hydrogen peroxide.