KR20110127164A - Granular detergent composition - Google Patents

Abstract

The present invention comprises (A) one or more kinds of particles selected from zinc oxide particles and aluminosilicate particles, and (B) carboxymethyl cellulose having a weight average molecular weight of 300,000 to 1,000,000, and (A) zinc oxide particles and / Or a mass ratio (A) / (B) of zinc aluminosilicate particles and (B) carboxymethyl cellulose is 10/1 to 1/4. According to this invention, the granular detergent composition excellent in the odor suppression effect which arises when drying the wash | cleaned clothing can be provided.

Description

Granular detergent composition {GRANULAR DETERGENT COMPOSITION}

The present invention relates to a granular detergent composition.

This application claims priority in accordance with Japanese Patent Application No. 2009-058517 for which it applied to Japan on March 11, 2009, and uses the content here.

BACKGROUND OF THE INVENTION In recent years, in addition to detergency, complex medical functions such as deodorization, deodorization, and disinfection have been demanded in medical detergents.

In response to this demand, for example, Patent Document 1 discloses a method of suppressing the occurrence of odors when drying laundry, including a substance having an antibacterial action against various germs, oxidation of contaminant components remaining on laundry after washing, and Into the granular detergent composition, a granulated deodorant component such as a substance having an antioxidant action to control decomposition or a odorant masking malodor and particles containing clay minerals and coated with a surface coating agent A method is disclosed.

Regarding the use of the zinc oxide particles in the granular detergent composition, Patent Literature 2 describes mixing zinc oxide as a whitening agent in a nonionic detergent composition.

In addition, Patent Document 3 discloses a method of blending zinc oxide particles with particles having an anionic surfactant as a main component to prevent odor deterioration during storage of the detergent composition.

Japanese Laid-Open Patent Publication No. 2004-204085 Japanese Patent Laid-Open No. 10-168497 Japanese Patent Laid-Open No. 2006-182862

In particular, there is a high demand for suppressing odor upon drying laundry, such as odor when laundry is dried indoors (smell of drying in a room), but it is not always sufficient in the conventional method.

This invention is made | formed in view of the said situation, and an object of this invention is to provide the granular detergent composition excellent in the suppression effect of the odor produced when drying the wash | cleaned clothing.

As a result of intensive studies by the present inventors and the like to solve the above problems, by blending at least one type of particles selected from zinc oxide particles and aluminosilicate silica particles with high molecular weight carboxymethyl cellulose in a specific ratio, It confirmed that the odor at the time of drying of laundry can be suppressed favorably, and came to this invention.

That is, the granular detergent composition of the present invention contains (A) one or more kinds of particles selected from zinc oxide particles and aluminosilicate particles, and (B) carboxymethyl cellulose having a weight average molecular weight of 300,000 to 1,000,000, (A) The mass ratio (A) / (B) of zinc oxide particles and / or zinc aluminosilicate particles and (B) carboxymethyl cellulose is characterized in that 10/1 to 1/4. It is preferable that the average particle diameter of said (A) zinc oxide particle and / or zinc aluminosilicate particle is 10 micrometers or less.

According to this invention, the granular detergent composition excellent in the odor suppression effect which arises when drying the wash | cleaned clothing can be obtained.

<(A) Zinc oxide particles and / or zinc aluminosilicate particles>

The zinc oxide particles and / or zinc aluminosilicate particles in the present invention preferably have an average particle diameter of 10 µm or less. The more preferable average particle diameter of zinc oxide particle and / or zinc aluminosilicate particle is 1 micrometer or less, More preferably, it is the range of 0.1 micrometer-0.01 micrometer. If it is less than 0.01 micrometer, a particle | grain will become fine and a problem, such as a fine powder scattering on handling, will arise easily, and the said range is preferable.

By keeping the average particle diameter of zinc oxide particles and / or zinc aluminosilicate particles within the above-mentioned range, the effect of suppressing the odor generated when the blood cells (laundries) are dried and dried in the room is obtained satisfactorily. Lose. It is considered that this is because the surface area of the particles increases and the adsorption to the blood cells becomes good by reducing the average particle diameter to 10 µm or less.

These (A) particles can be obtained from commercially available products. For example, zinc oxide (product name) manufactured by Honjo Chemical Co., Ltd. can be used as the zinc oxide particles.

The zinc aluminosilicate particles contain silica, zinc oxide and alumina, which are metal oxides, as constituents. As the aluminosilicate zinc particles, Lionite SF (product name) manufactured by Lion Co., Ltd. can be used. The aluminosilicate zinc particles are obtained as white or pale powder, and the water-soluble silicate and the water-soluble zinc salt, the water-soluble aluminum salt and / or the water-soluble aluminate, etc. are reacted in the presence of water, whereby the precipitation obtained is It can be prepared by heating in the presence.

This reaction proceeds easily by the so-called metathesis method. That is, a silicate alkali such as sodium silicate is used as the silica component, and a water-soluble zinc salt such as chloride, nitrate or sulfate is used as the zinc oxide component, and a water-soluble aluminum salt such as aluminum chloride and aluminum sulfate as the alumina powder and / Or soda aluminate is used, these are mixed in the presence of water, and reacted by metathesis.

In order to make this metathesis reaction homogeneous, it is preferable to perform reaction while adding silicate aqueous solution, the zinc salt aqueous solution, and the aqueous solution containing an alumina component simultaneously in the water which disperse | distributed silica previously. Although reaction by metathesis is enough at room temperature, it is also possible to carry out under heating, for example, reaction under heating to about 95 degreeC is of course possible. It is preferable to maintain the pH of the reaction system at the time of simultaneous stock price in the range of 5-10, especially 6-8. For this purpose, if necessary, it is preferable to add an acid or an alkali to the reaction system to maintain the pH of the reaction solution within the above range.

At the same time, precipitation of the aluminosilicate zinc salt having a composition almost corresponding to that of the aqueous solution is generated. This precipitate is separated or, if necessary, heated in the presence of water, thereby obtaining a white to pale fine powder.

The molar ratio (SiO ₂ : ZnO: AL ₂ O ₃ ) of the constituents of zinc aluminosilicate is preferably 5 to 80: 5 to 65: 1 to 60, furthermore, 10 to 70: 10 to 60: 1 to 50 This is preferred. The zinc aluminosilicate thus obtained exhibits an excellent deodorizing effect.

In addition, an aqueous solution containing a zinc salt and an aluminum salt may be coprecipitated by alkaline conditioning, and the resulting precipitate and hydrothermal reaction may be carried out under silica to produce zinc aluminosilicate.

The zinc aluminosilicate produced in this way can be adjusted after drying, and the average particle diameter can be adjusted by wet grinding or dry grinding. Examples of the grinding method include jet mill grinding and ball mill grinding, but are not particularly limited.

In the granular detergent composition of the present invention, the zinc oxide particles and / or zinc aluminosilicate particles may each be present in the form of a single particle, and in the form of coated particles coated with a surfactant, a pharmaceutical and / or a dye, or the like. It may exist, or may exist in the form containing the single particle of diameter smaller than the said surfactant containing particle in surfactant containing particle mentioned later. The coated particle is preferable at the point of preventing the classification of the particles in the granular detergent composition and at the point of suppressing the generation of dust during production.

(Measurement method of average particle diameter)

The average particle diameter of the zinc oxide particle and / or zinc aluminosilicate particle in this invention is the value measured by the following method.

The sample to be measured (zinc oxide particles or zinc aluminosilicate particles) was dispersed in 99% or more of ethanol solution using a homogenizer capable of rotation of 10000 rpm or more, and then air-dried on a sample bed. After that, it is measured by a scanning electron microscope or a transmission electron microscope which can be used at a magnification of several hundred thousand times.

More specifically, 200 ml of 99.5% ethanol was added to 5 g of the sample, and the mixture was stirred and dispersed at 1000 rpm for 5 minutes using a High Homogenizer Power Homogenizer DIAX900 (Shaft Generator 18F). It is droopy and is full. The sample after air drying is deposited with platinum palladium, preferably platinum, and the particle | grains are photographed by the magnification of 50,000-100,000 using the Hitachi Scanning Electron Microscope H-8010.

The particle size of 20 particles at 50,000 times and 10 particles at 100,000 times is measured, and the average value is obtained.

<(B) carboxymethyl cellulose>

Carboxymethyl cellulose (hereinafter sometimes abbreviated as CMC) in the present invention is a concept including the salt thereof. As a salt of carboxymethyl cellulose, alkali metal salts, such as sodium and potassium, an ammonium salt, etc. are mentioned, A mixture of these salts may be sufficient. Among the salts described above, sodium salts are suitably used.

By mix | blending CMC with the granular detergent composition in this invention, the effect of suppressing a bad smell at the time of drying and drying a blood cell indoors is obtained favorably. The reason for this is that when CMC is present in the tax solution, contaminants that cause odors, such as sebum, are more likely to be dispersed in the tax solution, and the residual amount of the pollutant in the blood cells can be reduced. It is considered that the zinc oxide particles and / or zinc aluminosilicate particles and CMC form a complex to improve the adsorption of zinc oxide particles and / or zinc aluminosilicate particles to blood cells.

Examples of CMC include anionic water-soluble cellulose ethers or water-insoluble cellulose ethers obtained by treating pulp as a raw material, treating it with caustic soda, and then reacting monochloroacetic acid. Specifically, the high molecular compound which has a repeating unit represented by following formula (I) is illustrated.

[Wherein in the formula (I), n represents the number of repetitions of the repeating units, R ¹ to R ³ are each independently a hydrogen atom or a carboxymethyl group ^{_{(-CH 2 COO-Z +;}} Z + is a large (對) ion is ).]

In the present invention, the weight average molecular weight of CMC is 300,000 or more and 1,000,000 or less. Preferably 300,000 to 700,000. If it is less than 300,000, the odor suppression effect is inferior. This is considered to be because the adsorption improvement effect of zinc oxide particle and / or zinc aluminosilicate particle is not fully acquired.

When the weight average molecular weight of CMC exceeds 1,000,000, dissolution or dispersion of CMC in the tax liquor becomes insufficient, and the effect by the blending of CMC is not sufficiently obtained.

(Measurement method of weight average molecular weight)

In the present invention, the weight average molecular weight of carboxymethyl cellulose is obtained by a system using gel filtration chromatography (GPC) and differential refractive index detection apparatus (RI), eluent: NaNO _{3 at} 0.1 M, flow rate: 1 ml / min, sample concentration: 0.02 to 0.3% by weight, solvent: NaNO _3, injection volume of 0.1M: the operating conditions of 200㎕, it refers to a value calculated on the weight average molecular weight of PEG (polyethylene glycol) as a number of terms. In addition, as an apparatus for measuring the weight average molecular weight, for example, a liquid pump: Shodex DS-4 (manufactured by Digestion Electric Co., Ltd.), Degasser: ERC3115 (manufactured by ERC Co.), column: Shodex SB-806MHQ (manufactured by Digestion Electric Co.), differential refractive index Detector: Shodex RI-71 can be used.

0.2-1.3 are preferable, as for the etherification degree of CMC, 0.2-1.0 are more preferable, 0.2-0.7 are further more preferable.

The degree of etherification of CMC in the present specification means the average number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit (of the three hydroxyl groups of the glucose ring, some of which are substituted by a carboxymethyl group or a salt thereof) It is up to 3). For example, in said Formula (I), R <^1> of -OR <^1> , -OR <^2> , and -OR <^3> . The average value of the number from R <^3> to a carboxymethyl group or its salt becomes an etherification degree.

The higher the degree of etherification, the stronger the negative charge of CMC in water, and the easier it is to form a complex with zinc oxide particles and / or zinc aluminosilicate particles that are positively charged in water. On the other hand, since normal cloth fibers are negatively charged, if the negative charge of CMC is too strong, the effect of improving the adsorption property of the composite onto the cloth tends to be lowered.

Therefore, if the degree of etherification of CMC is within the above range, a complex of CMC and zinc oxide particles and / or zinc aluminosilicate particles is likely to be formed, and the complex is easily adsorbed to the blood cells, and as a result, the blood cells are dried. Odor is well suppressed.

CMC can use a commercial item suitably. For example, 1110, 1120, 1130, 1140, 1150, 1160, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380, 2200 sold under the brand name "CMC Daicel" manufactured by Daicel Chemical Industries, Ltd. , 2260, 2280, 2450, 2340, and the like. Sun Rose F series such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, and F1400MG, which are sold under the trade name &quot; Sun Rose &quot; Sunrose A series such as A02SH, A20SH, and A200SH; SLD-F1 (above brand name) is mentioned. Among these, CMC dice 1130, 1180, and 1190, Sunrose F1400LC, and F1400MC, Sunrose SLD-F1, and Sunrose SLD-FM are especially preferable. All of these commercial CMCs are particulate.

In this invention, 1 type, or 2 or more types of CMC can be mixed and used.

In the granular detergent composition of the present invention, the CMC is preferably present in particulate form. It may exist in the form of individual particles, may exist in the form of coated particles coated with a nonionic surfactant, a pharmaceutical and / or a pigment, or the like, or smaller than the surfactant-containing particles in the surfactant-containing particles described later. It may exist in the form containing the single particle of a diameter. From the standpoint of solubility in water and storage stability of the granular detergent composition, it is preferable that some or all of the surface of the single particle of CMC is present in the form of coated particles coated with at least a nonionic surfactant.

<Amount of (A) and (B)>

The content of the (A) zinc oxide particles and / or zinc aluminosilicate particles in the granular detergent composition as a whole is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.3% by mass in order to obtain a sufficient addition effect. The above is more preferable. 10 mass% or less is preferable and, as for an upper limit, 5 mass% or less is more preferable from an odor suppression effect and economical point.

The content of (B) CMC in the granular detergent composition as a whole is preferably 0.1% by mass or more from the point that the effect of improving the adsorption properties of (A) zinc oxide particles and / or zinc aluminosilicate particles to blood cells is sufficiently obtained. 0.3 mass% or more is more preferable, and 1.0 mass% or more is more preferable. Since an upper limit prevents solidification of a product, 15 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is more preferable.

It is preferable that mass ratio (A) / (B) of (A) zinc oxide particle and / or zinc aluminosilicate particle and (B) CMC contained in a granular detergent composition is 10/1-1/4. If there are more (A) zinc oxide particles and / or zinc aluminosilicate particles than the mass ratio 10/1, the adsorption of (A) zinc oxide particles and / or zinc aluminosilicate particles to blood cells tends to be insufficient and economically. Not desirable When there are fewer (A) zinc oxide particles and / or zinc aluminosilicate particles than less than 1/4, an odor suppression effect will become inadequate easily.

It is preferable that the granular detergent composition of this invention contains surfactant other than (A) zinc oxide particle and / or zinc aluminosilicate particle, and (B) CMC. Moreover, various well-known additives can be contained as a containing component of a granular detergent composition.

In the granular detergent composition, the surfactant is preferably present in the form of particulate surfactant-containing particles. A surfactant, a fluorescent brightener, polymers, an enzyme stabilizer, an anti-caking agent, a reducing agent, a metal ion trapping agent, a pH adjuster, etc. can be mix | blended with surfactant containing particle | grains as needed.

These examples are given below.

<Surfactant>

As surfactant, a well-known surfactant can be used suitably as a containing component of a granular detergent composition. Surfactant can be used individually by 1 type or in combination of 2 or more types.

<Anion surfactant>

As an anionic surfactant, the following anionic surfactant is mentioned, for example.

(1) Alkyl ester salt ((alpha) -SF salt) of saturated or unsaturated (alpha)-sulfofatty acid of C8-20. The alkyl ester salt is preferably a methyl ester salt, an ethyl ester salt or a propyl ester salt. For example, α-sulfofatty acid methyl ester sodium salt (MES) is preferable.

(alpha)-sulfo fatty acid methyl ester sodium salt (MES) can disperse | distribute the (A) zinc oxide particle and / or the zinc aluminosilicate particle of this invention to a washing liquid favorably.

The amount of the α-sulfofatty acid alkyl ester salt in the granular detergent composition of the present invention is (A) 5 to 20% by mass in terms of good dispersibility and washing power of the zinc oxide particles and / or zinc aluminosilicate particles in the washing solution. Is preferable, More preferably, it is 7-18 mass%. By more than the said lower limit, necessary dispersibility and washing | cleaning power can be acquired. On the other hand, even if it is below the said upper limit, dispersibility and washing | cleaning power are fully acquired and it is economically advantageous.

(2) Alkali metal salts or alkaline earth metal salts of higher fatty acids having a mean carbon number of 10 to 20 fatty acids (soap).

(3) Straight or branched chain alkylbenzenesulfonate having an alkyl group having 8 to 18 carbon atoms (LAS or ABS).

(4) Alkanesulfonates having 10 to 20 carbon atoms.

(5) α-olefin sulfonates (AOS) having 10 to 20 carbon atoms.

(6) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(7) C10-C20 linear chain which added 0.5-10 mol of average of either C2-C4 alkylene oxide or ethylene oxide and a propylene oxide (molar ratio EO / PO = 0.1 / 9.9-9.9 / 0.1) Or alkyl (or alkenyl) ether sulfates having branched alkyl (or alkenyl) groups (AES).

(8) A straight chain having 10 to 20 carbon atoms, in which 3 to 30 moles of an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and a propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) are added on average. Or alkyl (or alkenyl) phenyl ether sulfates having branched alkyl (or alkenyl) groups.

(9) straight chain of 10 to 20 carbon atoms in which 0.5 to 10 moles of any one of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) are added; Or an alkyl (or alkenyl) ether carbonate having a branched alkyl (or alkenyl) group.

(10) Alkyl polyhydric alcohol ether sulfates, such as C10-C20 alkyl glyceryl ether sulfonic acid.

(11) long-chain monoalkyl, dialkyl or seskialkyl phosphates.

(12) polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphates. These anionic surfactants can be used as alkali metal salts such as sodium or potassium, amine salts, ammonium salts and the like. Of these anionic surfactants, α-sulfofatty acid methyl ester sodium salt (MES) is most preferred. In addition, you may use these anionic surfactant as a mixture.

<Nonionic surfactant>

As a nonionic surfactant, the following nonionic surfactant is mentioned, for example.

(1) polyoxyalkylenealkyl (or eggs) having an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Kenil) ether.

Among these, polyoxyethylene alkyl (or alkenyl) ether (AE) and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. As an aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. In addition, the alkyl group may have a branched chain. As aliphatic alcohol, primary alcohol is preferable.

(2) polyoxyethylene alkyl (or alkenyl) phenyl ether.

(3) Fatty acid alkyl ester alkoxylate which alkylene oxide added between the ester bonds of long-chain fatty acid alkyl ester, for example represented by the following general formula (II).

R ¹ CO (OA) _n OR ² . … (Ⅱ)

(Wherein 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, preferably 2 to 3 carbon atoms such as ethylene oxide or propylene oxide). N represents the addition unit of an oxide, n represents the average added mole number of alkylene oxide, and is generally 3-30, Preferably it is the number of 5-20. R <^2> is a lower grade which may have a C1-C3 substituent ( An alkyl group having 1 to 4 carbon atoms.)

(4) polyoxyethylene sorbitan fatty acid ester.

(5) polyoxyethylene sorbitan fatty acid ester.

(6) polyoxyethylene fatty acid ester.

(7) polyoxyethylene hardened castor oil.

(8) glycerin fatty acid ester.

Among the nonionic surfactants described above, the nonionic surfactant of (1) is preferable, and in particular, polyoxyalkylene alkyl (or alkenyl) in which 9 to 20 moles of ethylene oxide is added to an aliphatic alcohol having 12 to 16 carbon atoms. Ether is preferred.

In particular, fatty acids having ethylene oxide added to polyoxyethylene alkyl (or alkenyl) ethers, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers having a melting point of 50 ° C. or lower and HLB of 9 to 16, and fatty acid methyl esters. Fatty acid methyl ester ethoxy propoxylate which ethylene oxide and propylene oxide added to the methyl ester ethoxylate and fatty acid methyl ester is used suitably.

In addition, HLB of the nonionic surfactant in this invention is the value calculated | required by Griffin's method (Yoshida Shindo, Ogaki, Yamanaka Co., "New Surfactant Handbook", Industrial Books Co., 1991. , See page 234).

In addition, melting | fusing point in this invention is the value measured by the melting point measuring method described in JISK0064-1992 "Method of melting | fusing point and melting range of a chemical product."

<Cation surfactant>

As a cationic surfactant, the following are mentioned, for example.

(1) Di long-chain alkyl di short-chain alkyl type quaternary ammonium salt.

(2) Mono long-chain alkyl trishort-chain alkyl type quaternary ammonium salt.

(3) Tri-chain alkyl mono short-chain alkyl type quaternary ammonium salt.

However, said "long chain alkyl" represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.

"Short-chain alkyl" may contain substituents, such as a phenyl group, benzyl group, a hydroxy group, or a hydroxyalkyl group, and may have an ether bond between carbons. Especially, an alkyl group of 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; Benzyl group; Hydroxyalkyl groups having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; Polyoxyalkylene groups having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and the like are suitable.

<Positive surfactant>

As an amphoteric surfactant, the imidazoline type amphoteric surfactant, the amide betaine type amphoteric surfactant, etc. are mentioned, for example. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauric acid amidepropyl betaine, etc. are suitable.

In the granular detergent composition of this invention, 5 mass% or more is preferable in order to acquire a favorable washing | cleaning effect, 10 mass% or more is more preferable, and its 15 mass% or more is more preferable. 50 mass% or less is preferable at the point of the balance with another component, 40 mass% or less is more preferable, and 35 mass% or less is more preferable.

<Cleanability builder>

As a detergency builder, an inorganic builder and an organic builder are mentioned.

As an inorganic builder, For example, alkali metal carbonates, such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sodium sesquicarbonate; Alkali metal sulfites such as sodium sulfite and potassium sulfite; Crystalline sodium sodium silicate (for example, crystalline alkali metal silicates such as Clariand Japan trade name "Na-SKS-6" (δ-Na ₂ O ₂ SiO ₂ )); Amorphous alkali metal silicate; Sulfates such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; Phosphates such as oxophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytin salts; And crystalline aluminosilicate sodium salts, amorphous aluminosilicate sodium salts, and complexes of sodium carbonate and amorphous sodium metal silicate salts (for example, Rhodia's trade name "NABION15").

Among the inorganic builders, potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as those having an effect of improving solubility or sodium carbonate, sodium aluminosilicate, or solubility.

As the aluminosilicate except for the aluminosilicate zinc particles of (A), either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferable in terms of cation exchange capacity.

As crystalline aluminosilicate, A-type, X-type, Y-type, or P-type zeolite etc. can be mix | blended suitably, As for an average primary particle diameter, 0.1-10 micrometers is preferable. 1-40 mass% is preferable, and, as for content of the crystalline aluminosilicate in surfactant containing particle | grains, 2-30 mass% is especially preferable at the point of powder physical properties, such as washing performance and fluidity | liquidity.

As a commercial item, it is the product made by HAIXING CHEMICAL CO., LTD OF DONGYING CITY, brand name: ZEOLITE 4A; Fujian Ilsung Chemical Co., Ltd. (FUJIAN RISHENG C. L., LTD) make, brand name: 4A ZEOLITE; Made by Sanxi Yuchi Changli High-Tech Co., Ltd., trade name: 4A Zeolite; Made by ALUMINUM CORPORATION OF CHINA., LTD., Trade name: 4A ZEOLITE; Huiying Chemical Products Co., Ltd. make, brand name: 4A Zeolite; Thai Silicate Chemicals Co., Ltd., trade name: Zeolite 4A Type; Cosmo (COSMO FINE CHEMICALS CO., LTD.) Make, brand names: COLITE-P; PQ Chemicals Limited, trade name: VALFOR100 Zeolite NaA; And Mizuwa Chemical Co., Ltd., a brand name: Silton, etc. are suitable.

When mix | blending potassium carbonate, the content is 1-20 mass% in surfactant containing particle | grains from the point of the effect of solubility improvement, More preferably, it is 2-15 mass%.

When mix | blending an alkali metal chloride, the content is 1-10 mass%, More preferably, 2-8 mass%, More preferably, 3 in surfactant containing particle | grains from the point of the effect of the solubility improvement. To 7 mass%.

When mix | blending a crystalline alkali metal silicate, the content is from a viewpoint of washing | cleaning performance in surfactant containing particle | grains, Preferably it is 0.5-40 mass%, More preferably, it is 1-25 mass%, More preferably, 3 To 20% by mass, particularly preferably 5 to 15% by weight.

As an organic builder, For example, amino carbonates, such as a nitrilo triacetate, ethylenediamine tetraacetate, (beta) -alanine diacetate, aspartic acid diacetate, methylglycine diacetate, and imino diacetate; Hydroxyaminocarboxylic acid salts such as serine diacetate, hydroxyiminodi pumpkin salt, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine salt; Hydroxy carbonates such as hydroxyacetate, tartarate, citrate, and gluconate; Cyclocarbonates such as pyromellitate, benzopolycarbonate, and cyclopentane tetracarbonate; Ether carbonates such as carboxymethyl tartrate, carboxymethyloxysuccinate, oxydisuccinate, and tartaric acid mono or disuccinate; Salts of polyacetalcarboxylic acids such as polyacrylates, salts of acrylic acid-allyl alcohol copolymers, salts of acrylic acid-maleic acid copolymers, and polyglyoxylic acids; Salts of acrylic acid polymers or copolymers such as hydroxyacrylic acid polymers and polysaccharide-acrylic acid copolymers; Salts of polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, and aspartic acid; And polysaccharide oxides such as starch, cellulose, amylose, and pectin, or polysaccharide derivatives.

Among the organic builders, citrate, aminocarboxylic acid salts, hydroxyaminocarboxylic acid salts, polyacrylates, salts of acrylic acid-maleic acid copolymers, and salts of polyacetalcarboxylic acid are preferable. In particular, the hydroxyiminodi benzoate, the salt of the acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, the polyacrylate, the salt of the acrylic acid-maleic anhydride copolymer having a weight average molecular weight of 1000 to 80000, and the weight average molecular weight The polyacetal carbonate (for example, described in Japanese Patent Application Laid-Open No. 54-52196) such as polyglyoxylic acid of 800 to 1000000 (preferably 5000 to 200000) is suitable.

As for content of an organic builder, 1-20 mass% is preferable in surfactant containing particle | grains, More preferably, it is 1-10 mass%, Especially preferably, it is 1-5 mass%.

The said builders can be used individually by 1 type or in combination of 2 or more types.

Among the above-mentioned cleaning builders, since the cleaning power, the dispersibility of the contamination in the washing liquid, and the dispersibility of the (A) zinc oxide particles and the aluminosilicate particles are improved, the citrate, the amino carbonate, the hydroxyamino carbonate, It is preferable to use together an organic builder, such as a polyacrylate, a salt of an acrylic acid-maleic acid copolymer, or a salt of polyacetalcarboxylic acid, and an inorganic builder, such as a zeolite, and (A) zinc oxide particle and aluminosilicate silica particle are especially preferable. It is preferable to use together the salt / zeolite of the acrylic acid-maleic acid copolymer from the viewpoint of dispersibility of, and the ratio is preferably 1/99 to 30/70, more preferably 5/95 to 20/80.

10-80 mass% is preferable and, as for content of the cleaning builder in surfactant containing particle | grains, 20-75 mass% is more preferable.

<Fluorescent brightener>

As a fluorescent brightener, for example, 4,4'-bis- (2-sulphostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3- sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivatives, 4,4'-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like.

The said fluorescent brightener can be used individually by 1 type or in combination of 2 or more types.

As for content of the fluorescent brightener in surfactant containing particle | grains, 0.001-1 mass% is preferable.

Specifically as a commercial item, Whiteex SA and Whiteex SKC (above, a product made by Sumitomo Chemical Co., Ltd.); Chinopal S-GX, Chinopal S-X, and Chinopal S-X (above, brand names; product made by Chiba Specialty Chemicals Co., Ltd.); Lemonite CBUS-3B (above, trade name; manufactured by Khyati Chemicals) and the like are suitable. Especially, chinopal S-X and chinopal S-GX are more preferable.

<Polymers>

In the present invention, polyethylene glycol having a weight average molecular weight of 200 to 200000, as a binder or a powder physical modifier used for densifying surfactant-containing particles, or to impart a recontamination prevention effect to hydrophobic fine particles (contamination), Salts of acrylic acid and / or maleic acid polymers having a weight average molecular weight of 1000 to 100000, polyvinyl alcohol, cellulose derivatives such as hydroxypropylmethylcellulose (HPMC), and the like.

Moreover, the copolymer, terpolymer, etc. of the repeating unit derived from terephthalic acid, and the repeating unit derived from ethylene glycol and / or propylene glycol can be mix | blended as a contamination release agent.

Moreover, polyvinylpyrrolidone etc. can be mix | blended in order to provide the color shifting prevention effect.

Among the polymers, HPMC is preferable, and HPMC is more preferably 20,000 or more in weight average molecular weight from the viewpoint of the effect of imparting flexibility to the object to be cleaned and the prevention of recontamination.

These polymers can be used individually by 1 type or in combination of 2 or more types.

As for content of the said polymer in surfactant containing particle | grains, 0.05-5 mass% is preferable.

Enzyme Stabilizer

As an enzyme stabilizer, calcium salt, magnesium salt, polyol, formic acid, a boron compound, etc. can be mix | blended, for example. Especially, sodium tetraborate, calcium chloride, etc. are preferable.

An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types.

As for content of the enzyme stabilizer in surfactant containing particle | grains, 0.05-2 mass% is preferable.

<Caking inhibitor>

As an anti-caking agent, paratoluene sulfonate, xylene sulfonate, acetate, sulfo pumpkin salt, talc, fine powder silica, clay, magnesium oxide, etc. can be mix | blended.

<Reduction agent>

Examples of the reducing agent include sodium sulfite, potassium sulfite, and the like.

Metal ion trapping agent

The metal ion trapping agent captures trace metal ions and the like in tap water, and has an effect of suppressing the adsorption of metal ions onto the fiber (a target object).

As a metal ion trapping agent, Amino polyacetic acids, such as ethylenediamine tetraacetic acid, nitrilo triacetic acid, and glycol ethylenediamine hexaacetic acid, besides being contained in the said cleaning builder; 1-hydroxyethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2 Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethylimide Organic phosphonic acid derivatives or salts thereof such as nodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), and diethylenetriaminepenta (methylenephosphonic acid); And organic acids such as diglycolic acid, citric acid, tartaric acid, hydroxyl acid, and gluconic acid or salts thereof.

The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types.

As for content of the metal ion trapping agent in surfactant containing particle | grains, 0.1-5 mass% is preferable, More preferably, it is 0.5-3 mass%. If it is 0.1 mass% or more, the effect which captures the metal ion in tap water will improve. On the other hand, when it is 5 mass% or less, the effect which captures a metal ion is fully acquired.

<pH regulator>

Although the pH in particular does not restrict | limit the surfactant containing particle | grains of this invention, It is preferable that pH in 1 mass% aqueous solution of surfactant containing particle | grains is 8 or more from the point of washing performance, In the said 1 mass% aqueous solution It is more preferable that pHs are 9-11. When the said pH is 8 or more, a washing | cleaning effect becomes easy to be exhibited.

As a technique for controlling pH of surfactant containing particle | grains, pH adjustment is normally performed by the alkali agent, Alkanolamines, such as monoethanolamine, diethanolamine, and triethanolamine, in addition to the alkali agent described in the said cleaning builder, Sodium hydroxide, potassium hydroxide and the like.

Specifically, for example, in terms of solubility in water and alkalinity, the ratio of sodium carbonate, sodium silicate, and water is a mixture of 55/29/16 (mass ratio) using NABION15 (trade name, manufactured by Rhodia Co., Ltd.). It is preferable.

Moreover, in order to prevent the pH of surfactant containing particle | grains becoming too high, you may adjust to the said pH range using acid etc.

Examples of such acids include alkali metal phosphate dihydrogen salts such as the metal ion trapping agent and potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids, citric acid, sodium hydrogen carbonate, sulfuric acid, or Hydrochloric acid and the like can be used.

It is also possible to use a buffer for preventing a drop in pH due to an acid component resulting from contamination of the fiber at the time of washing.

The said pH adjuster can be used individually by 1 type or in combination of 2 or more types.

Surfactant-containing particle | grains can be manufactured by a well-known manufacturing method. For example, the method of manufacturing via a slurry preparation process, a spray drying process, a kneading process, a grinding | pulverization process, etc. can be used.

(A) zinc oxide particles and / or zinc aluminosilicate particles, by mixing the prepared surfactant-containing particles with (A) zinc oxide particles and / or zinc aluminosilicate particles, and (B) CMC in particulate form, And (B) a granular detergent composition in which CMC is present in the form of a single particle. Furthermore, after mixing them, coating is carried out to obtain granular detergent compositions in which surfactant-containing particles, (A) zinc oxide particles and / or zinc aluminosilicate particles, and (B) CMC are present in the form of coated particles. have.

Alternatively, (A) zinc oxide particles and / or zinc aluminosilicate particles, and / or particulate (B) CMC may be blended in a slurry preparation step or a kneading step, respectively. In this case, the granular detergent of the form which contains (A) zinc oxide particle and / or zinc aluminosilicate particle, and / or (B) CMC particle of diameter smaller than the said surfactant containing particle in surfactant containing particle | grains. A composition can be obtained.

&Lt; Other components >

Moreover, a bleach, a bleach activator, a bleach activating catalyst, an enzyme, an antifoamer, a coloring agent, a pigment, etc. can be mix | blended with a granular detergent composition as needed. The bleaching agent, the bleaching activator, the bleach activating catalyst, the enzyme, and the antifoaming agent are each preferably present in the form of separate particles. It is preferable that a pigment | dye and a pigment exist as a coating layer of particle | grains in a granular detergent composition.

These examples are given below.

<Bleach>

As the bleaching agent, an oxygen-based bleaching agent such as hydrogen peroxide or percarbonate such as sodium percarbonate and a chlorine-based bleaching agent called sodium hypochlorite or thiourea dioxide can be used. Of these, oxygen-based bleaches are preferred, percarbonates are more preferred, and sodium percarbonate is most preferred. As a commercial item of sodium percarbonate, SPC-D and SPC-HGD (made by Mitsubishi Chemical Co., Ltd.); PC-NK (manufactured by Nippon Peroxide Co., Ltd.); And SPCC (Zhejiang Jinke Chemicals Co., Ltd.); Sodium Percarbonate (Zhejiang DC Chemical CO., Ltd.) is suitable.

1 mass% or more and 20 mass% or less are preferable, and, as for the compounding quantity of the bleach in a granular detergent composition, More preferably, they are 2 mass% or more and 10 mass% or less. Even if it exceeds the said range, the bleaching effect may not become high anymore, and below the said range, sufficient bleaching effect may not be acquired.

<Bleach activator, bleach activator catalyst>

As a bleaching activator, a well-known compound can be used, Preferably, an organic peracid precursor is used.

Examples of the organic peracid precursor include tetraacetylethylenediamine, alkanoloxybenzenesulfonic acids having 8 to 12 carbon atoms, alkanoloxybenzoic acids having 8 to 12 carbon atoms, or salts thereof. Among these, 4-decanoyloxybenzoic acid and 4-dode Sodium carnoyloxybenzenesulfate and sodium 4-nonanoyloxybenzenesulfate are preferable. These can be used 1 type or in combination of 2 or more types as appropriate.

Particles containing a bleach activator can be produced by a known production method. For example, it can manufacture by the extrusion granulation method and the granulation method by the tablet shape using a briquette machine.

Specifically, the organic peracid precursor particle is an organic peracid precursor and an olefin sulfonic acid while the solid binder material is heated and melted at room temperature such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000. Powder of surfactant, such as a salt, an alkylbenzene sulfonate, or an alkyl sulfate ester salt, is grind | pulverized and extruded, and the noodle-shaped organic peracid precursor granulated material of about 1 mm in diameter is produced, and thereafter, length 0.5 thru | or It is preferable to grind | pulverize lightly about 3 mm, and to mix | blend. As a powder of surfactant, the alpha-olefin sulfonate of alkyl chain length 14 is preferable.

As a bleaching activation catalyst, a well-known compound can be used. As a specific example, transition metal atoms and ligands, such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, or molybdenum, form a complex through a nitrogen atom, an oxygen atom, etc. As the transition metal to be included, cobalt and manganese are preferable, and manganese is particularly preferable. In particular, the bleaching activation catalyst of Unexamined-Japanese-Patent No. 2004-189893 is preferable.

Particles containing a bleach activating catalyst can be produced by a known granulation method. For example, it can manufacture by the extrusion granulation method or the granulation method by tablet shape using a briquette machine.

<Enzyme>

Examples of enzymes classified as reactive enzymes include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be used in the present invention.

Among them, proteases, esterases, lipases, nucleases, cellulases, amylases, pectinases and the like are preferred.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, butyllysine, papain, furomerine, carboxypeptidase A or B, aminopeptidase, and aspergillopeptipeptides. Other agent A, B, etc. are mentioned.

As a commercial item, savinase, alcarase, porazime, cannase, ebarase, and deozyme (above, brand name; novozyme injection); API21 (brand name, Fire Hydrant Co., Ltd. product); Makusakal and Makusa fem (above, brand names; made by Genenko Co.); And protease K-14 or K-16 (the protease described in Japanese Patent Laid-Open No. 5-25492).

Specific examples of esterases include gas lipases, pancreatic lipases, plant lipases, phospholipases, cholinesterases, and phosphatases.

As a specific example of a lipase, commercial lipases, such as a lipoase and a Lipex (above, brand name; Novozyme injection product), and a liposam (brand name, the electric fire electric tool company make), etc. are mentioned.

As a cellulase, For example, Cellzyme (brand name, Novozyme injection product) of a commercial item; Alkali Cellulase K, Alkali Cellulase K-344, Alkali Cellulase K-534, Alkali Cellulase K-539, Alkali Cellulase K-577, Alkali Cellulase K-425, Alkali Cellulase K-521, Alkali Cellulase K-580, Alkali Cellulase K- 588, alkaline cellulase K-597, alkali cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkali cellulase E-III (the cellulase described in Japanese Patent Laid-Open No. 63-264699) Etc. can be mentioned.

Examples of the amylase include commercially available stainzyme, tamil, and duramyl (Novozyme injection).

The said enzyme can be used individually by 1 type or in combination of 2 or more types.

<Defoamer>

As an antifoamer, a conventionally well-known thing, for example, a silicone / silica type thing is mentioned. In addition, it is preferable to use such an antifoamer as the following antifoamer granulated material.

[Method of Manufacturing Antifoam Granule]

First, 20 g of silicone (compound type, trade name: PS antifoam, manufactured by Dow Corning Co., Ltd.) is added to 100 g of maltodextrin (trade name, manufactured by Japan Electrochemical Co., Ltd .; enzyme modified dextrin), and mixed to obtain a homogeneous mixture. Next, after mixing 50 mass% of the obtained homogeneous mixture, 25 mass% of polyethyleneglycol (PEG-6000, melting | fusing point 58 degreeC), and 25 mass% of neutral anhydrous forages at 70-80 degreeC, an extrusion granulator (model EXKS-1, It is granulated by Fuji Powder Co., Ltd., and an antifoamer granulated material is obtained (refer Unexamined-Japanese-Patent No. 3-186307).

<Terminal>

The term "coat" as used herein refers to a mixture (pattern composition) comprising a ingredient, a solvent, a drug stabilizer and the like.

As such a coating agent, the thing of Unexamined-Japanese-Patent No. 2002-146399, the Japan Unexamined-Japanese-Patent No. 2003-89800, etc. can be used, for example.

0.001-2 mass% is preferable, and, as for content of the coating agent in a granular detergent composition, 0.01-1 mass% is more preferable.

<Color>

In order to improve the external appearance of a granular detergent composition, various pigment | dyes, such as dye or a pigment, can be used. Especially, a pigment is preferable at the point of storage stability, and it is especially preferable to have oxidation resistance.

As such a pigment | dye, an oxide etc. are mentioned, for example, Preferably, a titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, an ultramarine blue, a blue color, cyanine blue, cyanine green, etc. are mentioned.

<Surface Treatment Water Soluble Inorganic Compound Particles>

The granular detergent composition of the present invention may optionally contain surface-treated water-soluble inorganic compound particles. As the surface-treated water-soluble inorganic compound particles, for example, the surface-treated water-soluble inorganic compound particles described in pages 3 to 25 of the International Publication No. 2004/094313 pamphlet are suitably used.

Example

Although an Example demonstrates this invention further in detail below, this invention is not limited to these Examples. Below, unless otherwise indicated,% is mass%.

<Used raw material>

The raw materials shown in Tables 1-4 are as follows.

LAS-Na salt: LAS-H (straight chain alkyl (C10-C14) benzenesulfonic acid (manufactured by Lion Co., Ltd., product name: Ripon LH-200 (96 parts by mass)), concentration 48% by mass sodium hydroxide The compound neutralized with the aqueous solution and the compound neutralized with the 48 mass% potassium hydroxide aqueous solution instead of the said sodium hydroxide aqueous solution are mixed by mass ratio 2: 1. The compounding quantity in a table | surface shows the value (mass%) as these mixtures.

MES mixed concentrate: What was manufactured by the following [Manufacture example 1].

Soap: C12-18 fatty acid sodium (Lion Co., Ltd., pure content: 67 mass%, titer: 40-45 degreeC; Fatty acid composition: C12 11.7 mass%, C14 0.4 mass%, C16 29.2 mass%, C18F0) (Stearic acid) 0.7 mass%, C18F1 (oleic acid) 56.8 mass%, C18F2 (linoleic acid) 1.2 mass%; Molecular weight: 289).

POE alkyl ether (AE): Ethylene oxide average 15 mole adduct (90% of pure parts) of ECOROL26 (product name, the product made by ECOGREEN, the alcohol having a C12-C16 alkyl group).

MA agent: Acrylic acid / maleic anhydride copolymer sodium salt (brand name: Aquaric TL-400, Nippon Catalyst Co., Ltd. product; 40 mass% of pure components aqueous solution).

Zeolite: A-type zeolite, Silton B (brand name, Mizuwa Chemical Co., Ltd. make; 80 mass% of pure parts).

Sodium carbonate: grain ash (Asahi Glass Co., Ltd. make, average particle diameter 320 micrometers, bulk density 1.07 g / cm <3>).

Potassium carbonate: potassium carbonate (powder) (Asahi Glass Co., Ltd. make, average particle diameter 490 micrometers, bulk density 1.30 g / cm <3>).

Sodium sulfate: Neutral anhydride (manufactured by Nippon Chemical Industries, Ltd.).

Enzyme particles: Savinase 12T (Novozyme injection).

Cellulose: ARBOCEL BE600 / 30 (manufactured by Retenmeier Co., Ltd., average fiber length 30 μm, average fiber diameter 18 μm).

[Zinc Oxide Particles]

A-1: Product made from Honjo Chemical Co., Zincoxide (product name), two kinds of zinc oxide, 0.55 micrometer in average particle diameter.

A-2: Kanto Chemical Co., Ltd., zinc oxide 3N5, average particle diameter 7.5micrometer.

A-3: FINEX-30, a fine particle zinc oxide, 0.035 micrometer of average particle diameters manufactured by Sakai Chemical Industries, Ltd ..

[Alumino silicate]

A-4: manufactured by Lion, Lioness Naito _{SF (SiO 2: ZnO: AL} 2 O 3 molar ratio = 52: 32: 16), the mean particle size 3.5㎛ alumino-zinc silicate of the granular material of.

A-5: 14 g of lionite SF of A-4 was dispersed in 686 g of ion-exchanged water, and the aqueous dispersion was adjusted to 2 mass%. This aqueous dispersion was made by a hand-made bead mill (ultra-apex mill: UAM-015) using a 0.1 mm diameter zirconium oxide bead at a speed of 10 m / sec (rotor rotation speed 4,300 rpm). It pulverized for 10 minutes on condition, and obtained the aluminosilicate silicate particle dispersion. This was filtered by suction, washed with water and dried at 100 ° C. The cake obtained was jet milled to obtain Lionite SF having an average particle diameter of 0.42 탆.

A-6: Synthesis Example 1

The molar ratio of SiO ₂ : ZnO: AL ₂ O ₃ of zinc aluminosilicate was adjusted as follows: 31:54:15.

No. 3 Sodium Silicate (Fuji Chemical, 29% by weight of SiO ₂ , 9.5% by weight of Na ₂ O) and 82.6 g of sodium hydroxide (Kanto Chemical, Limited) were dissolved in ion-exchanged water to make 1 L of this. It is liquid. On the other hand, 95 g of zinc chloride (Kanto Chemical Co., Ltd.) and 97 g of aluminum chloride hexahydrate (Kanto Chemical Co., Co., Ltd.) are dissolved in ion-exchanged water to make the total amount 1 L, which is B liquid. 1 L of ion-exchanged water was put into a 5 L beaker, and while stirring, the liquid A and the liquid B were each simultaneously charged at a rate of about 25 ml / min. After completion of the stock price, the pH of the reaction solution was 6.9. After stirring was continued and aged for 30 minutes, it heated at 85-90 degreeC on the water bath for 2 hours. The reaction solution was suction filtered, washed with water and dried at 100 ° C. The obtained cake was jet-milled and the granular material of the aluminosilicate was obtained as a granular material of 3.5 micrometers of average particle diameters.

[Carboxymethyl cellulose particles]

B-1: Japan Paper Chemical Co., Ltd., Sunrose SLD-F1, weight average molecular weight (henceforth Mw) 300,000, and etherification degree 0.30.

B-2: Daicel Chemical Co., Ltd. product, CMC dice 1290, Mw 990,000, etherification degree 0.90.

B-3: Daicel Chemical Co., Ltd., CMC Daicel 1170, Mw 680,000, etherification degree 0.64.

B-4: Daicel Chemical Co., Ltd. make, CMC dice 1130, Mw 300,000, etherification degree 0.70.

B-5: Nippon Paper Chemical Co., Ltd., Sunrose B1B, Mw 60,000 only, etherification degree 0.50.

B-6: Daicel Chemical Co., Ltd. make, CMC dice 1380, Mw 111 million, etherification degree 1.25.

Preparation Example 1 Preparation of MES Mixture Concentrate

(Sulfonation process)

First, methyl parmitate (manufactured by Lion Corporation, trade name: Pastel M-16) and methyl stearate (manufactured by Lion Corporation, brand name: Pastel M-180) are mixed to 80:20 (mass ratio), Furthermore, by hydrotreating by the usual method, iodine number was reduced to 0.2 and purified, and purified fatty acid methyl ester was obtained. By using this purified fatty acid methyl ester to flow down type (流下型) thin film reactor, a dehumidified reaction with the air in the SO ₃ gas diluted to a 7% molar ratio (SO ₃ / saturated fatty acid ester) = 1.18, reaction temperature of 80 ℃ Sulfonated to give the sulfonated product.

(Aging process)

Next, the obtained sulfonated product was introduced into a loop aged tube with a double tube jacket having an average residence time of 20 minutes. This loop aged tube was connected three times in succession, and the average residence time was 60 minutes. In order to maintain sufficient agitation and a constant temperature, the sulfonated product was poured into a loop mating tube at a line speed of 0.16 m / s, controlled at 78 to 82 ° C. to undergo a aging reaction to complete the sulfonation, and thereby to form α-sulfo. Fatty acid methyl ester was obtained.

(Esterification, bleaching process)

Subsequently, 20 mass parts of methanol (Methanol by Sumitomo Chemical Co., Ltd .: industrial grade, water 500 ppm or less) was introduce | transduced into 100 mass parts of (alpha)-sulfo fatty acid methyl esters obtained, and this mixture and 35% hydrogen peroxide (35 made by Mitsubishi Gas Chemical Co., Ltd.) % Industrial Hydrogen Peroxide: Industrial Grade) 5.7 parts by mass were introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger to bleach to obtain an α-sulfofatty acid methyl ester bleaching treatment.

(Neutralization process)

Subsequently, with respect to 125 mass parts of obtained alpha-sulfofatty acid methyl ester bleaching process, 28 mass parts of 48% NaOH aqueous solution (caustic soda made by Daiso Corporation: industrial grade), 25 mass parts of nonionic surfactants (POE alkyl ether), 69 parts by mass of water, 24 parts by mass of methanol (methanol manufactured by Sumitomo Chemical Co., Ltd.), and 5 parts by mass of linear alkylbenzenesulfonic acid (LAS-H) were continuously supplied to the neutralization line.

The neutralization method employ | adopted the neutralization method of Unexamined-Japanese-Patent No. 2001-64248, and 48 mass% sodium hydroxide aqueous solution was quantitatively fed between a premixer and a neutralization mixer, and it was able to neutralize continuously. The neutralized product of the α-sulfofatty acid methyl ester bleaching product neutralized in advance and the α-sulfofatty acid methyl ester bleaching mixture were thoroughly mixed in a premixer, and then mixed with an aqueous sodium hydroxide solution to obtain a neutralized product.

(Concentration process)

Further, using the above neutralized product as an aqueous solution of the raw material surfactant, recycling flash evaporation described in Japanese Patent Laid-Open No. 2004-210807 was performed, and lower alcohol was removed and concentrated to obtain MES concentrated mixture (MES 62) having a water content of 10.8%. Mass%, 3.5 mass% of LAS-Na, and 16.8 mass% of nonionic surfactants) were obtained.

[Examples 1 to 8 and Comparative Examples 1 to 13]

According to the mixing | blending ratio shown in Table 1-Table 4, the granular detergent composition was prepared by the following preparation method. Washing was performed using the obtained granular detergent composition, and the odor (odor drying in room) inhibitory effect when the blood cells were dried indoors was evaluated.

In addition, in Table 1-Table 4, the unit of a compounding ratio is "mass%", and mixing ratio A / B is a mass ratio.

[Preparation method of granular detergent composition]

(Slurry Preparation Process and Spray Drying Process)

Water was put into the mixing vessel with a jacket provided with a stirring device, and the temperature was adjusted to 60 degreeC. Surfactant (except MES mixed concentrate and nonionic surfactant (POE alkyl ether)) was added to this, and it stirred for 10 minutes.

Subsequently, MA agent was added. After stirring for 10 minutes, a part of the zeolite (for addition at 1.0% of the printing time, 5.0% of crushing aid, and 1.5% for surface coating) than the addition amount shown in Tables 1 to 4, sodium carbonate , Potassium carbonate, and sodium sulfate were added. Furthermore, it stirred for 20 minutes and prepared the spray drying slurry of 38% of moisture.

The slurry was spray dried on a hot air temperature of 280 ° C. using a countercurrent spray drying tower to obtain spray dried particles having an average particle diameter of 320 μm, a bulk density of 0.30 g / cm 3, and a moisture of 5%.

(Chemical process)

The obtained non-ionic surfactant, water, and Example 17 except for the spray-dried particles obtained, the MES mixed concentrate, the zeolite (for the addition at the time of kneading, 1.0%), the non-ionic surfactant for the spray addition, water, and Example 17 were (A) oxidation Zinc particles, and Example 18, (A) zinc aluminosilicate particles were charged into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Iron Works Co., Ltd.), and then kneaded under conditions of 120 kg / hr and 60 ° C. A mixture of 6% moisture containing a surfactant was obtained.

(Grinding process)

The mixture obtained in the kneading process is cut with a cutter while extruding using a pelleter double (manufactured by Fuji Powder Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (the cutter circumferential speed is 5 m / s). ), Pellets having a length of about 5 to 30 mm were obtained.

Subsequently, zeolite (for grinding aid, 5.0%) was added to the resulting pellets, and a Pitts Mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) was disposed in three stages under coexistence of cold air (10 ° C, 15 m / s). It grind | pulverized using (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3mm, and rotation speed: 4700 rpm of 1st stage / 2nd stage / 3rd stage).

(Post-processing process)

The powder obtained by the grinding | pulverization process, particulate-form (B) CMC, and Examples 1-8 and Comparative Examples 1-7 are (A) zinc oxide particles, and Examples 9-16 and Comparative Examples 8-13 are aluminum Zinc silicate particles have a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, volume 131.7 L, drum 20 mm clearance with the inner wall surface and two block plates of 45 mm height). 1) while adding a zeolite (1.5% for surface coating) and spraying a nonionic surfactant (for spraying, 0.5%) under conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm and 25 ° C. Motorized for minutes to obtain surface modified particles.

In addition, the surface-modified particle | grains and enzyme particle | grains obtained above were thrown into the same horizontal cylindrical electric mixer, and it mixed for 5 minutes on the conditions of 30 volume% of filling rates, 22 rpm, and 25 degreeC, and obtained the granular detergent composition.

[Assessment Methods]

Using the granular detergent composition obtained in the Example and the comparative example, after washing and drying the fibers according to the following washing method, the smell of the fibers was smelled, and the effect of suppressing the occurrence of odor was evaluated according to the following evaluation criteria. The results are shown in Tables 1-4.

(Washing method)

After using 20 pieces of towels wiping 100% of new cotton each hand for approximately one day in normal life, we put in fully automatic washing machine (NA-F70AP made in Matsushita electric appliance company, NA-F70AP), temperature approximately 20 degrees Celsius, hardness approximately 3 degrees DH tap water was poured in and washed with a standard course. In addition, detergent input amount followed the detergent amount indication of the washing machine. After the completion of dehydration, the resultant was dried at a room temperature of about 25 ° C. and 70% RH of humidity, and dried for 12 hours.

(Evaluation standard)

Evaluation was performed by 10 professional panelists, scored based on the following evaluation criteria, and the average score was computed. The average point is less than 0.5 points A: More than 0.5 points and less than 2 points which do not feel bad smell B: More than 2 points and less than 3 points which hardly feel odor C: More than 3 points which feel a little odor D: More than 3 points The effect of suppressing the smell of drying in the room was evaluated.

5 points | pieces: An intense smell.

4 points | pieces: Strong smell.

3 points | pieces: The smell which can be sensed comfortably.

2 points | pieces: The mild smell which knows what kind of smell it is.

1 point | piece: The smell which seems faint.

0 points | pieces: There is no smell.

TABLE 1

TABLE 2

[Table 3]

[Table 4]

As shown in the results of Tables 1 to 4, (A) zinc oxide particles or aluminosilicate silica particles and (B) Mw are CMC within the range of 300,000 to 1 million, and (A) / (B) is 10 The granular detergent composition of Examples 1 to 18 contained in the range of 1/1 to 1/4 had a good effect of suppressing the smell of drying in the room.

On the other hand, Comparative Examples 1 and 8 in which the Mw of the CMC is too large, and Comparative Examples 2 and 9 in which the Mw is too small have not sufficiently obtained an inhibitory effect of odor drying in the room.

In addition, Comparative Example 3 contains the same amount of (A) zinc oxide particles or aluminosilicate silica particles as in Example 1 and Comparative Example 10, but (B) suppresses the smell of drying in a room because the content of CMC is small. The effect was not obtained sufficiently.

In Comparative Example 4 and 11, (A) / (B) was 1/6 small and the inhibitory effect of the smell of drying in a room was not acquired.

In Comparative Examples 5 and 12, CMC was not used and cellulose was used instead, but the effect of suppressing the smell of drying in the room was not obtained.

In addition, as in Comparative Examples 6, 7, and 13, even when only one of (A) zinc oxide particles or aluminosilicate silica particles and (B) CMC was contained, the effect of suppressing the smell of drying in the room was not obtained.

[Industrial Availability]

According to this invention, the granular detergent composition excellent in the odor suppression effect which arises when drying the wash | cleaned clothing can be provided.

Claims (2)

(A) one or more kinds of particles selected from zinc oxide particles and zinc aluminosilicate particles, and (B) carboxymethyl cellulose having a weight average molecular weight of 300,000 to 1,000,000, and (A) zinc oxide particles and / or aluminosilicate The mass ratio composition (A) / (B) of zinc particle and (B) carboxymethyl cellulose is 10/1-1/4, The granular detergent composition characterized by the above-mentioned. The method of claim 1,
(A) Granular detergent composition characterized in that the average particle diameter of the zinc oxide particles and / or zinc aluminosilicate particles is 10㎛ or less.