JP5282280B2 - Powder detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-foamable powdered detergent composition having high detergency and good rinsing performance in combination. <P>SOLUTION: The powdered detergent composition contains (a) a polyoxyethylene alkyl (or alkenyl) ether having a 16-20C alkyl or alkenyl group and an average addition number of moles of ethylene oxide of 3-20: 3-20 mass%, (b) one or more water-soluble chelating agents selected from the group consisting of amino carboxylic acid, condensed phosphoric acid, and salts thereof: 7-50 mass%, (c) a silicate with SiO<SB>2</SB>/M<SB>2</SB>O(M represents an alkali metal)=1/1-1/2(molar ratio): 5-30 mass%, and (d) M<SB>2</SB>CO<SB>3</SB>(M represents an alkali metal): 10-40 mass%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a powder detergent composition suitable for use in textile products such as clothing.

When washing linens such as hotel and hospital sheets, wrapping cloth, towels, and restaurant cloths, a continuous washing machine that performs a series of operations from washing to dehydration, drying, etc. at once, and a large batch type fully automatic washing and dehydration 2. Description of the Related Art A washing machine capable of washing a large amount of objects to be washed such as a batch washer is used. Such a washing machine is mainly used by a cleaning company, but a low-foaming detergent is preferable in order to improve work efficiency. Therefore, the cleaning composition which uses a nonionic surfactant or soap as the main base material is mainly used (for example, refer patent documents 1-11). However, in general, low-foaming detergents have good rinsing properties but low detergency. Conversely, increasing the detergency tends to improve foaming and tend to deteriorate rinsing properties.
On the other hand, in order to improve the cleaning power of the cleaning agent, it is desirable to increase the pH of the cleaning liquid. As the pH improver, it is desirable to add a strong alkaline agent, but when the rinsing is insufficient and the alkaline agent remains in the article to be washed after rinsing, the article to be washed turns yellow after drying. It is known that it is easy to produce (for example, refer patent document 2).
In the field of business use, washing with a high detergent concentration and high alkali compared to household goods, alkali rinsing is likely to occur if rinsing is insufficient. In particular, sheets and the like may be dried at a high temperature with a calender roll, and one of the problems is to make the objects to be washed with alkali.

JP 2002-180087 A Japanese Patent Laid-Open No. 2001-139988 Japanese Patent Laid-Open No. 2002-194397 JP 2003-013094 A JP 2001-164195 A Japanese Patent Laid-Open No. 11-080798 JP 2001-172681 A JP 2000-336399 A JP 2000-096094 A JP 2002-235094 A JP 2007-016246 A

  This invention makes it a subject to provide the low-foaming powdery detergent composition which has high detergency and favorable rinse property in view of the said situation.

As a result of intensive studies to solve the above problems, the present inventors combined a specific nonionic surfactant with a silicate and a carbonate represented by a specific molar ratio as an alkali agent. The inventors have found that the above-described problems can be achieved by using a specific water-soluble chelating agent in combination and further defining the amount of each compound, and the present invention has been completed.
That is, the present invention
(A) a polyoxyethylene alkyl (or alkenyl) ether having an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average addition mole number of ethylene oxide of 3 to 20: 3 to 20% by mass;
(B) one or more water-soluble chelating agents selected from the group consisting of aminocarboxylic acids, condensed phosphoric acids and salts thereof: 7 to 50% by mass;
(C) SiO ₂ / M ₂ O (M represents an alkali metal) = 1/1 to 1/2 (molar ratio) silicate: 5 to 30% by mass, and (d) M ₂ CO ₃ (M Represents an alkali metal): 10 to 40% by mass
A powder detergent composition containing

The present invention also provides
(B) a first composition comprising one or more water-soluble chelating agents selected from the group consisting of aminocarboxylic acids, condensed phosphoric acids and salts thereof;
(A) a polyoxyethylene alkyl (or alkenyl) ether having an alkyl group or an alkenyl group having 16 to 20 carbon atoms and an average addition mole number of ethylene oxide of 3 to 20, (c) SiO ₂ / M ₂ O ( A second composition comprising a silicate, wherein M represents an alkali metal) = 1/1 to 1/2 (molar ratio) and (d) M ₂ CO ₃ (M represents an alkali metal),
Based on the total amount of the first composition and the second composition, the component (b) is 7 to 50% by mass, the component (a) is 3 to 20% by mass, and the component (c) is 5 to 30% by mass. , (D) The powder detergent kit characterized by combining in the quantity used as 10-40 mass% is provided.

The present invention also provides
Based on the total amount of the composition,
(A) a polyoxyethylene alkyl (or alkenyl) ether having 3 to 20% by mass of an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average added mole number of ethylene oxide of 3 to 20,
(B) one or more water-soluble chelating agents selected from the group consisting of 7 to 50% by weight of aminocarboxylic acid, condensed phosphoric acid and salts thereof;
(C) 5 to 30% by mass of SiO ₂ / M ₂ O (M represents an alkali metal) = 1/1 to 1/2 (molar ratio), and (d) 10 to 40% by mass of silicate M ₂ CO ₃ (M represents an alkali metal)
Use of the component (b) for producing a powder detergent composition containing

  According to the present invention, a low-foaming powder detergent composition having improved detergency and rinsing properties can be obtained.

Component (a) The non-nonionic surfactant used as the component (a) of the present invention is an alcohol having an alkyl group or alkenyl group having 16 to 20 carbon atoms, and an average of 3 to 20 moles of ethylene oxide, preferably 5 Polyoxyethylene alkyl (or alkenyl) ether added at -18, more preferably an alkyl group or alkenyl group having 16 to 18 carbon atoms, preferably an average mole number of 7 to 15 ethylene oxide in an alcohol having an alkyl group. Is a polyoxyethylene alkyl (or alkenyl) ether added in The alkyl group or alkenyl group of the alcohol may be linear or branched, but is preferably linear. In addition, the average added mole number of ethylene oxide in the component (a) can be measured using proton NMR or the like.
(A) A component may be used independently or may use 2 or more types together. When used in combination, the alkyl group or alkenyl group of the alcohol is preferably a mixture of C16 and C18. At this time, the component (a) in which the alkyl group or alkenyl group of the alcohol is C16 and the component (a) in which the alkyl group or alkenyl group of the alcohol is C18 in particular are C16 / C18 = 0 / It is preferably 10 to 10/1.
The HLB of the component (a) is preferably 6 to 17, more preferably 8 to 16, and particularly preferably 9 to 15 from the viewpoint of detergency. The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The component (a) can be produced by a method known in the art, or a commercially available product can be used. As a commercial item, the product name Emarex 611 by Nippon Emulsion Co., Ltd. is mentioned, for example.

  The blending amount of the polyoxyethylene alkyl (or alkenyl) ether of the component (a) in the powder detergent composition is 3% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and 20 It is not more than mass%, preferably not more than 18 mass%, more preferably not more than 15 mass%. When the proportion of the component (a) is 3% by mass or more, sufficient cleaning performance can be obtained. On the other hand, even if the proportion of the component (a) exceeds 20% by mass, the cleaning effect does not improve and is not economical, but if it is 20% by mass or less, the amount of other active ingredients can be sufficiently secured, The effects of the present invention are sufficiently obtained, and the fluidity of the manufactured powder detergent composition is improved.

(B) Component The water-soluble chelating agent used as the component (b) of the present invention is one or more selected from the group consisting of aminocarboxylic acids, condensed phosphoric acids, and salts thereof. Specifically, it is one or more chelating agents selected from the following (1) to (2).

(1) Aminocarboxylic acid (salt)
Nitrilotriacetic acid (salt) (NTA), methylglycine diacetate (salt) (MGDA), β-alanine diacetate (salt) (ADAA), isoserine diacetate (salt) (ISDA), aspartate diacetate (salt) (ASDA) , Serine diacetate (salt), glutamate diacetate (salt) (GLDA), iminodisuccinic acid (salt) (IDS), hydroxyiminodisuccinic acid (salt) (HIDS), ethylenediaminetetraacetic acid (salt) (EDTA), hydroxyethyl Ethylenediaminetriacetic acid (salt), dihydroxyethylglycine (salt), and the like. Examples of counter ions of these salts include alkali metal ions such as sodium ions and potassium ions.
(2) Condensed phosphoric acid (salt)
Examples include orthophosphoric acid (salt), pyrophosphoric acid (salt), tripolyphosphoric acid (salt) (STPP), metaphosphoric acid (salt), hexametaphosphoric acid (salt), and phytic acid (salt). Examples of counter ions of these salts include alkali metal ions such as sodium ions and potassium ions.

The aminocarboxylic acid (salt) in the present invention is preferably nitrilotriacetate, methylglycine diacetate, isoserine diacetate, aspartate diacetate, or hydroxyiminodisuccinate. In particular, sodium nitrilotriacetate (product example: “Trilon A92R” (manufactured by BASF Japan)), methyl glycine diacetate trisodium (product example: “Trilon (registered trademark) M powder” (manufactured by BASF Japan) ), Hydroxyiminodisuccinate tetrasodium (product example: “HIDS” (manufactured by Nippon Shokubai Co., Ltd.)), aspartate diacetate tetrasodium (product example: “Crewat Bi-ADS” (manufactured by Nagase ChemteX Corporation) )), Trisodium isoserine diacetate (commercial example: “Trilon (registered trademark) ES9910” (manufactured by BASF Japan Ltd.)).
As the condensed phosphoric acid (salt) in the present invention, tripolyphosphate and pyrophosphate are preferable. In particular, sodium tripolyphosphate (product example: “tripolyphosphate sodium” (manufactured by Mitsui Chemicals, Inc.)) and sodium pyrophosphate (product example: “sodium pyroacid” (manufactured by Mitsui Chemicals, Inc.)) are preferred.
As the component (b), an aminocarboxylate is preferable. Among the components (b), methyl glycine diacetate and hydroxyimino disuccinate are particularly preferable. More particularly, trisodium methylglycine diacetate and tetrasodium hydroxyiminodisuccinate are preferred.

  The blending amount of the component (b) in the powder detergent composition is 7% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more. On the other hand, the upper limit is 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less. When the proportion of the component (b) is 7% by mass or more, the washing performance of the manufactured powder detergent composition is improved and the rinsing property is improved, and further, the precipitation of insoluble alkali salt is suppressed by the chelating effect, As a result, it becomes difficult for alkali to be generated. On the other hand, when the proportion of the component (b) is 50% by mass or more, the fluidity of the powder detergent composition is lowered, and the raw material tends to adhere to the production apparatus during the production of the powder detergent composition.

  There are various grades of chelating agent powder which is commercially available component (b), and any grade can be used. For example, those containing impurities mixed in the manufacturing process, storage stabilizers for stabilizing the quality, and antioxidants are also included in the scope of the present invention. Moreover, it is good also as a powder state by drying the liquid or slurry-form chelating agent which can be obtained commercially. In the case of using a liquid or slurry-like chelating agent, it may be made into a powder by making it into a liquid or slurry containing, for example, an inorganic salt, a surfactant, a polymer or the like as another component and then drying. Although there is no restriction | limiting in particular as a drying method, Spray drying and fluidized-bed drying are used suitably. In addition, the amount of the pure component of the chelating agent in the component (b) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. Moreover, it is preferable that the water | moisture content of (b) component is 10 mass% or less from the surface of manufacturability. The water content is measured by the heat loss method described in JIS K3362-1998.

(C) Component The silicate used as the (c) component of the present invention is selected from silicates of SiO ₂ / M ₂ O (M represents an alkali metal) = 1/1 to 1/2 (molar ratio). One or more.
Examples of the silicate used as the component (c) of the present invention include sodium silicate salts having a SiO ₂ / M ₂ O (molar ratio) of 1/1 to 1/2 and those containing potassium silicate as a main component. .
Specific examples of preferred silicates include sodium orthosilicate (product example: “granular ortho” (manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ / Na ₂ O (molar ratio) = 1/2)), sodium sesquisilicate ( SiO ₂ / Na ₂ O (molar ratio) = 1 / 1.5), sodium metasilicate (product example: “anhydrous sodium metasilicate” (produced by Occidental Chemical Co., Ltd., SiO ₂ / Na ₂ O (molar ratio)) = 1/1).

  As for the compounding quantity of the said (c) component in a powder detergent composition, a lower limit is 5 mass% or more, Preferably it is 7 mass% or more, More preferably, it is 10 mass% or more. On the other hand, the upper limit is 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. If the compounding amount in the component (c) in the powder detergent composition is 5% by mass or more, the alkali concentration in the cleaning liquid becomes sufficient, and thus the cleaning power is improved. On the other hand, if it is 30% by mass or more, the hygroscopicity of the powder detergent composition is increased, and the productivity is lowered.

(D) (d) of component present invention (where M represents an alkali metal) M ₂ CO ₃ is at least one selected from carbonates is.
Specific examples of preferred carbonates include sodium carbonate (product examples: “grain ash” (manufactured by Soda Ash Japan), “light ash” (manufactured by Soda Ash Japan)), potassium carbonate (product examples: “Potassium carbonate (powder)” (manufactured by Asahi Glass Co., Ltd.). Sodium carbonate is particularly preferred.

  The blending amount of the carbonate of component (d) in the powder detergent composition is in terms of manufacturability, and the lower limit is 10% by mass or more, preferably 12% by mass or more, more preferably 15% by mass or more. is there. The upper limit is 40% by mass or less, preferably 37% by mass or less, and more preferably 35% or less. When the carbonate is 40% by mass or more, not only the effect of improving the detergency is not substantially recognized, but also the rinsing property is deteriorated and the problem of alkali burning occurs, which is not preferable.

In the powder detergent composition of the present invention, in addition to the above essential components, the following optional components that are usually blended in the detergent composition can be blended as necessary within a range not impeding the effects of the present invention.
In the present invention, it is preferable to further blend a carboxylic acid polymer or a salt thereof as the component (e) in terms of detergency.
Specific examples of the component (e) include acrylic acid, maleic acid, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid and other polymers or copolymers, starch, cellulose, Examples thereof include polysaccharide oxides such as amylose and pectin, polysaccharides such as carboxymethylcellulose, and polyacetal carboxylates.
In this invention, (e) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
Examples of the carboxylic acid-based polymer salt in the present invention include polyacrylate (product example: “Sokalan PA30 Granules” (manufactured by BASF Japan Ltd.)), a salt of a copolymer of acrylic acid and maleic acid (product example: “ Sokalan CP7 Granules "(manufactured by BASF Japan Ltd.)) is preferred. A copolymer salt of acrylic acid and maleic acid is more preferred.

The copolymerization ratio of acrylic acid / maleic acid in the acrylic acid / maleic acid copolymer salt of component (e) of the present invention is preferably acrylic acid / maleic acid = 50 / 50-80 / 20, more preferably in molar ratio. 60/40 to 70/30. The weight average molecular weights of the polyacrylate and the copolymer salt of acrylic acid and maleic acid are each 1000 or more, preferably 2,000 to 200,000, more preferably 5,000 to 100,000, Preferably it is 10,000-70,000. In addition, the weight average molecular weight of the salt of the polyacrylic acid salt and the copolymer of acrylic acid and maleic acid in the present invention is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.
The blending amount of the component (e) is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and the upper limit is 20% or less, preferably with respect to the composition. Is preferably contained in a mass of 18% by mass or less, particularly preferably 15% or less. The effect of this invention improves because this compounding quantity is 1 mass% or more. On the other hand, even if the upper limit value is 20% by mass or less, sufficient detergency can be obtained, which is economically advantageous.

(A) Surfactant Nonionic surfactants other than the component (a), anionic surfactants, cationic surfactants and amphoteric surfactants may be mentioned, and these may be used alone or in combination of two or more. be able to.
Examples of the nonionic surfactant other than (a) include the following.
(1) Polyoxyethylene alkyl (or alkenyl) ethers other than those described in component (a) (2) Polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether (3) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(4) Fatty acid alkyl ester alkoxylates represented by, for example, the following general formula (I) in which alkylene oxide is added between ester bonds of long-chain fatty acid alkyl esters.
R ¹ CO (OA) _n OR ² (I)
(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 carbon atoms. Represents an addition unit of oxide, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ₂ may have a substituent of 1 to 4 carbon atoms. A good lower (C1-C4) alkyl group is shown.)

(5) Polyoxyethylene sorbitan fatty acid ester.
(6) Polyoxyethylene sorbite fatty acid ester.
(7) Polyoxyethylene fatty acid ester.
(8) Polyoxyethylene hydrogenated castor oil.
(9) Glycerin fatty acid ester.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
The blending amount of the nonionic surfactant other than (a) in the composition of the present invention is preferably 20% by mass or less, and more preferably 10% by mass or less. In particular, when (1) is included, the blending amount of (1) is preferably 50% by mass or less with respect to the total amount of component (a) contained in the composition.

The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkane sulfonate (SAS) having 10 to 20 carbon atoms.
(3) Alkyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less, ethylene oxide, propylene oxide, butylene oxide or a mixture thereof. Sulfate (AES) or alkenyl ether sulfate.
(4) Alkyl ether added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less. Carboxylate or alkenyl ether carboxylate.
(5) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(6) A higher fatty acid salt having 10 to 20 carbon atoms.
(7) C8-20 saturated or unsaturated α-sulfo fatty acid (α-SF) salt or methyl, ethyl or propyl ester thereof.
As the anionic surfactant, a higher fatty acid salt is preferable.

  Examples of the cationic surfactant include mono, di, and trialkyl cations having 1 to 3 long chain hydrocarbon groups. In particular, a cationic surfactant containing 1 to 2 ester groups and 1 to 2 long-chain hydrocarbon groups in the molecule is preferable. Specifically, long-chain alkyl groups having 8 to 22 carbon atoms, mono-long-chain alkyltrimethylammonium chloride containing one alkenyl group, long-chain alkyl groups having 8 to 22 carbon atoms, and di-long-chain alkyl containing two alkenyl groups Dimethylammonium chloride, long-chain alkyl group having 8 to 22 carbon atoms, tri-long-chain alkylmethylammonium chloride containing 3 alkenyl groups, long-chain alkyl group having 8 to 22 carbon atoms, and N-acyllo having 1 alkenyl group Iroxyethyl-N, N-dimethyl-N-hydroxyethylammonium chloride, long chain alkyl group having 8 to 22 carbon atoms, N, N-di (acyloyloxyethyl) -N, N- containing two alkenyl groups Examples thereof include dimethylammonium chloride.

  As the amphoteric surfactant, sulfobetaine or carboxybetaine having one or two long chain groups can be used.

(B) Water-soluble chelating agents other than (b) component Water-soluble chelating agents other than (b) component are mentioned, These can be used individually by 1 type or in combination of 2 or more types. As chelating agents other than the component (b), hydroxyacetate, tartrate, citrate, gluconate, pyromellitic acid salt, benzopolycarboxylate, cyclopentanetetracarboxylate, carboxymethyltaltronate, Examples include ether carboxylates such as carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate.

(C) Inorganic salt Examples of inorganic salts other than the components (c) and (d) include the following water-soluble inorganic salts and water-insoluble inorganic salts.
(1) Water-soluble inorganic salt Examples of the water-soluble inorganic salt include sodium bicarbonate, sodium sesquicarbonate, and sulfate.
Specific examples of sodium sesquicarbonate (product example: “Sesqui ™ Sodium Sequicalbonate” (manufactured by FMC, USA)), sodium bicarbonate (product example: “sodium bicarbonate industrial weight” (manufactured by Asahi Glass Co., Ltd.)), and sulfate Examples thereof include sodium sulfate (product example: “neutral anhydrous sodium sulfate” (manufactured by Shikoku Kasei Kogyo Co., Ltd.)) and potassium sulfate (product example: “potassium sulfate” (manufactured by Takasugi Pharmaceutical Co., Ltd.)).
(2) Water-insoluble inorganic salts Examples of water-insoluble inorganic salts include crystalline and amorphous aluminosilicates, etc., but continuous washing machines (multiple drum-type washing machine tanks) used in the linen supply field. Since the used water is circulated in the continuous washing machine), it may remain in the washing machine equipment or adhere to the cloth to be washed. The amount is preferably less than 3% by mass, more preferably less than 1% by mass, and particularly preferably 0% by mass.

(D) Dissolution accelerator Examples of the dissolution accelerator include inorganic ammonium salts such as ammonium sulfate and ammonium chloride, short chains having 1 to 5 carbon atoms such as sodium p-toluenesulfonate, sodium xylenesulfonate, and sodium cumenesulfonate. Examples thereof include water-soluble substances such as benzenesulfonate having alkyl, sodium benzoate, sodium benzenesulfonate, sodium chloride, D-glucose, urea, and sucrose.

(E) Swellable water-insoluble substance Examples of the swellable water-insoluble substance blended in the powder detergent include clay minerals such as powdered cellulose, crystalline cellulose, and bentonite.

(F) Anti-staining agent Examples of anti-staining agents include polyethylene glycol (PEG), carboxymethyl cellulose (CMC), polyalkyl terephthalate / polyoxyalkyl terephthalate polymer and derivatives thereof, polyvinyl pyrrolidone and derivatives thereof, and the like. It is done. Of these, polyethylene glycol (PEG) and carboxymethyl cellulose (CMC) are preferable. The polyethylene glycol is particularly preferably polyethylene glycol having a weight average molecular weight of 1,000 to 20,000.
These anti-contamination agents may be used alone or in combination of two or more, and from the standpoint of anti-contamination performance, preferably 0.1 to 4% by mass, more preferably based on the total amount of the powder detergent composition. It is 0.5-3 mass%.

(G) Enzyme As the enzyme, commercially available enzyme particles that are currently used in granular laundry detergents can be used as they are. Specifically, proteases such as Esperase 4.0T, Sabinase 12T, Cannase 12T, 24T, Evalase 8T, Dezyme, Lipases such as Lipolase Ultra 50T, LIPEX100T, Amylases such as Steinzyme 12T, Termamyl 100T, Cellzyme 0.7T And the like, such as Cellulase (manufactured by Novozymes), Maxacal 45G, Maxapem 30G, Properase 1000E (manufactured by Diencore). Of these, protease, amylase and lipase are preferred.
The blending amount of the enzyme particles is preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass with respect to the total amount of the powder detergent composition from the viewpoint of cleaning performance.

(H) Fluorescent whitening agent Examples of the fluorescent whitening agent include bis (triazinylaminostilbene) disulfonic acid derivative (Tinopearl AMS-GX), bis (sulfostyryl) biphenyl salt (Tinopearl CBS-X) and the like. It is done.

(I) Bleaching component Examples of the bleaching component include a bleaching agent and a bleaching activator.
Examples of the bleaching agent include inorganic peroxides such as sodium persulfate, sodium percarbonate, and sodium perborate, and these can be used alone or in combination of two or more. In order to improve the stability of these, those coated with silicic acid and / or silicate and boric acid and / or borate, and those coated with a water-insoluble organic compound such as paraffin and wax are more preferable. The average particle size of the inorganic peroxide is preferably 200 to 1000 μm, more preferably 300 to 800 μm. In order to satisfy both solubility and stability, particles having a particle size of less than 125 μm and particles having a particle size exceeding 1000 μm are: It is preferable that it is 10 mass% or less in a component. Here, the average particle diameter can be obtained by a method of obtaining a particle size distribution by a method described later and calculating from the particle size distribution.
Examples of the bleach activator include tetraacetylethylenediamine, alkanoyloxybenzenesulfonate, alkanoyloxybenzoic acid, and salts thereof, among which 4-decanoyloxybenzoic acid, 4-dodecanoyloxybenzenesulfonic acid. Sodium and sodium 4-nonanoyloxybenzenesulfonate are preferable, and 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are more preferable from the viewpoint of bleaching effect.
When these bleaching components are contained, it is preferable to add and mix them after the completion of spraying of the liquid component containing the nonionic surfactant (a) as a component from the viewpoint of stability.
The bleach activator is a PEG # 3000 to # 20000, preferably a binder material that is solid at room temperature, such as polyethylene glycol of PEG # 4000 to # 6000, and is granulated to an average particle size of about 200 to 1500 μm. Addition and mixing are preferable from the viewpoint of stability.

(J) Other components Other components that can be blended include antifoaming agents typified by silicone, reducing agents typified by sodium sulfite and potassium sulfite, dyes, and fragrances.

Next, the manufacturing method of the powder detergent composition of this invention is demonstrated. For example, it can be obtained by mixing each component in powder form or liquid.
Although it does not specifically limit as a mixer used, A stirring type mixer and a container rotation type mixer are used suitably.
The agitation type mixer is not particularly limited when mixing in a batch type. For example, a horizontal agitation mixer of a type in which a stirring blade is attached to the inside of a horizontal type mixing tank and mixing is performed at the bottom of the vertical type. A vertical stirring mixer that has blades and performs mixing by rotation of the stirring blades is suitable. Specific examples include the following. As horizontal stirring mixers, Laedige mixer (manufactured by Matsubo Co., Ltd.), Proshear mixer (manufactured by Ohira Yoko Co., Ltd.), ribbon mixer (manufactured by Yoshida Seisakusho Co., Ltd.), Spartan mixer (Dalton Co., Ltd.) , Pug mixer (Fuji Powdal Co., Ltd.), turbulizer (Hosokawa Micron Co., Ltd.), etc. The high-speed mixer (Fukae Powtec Co., Ltd.), Henschel mixer (Mitsui) Mine Co., Ltd.), New Gramachine (Seisin Corporation), etc. Among the agitation mixers, a Raedige mixer, a Proshear mixer, and a ribbon mixer are particularly preferable. Moreover, when mixing by a continuous type, if it uses a continuous stirring type mixer, it will not specifically limit, For example, you may mix using a continuous type apparatus among said stirring type mixers.
The stirring mixer is a mixer having a structure having a jacket, and the temperature at which the nonionic surfactant is added is not particularly limited, but it is preferably 20 to 50 ° C., more preferably 25 to 35 ° C. By supporting the nonionic surfactant under such a heat retaining condition, it becomes possible to produce a detergent composition having a stable quality even in winter.

Preferred embodiments of the mixing conditions by the stirring type mixer are exemplified below.
(1) Treatment time The mixing time (in the case of batch type) and the average residence time (in the case of continuous type) are preferably, for example, 1 to 60 minutes, and particularly preferably 2 to 30 minutes. If it is less than 1 minute, mixing may be insufficient, and if it exceeds 60 minutes, productivity may be reduced.
(2) Froude number (Fr)
The Froude number defined by the following mathematical formula (2) is preferably less than 1, and more preferably 0.01 to 0.8. When the fluid number is 1 or more, consolidation is promoted, which is not preferable.
Fr = V / (R × g) ^0.5 (2)
V: peripheral speed at the tip of the stirring blade [m / s]
R: Rotating radius of stirring blade [m]
g: Gravity acceleration [m / s ² ]
(3) Volume filling rate The filling rate (preparation amount) of the detergent raw material into the stirring type mixer is preferably 10 to 70% by volume or less, more preferably 15 to 40% by volume or less of the total internal volume of the mixer. . In addition, when it exceeds 70 volume%, since the mixing efficiency of the detergent raw material in a mixer falls, suitable granulation may not be performed, and when less than 10 volume%, production efficiency may worsen.

The container rotation type mixer is not particularly limited when batch mixing is performed. For example, a V mixer, a cylindrical mixer, a mixer that mixes by rotating a double conical mixing tank, and the like are suitable. is there.
Mixers that are mixed by rotating a V-shaped mixing tank include V-type mixers (Fuji Powder Co., Ltd.), V-type mixers (Seishin Enterprise Co., Ltd.), etc. As a mixer that is mixed by rotating the mixed tank, a rocking mixer (manufactured by Aichi Electric Trading Co., Ltd.), a Doria coater (manufactured by Paulek Co., Ltd.), a rotary mixer (manufactured by Meiwa Kogyo Co., Ltd.) , Drum mixers (manufactured by Sugiyama Heavy Industries Co., Ltd.), etc., and mixers that mix by rotating a double-conical mixing tank are W-type mixers (manufactured by Seishin Enterprise Co., Ltd.), double cones There are mixers (manufactured by ASR), etc., and mixers that mix by rotating and revolving a cylindrical mixing tank include Dynamixer (manufactured by Mori Machinery Co., Ltd.), cross rotary mixer (Maywa) Made business Co., Ltd.), and the like.
Moreover, when mixing by a continuous type, although it does not specifically limit, if it mixes using a continuous cylindrical mixer, for example, a rocking mixer (made by Aichi Electric Corporation), a doria coater (made by Powrec Co., Ltd.), Good.

Preferred embodiments of the mixing conditions by the container rotating type mixer are exemplified below.
(1) Treatment time The mixing time (in the case of batch type) and the average residence time (in the case of continuous type) are preferably, for example, 1 to 60 minutes, particularly preferably 2 to 30 minutes. If it is less than 1 minute, mixing may be insufficient, and if it exceeds 60 minutes, productivity may be reduced.
In addition, the average residence time in a continuous type is defined by the following numerical formula (3).
Tm = (m / Q) × 60 (3)
Tm: Average residence time (hr)
m: Retained amount of detergent granules in the container rotating mixer (kg)
Q: Capacity in continuous operation (kg / hr)
In the case of the continuous type, the granule retention amount m can be adjusted by the exit weir height.

(2) Froude number (Fr)
A condition is selected such that the Froude number (Fr) defined by the following formula (4) is 0.01 to 0.50. More preferably, it is 0.01-0.45, More preferably, it is 0.02-0.40. From the viewpoint of obtaining a well-mixed powder detergent, the fluid number is preferably 0.01 or more. For example, in the case of a drum type mixer, normal shear mixing that can be reversed without splashing the detergent granulated particles is generated. From the viewpoint of making it, 0.5 or less is preferable.
Fr = V2 / (R × g) ^0.5 (4)
V2: peripheral speed (m / s) at the outermost periphery of the container rotating type mixer
R: Radius (m) from the rotation center on the outermost periphery of the container rotation type mixer
g: Gravity acceleration [m / s ² ]

(3) Volume filling rate (x)
The filling rate (preparation amount) of the detergent raw material into the container rotation type mixer is preferably 10 to 60% by volume or less, more preferably 20 to 40% by volume or less of the total internal volume of the mixer. In addition, when it exceeds 60 volume%, since the mixing efficiency of the detergent raw material in a mixer falls, suitable granulation may not be performed, and when less than 10 volume%, production efficiency may worsen.
In addition, the volume filling rate of a container rotation type mixer is defined by the following numerical formula (5).
x = (M / ρ) / V × 100 (5)
M: Amount of detergent granulated particles charged into the container rotating mixer (g)
ρ: Bulk density (g / L) of detergent granulated particles
V: Volume of container rotation type mixer (L)

  The detergent particles can be produced either batchwise or continuously. In order to produce a powder detergent continuously, a mixer having mixing characteristics close to a plug flow (extrusion flow) is preferable. The raw material is continuously supplied from one side (side flat plate portion of the container rotating mixer), transferred in a flow-through manner, and discharged from the other end (side flat plate portion opposite to the charging of the container rotating type mixer). It is also possible to make the discharge easier by inclining the container rotation type mixer in the direction of descending from the input side to the discharge side. The inclination angle is preferably 0 to 20 °, and more preferably 0 to 5 °. From the viewpoint of preventing mixing of ungranulated particles, the inclination angle is preferably 20 ° or less.

As a method for adding the nonionic surfactant as component (a), a mixture of powder components including component (b), component (c), component (d), and optional component (e) as necessary is in a fluid state. Then, a liquid component containing a nonionic surfactant as component (a) is added and mixed to form a liquid-powder mixture. The method of adding the liquid component is not limited, but in order to avoid the localization of the liquid component and form a uniform liquid-powder mixture efficiently in a shorter time, mixing using a spray nozzle The method is more preferable. Specifically, a mixture of powder components including the component (b), the component (c), the component (d), the component (e), and other optional components is put into a mixer, and then the above (a) ) A liquid component containing a nonionic surfactant as a component is sprayed. A normal spray nozzle can be used for spraying the liquid component, but in order to obtain a cleaning composition having a preferred angle of repose, average particle diameter, and particle size distribution, a fan-shaped nozzle, a full cone nozzle, an empty nozzle It is preferable to use a conical nozzle.
The component (a) may be added as the component (a) alone or after the component (a) is diluted with a solvent such as water. Further, other components may be added in the state of being dissolved or dispersed only in component (a) or in component (a) diluted with a solvent such as water.
Next, after the spraying of the liquid component, the powder detergent of the present invention is obtained. Any powder component containing the enzyme is preferably added and stirred after the spraying of the liquid component. It is possible to improve fluidity and the like by introducing the oil-absorbing powder into an agitator / mixer at an arbitrary timing and stirring and coating. The oil-absorbing powder may be added after the spraying of the liquid component and stirred, and the powder detergent of the present invention can also be obtained by this production method.

The oil-absorbing powder is one component selected from silicic anhydride, hydrous silicic acid, talc, barium sulfate, titanium oxide, and zinc oxide. These components are powder with oil ability, preferably, the oil absorption measured by the method of Junsho to JIS K5101 is 20 cm ^3/100 g or more. More preferred oil absorption ranges are 100~400cm ³ / 100g. These components may be used alone or in combination of two or more. In particular, anhydrous silicic acid or hydrous silicic acid silicate and talc are preferable from the viewpoint of oil absorption ability, difficulty in solidification, and ease of rinsing, and more preferred are anhydrous silicic acid or hydrous silicic acid.
The content of the oil-absorbing powder is 0.5 to 3% by mass. Preferably, it is 0.8-2 mass%. If the amount is less than 0.5% by mass, sufficient oil absorption capacity may not be obtained, and powder fluidity may deteriorate. If the amount exceeds 3% by mass, the oil absorption capacity reaches a peak, and a marked improvement in powder fluidity is observed. The water used in a continuous washer used in the linen supply field (a washer in which multiple drum-type washer tanks are continuously combined) circulates, It may adhere to the cloth to be cleaned.
It is also preferable to perform a classification operation such as sieving on the obtained powder mixture to obtain a cleaning composition from which coarse powder and / or fine powder has been removed.

As for the average particle diameter of the powder particle which comprises the powder detergent composition of this invention, 100-1500 micrometers is preferable, More preferably, it is 200-1000 micrometers. If the average particle size is less than 100 μm, powdering may occur during production, and if it exceeds 1500 μm, the solubility may decrease. The average particle diameter can be measured as follows.
Each sample and the mixture thereof are classified using a 9-stage sieve having a mesh opening 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 on a tray in the order of a large opening, and a base sample of 100 g / time is placed on the top of the top 1680 μm sieve. Attached to Iida Seisakusho Co., Ltd., Tapping: 156 times / minute, Rolling: 290 times / minute), and after vibrating for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, Measure the mass of
When 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 set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (weight 50%) is determined by the following equation, where c is the integration of the mass frequency from the sieve to the aμm sieve, and d% is the mass frequency on the aμm sieve.

In the composition of the present invention, the bulk density of the detergent composition measured by JIS K3362 is 0.4 to 1.5 g / L, preferably 0.5 to 1.2 g / L.
The cleaning composition of the present invention is not particularly limited to the object to be cleaned, but particularly in the field of linen linen supply, yukata, sheets, pillow covers, towels, hotels and restaurants in hotels and inns. The present invention can also be suitably used for colored textile products and / or white textile products such as cook clothes, cloths and shirts in the field of home cleaning. Also in the field of dust control, it can be suitably used for washing objects such as mops and mats.
Although it does not specifically limit as a washing machine used for washing | cleaning using the powder detergent composition of this invention, For example, a large-sized batch washer and a continuous-type washing machine in which a plurality of rotary drum tanks are continuous ( Cleaning system).

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Indicates “% by mass” unless otherwise specified, and the ratio indicates a mass ratio. Example 9 is a reference example .
<The granular detergent composition of an Example and a comparative example>
<Manufacturing method>
The granular detergent composition having the composition shown in Table 1 below was stopped using a ribbon mixer (manufactured by Yoshida Seisakusho, Model 1102-20) under the conditions of a filling rate of 40 vol% and a jacket temperature of 25 ° C. (C) component, (d) component, (b) component, (e) component, and other components f-1, f-2, f-3, f-5, f-6, and f- 8 components were added to the mixer in this order, and then the main shaft was stirred and mixed at 30 rpm while spraying the component (a) preheated to 65 ° C. over 25 minutes, and then the other components f-4, F-7 component was added and prepared by stirring and mixing for 5 minutes, and each item was evaluated. The temperature was 25 to 35 ° C.

<Evaluation method>
(1) Detergency evaluation method Detergency evaluation cloth (EMPA101: manufactured by EMPA TESTMATERIAL) cut into 5 cm x 5 cm sheets, and 10 kg of batch washer (MOX- 15, manufactured by Tokyo Washing Machine Co., Ltd., using 120 g of powder detergent composition (total detergent concentration: 1.2% by mass with respect to the object to be washed), 60 ° C., water level 1 (low water level; bath ratio of about 5) Times) and was washed for 10 minutes by low-speed washing. Thereafter, the step of rinsing at a water temperature of 20 to 25 ° C. and a water level 1 (low water level) for 3 minutes and dehydration 3 for 3 minutes was repeated twice. Subsequently, the evaluation cloth was taken out from the batch washer, and after natural drying, the reflectance of the evaluation cloth was measured, the washing rate was determined by the following formula, and the cleaning power was determined according to the following criteria.

[Formula 1]
(Reflectance of evaluation cloth after washing)-(Reflectance of evaluation cloth before washing)
Cleaning rate (%) = ―――――――――――――――――――――――――― × 100
(Reflectance of clean cloth)-(Reflectance of evaluation cloth before cleaning)

◎◎: 35% or more
A: 31 or more and less than 35 (%)
○: 27 or more and less than 31 (%)
Δ: 23 or more and less than 27 (%)
X: Less than 23 (%)

(2) Rinsing evaluation method (2-1) Low foaming evaluation method The height of the foam at the end of the second rinsing (3 minutes after the start of rinsing) at the time of detergency evaluation was measured visually. Judgment was made according to the criteria.
◎◎: Bubble height is less than 2cm from the water surface
A: The height of the foam is 2 cm or more to less than 4 cm from the water surface.
○: The height of the foam is 4 cm or more to less than 6 cm from the water surface.
Δ: The height of the foam is 6 cm or more to less than 8 cm from the water surface.
X: The height of the foam is 8 cm or more from the water surface.

(2-2) Evaluation Method for Alkali Burning When there is a large amount of residual alkali component, when the object to be washed is dried at high temperature with an iron or the like, the color changes to brown and becomes a problem. Therefore, as an evaluation of defects due to residual alkali, the degree of alkali burning was used as an index.
Evaluation method An evaluation test of detergency was performed, and an iron (TA-D22, manufactured by TOSHIBA ELECTRIC CO., LTD.) Was used for the sheets immediately after the second rinsing / dehydration step, and the set temperature was set to a dry high temperature (about 170 ° C. ± 10 C.) and ironing using a time of 1 minute per 15 cm × 15 cm area. The color of the sheet after ironing was determined visually by five testers according to the following criteria, and the average score was calculated by evaluation based on the following criteria.
4 points: Whiteness equivalent to clean sheets before cleaning experiment 3 points: Slightly colored compared to clean sheets before cleaning experiment 2 points: Compared with clean sheets before cleaning experiment Slightly colored 1 point: Clearly colored compared to clean sheets before washing experiment

Claims (6)

Based on the total amount of the composition,
(A) a polyoxyethylene alkyl ether having 3 to 20% by mass of an alkyl group having 16 to 20 carbon atoms and an average added mole number of ethylene oxide of 3 to 20,
(B) one or more water-soluble chelating agents selected from the group consisting of 7 to 50% by weight of aminocarboxylic acid and salts thereof ,
(C) 5 to 30% by mass of SiO ₂ / M ₂ O (M represents an alkali metal) = 1/1 to 1/2 (molar ratio), and (d) 10 to 40% by mass of silicate M ₂ CO ₃ (M represents an alkali metal)
A powder detergent composition comprising: The component (a) in which the alkyl group of the alcohol is C16 and the component (a) in which the alkyl group of the alcohol is C18 are C16 / C18 = 0/10 to 10/1 in terms of mass ratio. The composition as described. The composition according to claim 1 or 2 , wherein the component (b) is methyl glycine diacetate or hydroxyiminodisuccinate. (E) Furthermore, the composition of any one of Claims 1-3 which contains 1-20 mass% carboxylic acid type polymer on the basis of the whole quantity of a composition. (B) a first composition comprising one or more water-soluble chelating agents selected from the group consisting of aminocarboxylic acids and salts thereof ;
(A) a polyoxyethylene alkyl ether having an alkyl group having 16 to 20 carbon atoms and an average addition mole number of ethylene oxide of 3 to 20, (c) SiO ₂ / M ₂ O (M represents an alkali metal) A second composition comprising a silicate of = 1/1 to 1/2 (molar ratio) and (d) M ₂ CO ₃ (M represents an alkali metal),
Based on the total amount of the first composition and the second composition, the component (b) is 7 to 50% by mass, the component (a) is 3 to 20% by mass, and the component (c) is 5 to 30% by mass. (D) The powder detergent kit characterized by combining the component in the quantity used as 10-40 mass%. Based on the total amount of the composition,
(A) a polyoxyethylene alkyl ether having 3 to 20% by mass of an alkyl group having 16 to 20 carbon atoms and an average added mole number of ethylene oxide of 3 to 20,
(B) one or more water-soluble chelating agents selected from the group consisting of 7 to 50% by weight of aminocarboxylic acid and salts thereof ,
(C) 5 to 30% by mass of SiO ₂ / M ₂ O (M represents an alkali metal) = 1/1 to 1/2 (molar ratio), and (d) 10 to 40% by mass of silicate M ₂ CO ₃ (M represents an alkali metal)
Use of the said (b) component for manufacturing the powder detergent composition containing this.