KR101944345B1

KR101944345B1 - Granular detergent composition and method for producing same

Info

Publication number: KR101944345B1
Application number: KR1020157020946A
Authority: KR
Inventors: 다이스케 사사키; 토시히코 타치카와
Original assignee: 라이온 가부시키가이샤
Priority date: 2013-07-22
Filing date: 2014-07-18
Publication date: 2019-01-31
Also published as: JP6414986B2; JPWO2015012235A1; KR20160033066A; WO2015012235A1

Abstract

A granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c), wherein the granular detergent composition is prepared by spray drying a slurry comprising the surfactant (a) and a portion of the zeolite (X) containing the inorganic peroxide (b) and particles (Y) containing the inorganic peroxide (b); The content of the zeolite (c) is 5 to 15 mass% with respect to the total mass of the granular detergent composition; The zeolite (c) comprises a zeolite (c1) blended with the slurry and a zeolite (c2) other than the zeolite (c1), and the mass ratio c1 / c2 of the zeolite (c1) to the zeolite 0.0 > 0.7 < / RTI >

Description

TECHNICAL FIELD [0001] The present invention relates to a granular detergent composition,

The present invention relates to a granular detergent composition and a manufacturing method thereof.

The present application claims priority based on Japanese Patent Application No. 2013-151505 filed on July 22, 2013, the content of which is incorporated herein by reference.

BACKGROUND ART [0002] Conventionally, as particulate detergents used in laundry for medical treatment at home and the like, spray-dried particles in which a slurry containing a surfactant, a cleaning builder (water-soluble inorganic salt, etc.) are spray-dried are used. However, spray-dried particles are bulky, and granular detergents, so-called compact detergents, which increase the bulk density of detergent particles in place of granular detergents composed of spray-dried particles at present, have become mainstream. Examples of the method for producing the detergent particles having a high bulk density include a method of pulverizing a kneaded product obtained by kneading the spray-dried particles and the other components with water in a kneader (kneader), or a method of pulverizing a kneaded product obtained by kneading the spray- A method of impregnation is known.

The granular detergent generally contains inorganic peroxide particles such as sodium percarbonate as an external bleaching agent.

Since zeolite has various advantages in terms of the quality and the production surface of the granular detergent, it is often incorporated into granular detergent. For example, the merits of quality include various improvements such as improvement of cleaning performance by capturing Ca ions in tap water, suppression of solidification of surfactant, improvement of fluidity, and the like. Further, in terms of production, zeolite is incorporated in the slurry used for producing the spray-dried particles and contributes to the skeleton formation of the detergent particles. It is also used as a lubricant or a pulverizing auxiliary in order to ensure the fluidity of the detergent particles in the production process.

However, in the granular detergent containing the detergent particles and the inorganic peroxide particles, the zeolite has a problem that the storage stability of the functional ingredient, particularly the inorganic peroxide, is lowered.

In order to solve such problems, various techniques for improving the stability of inorganic peroxide have been studied (for example, Patent Documents 1 and 2). However, the effect still has room for improvement.

Japanese Patent Application Laid-Open No. 2000-256699 Japanese Patent Application Laid-Open No. 2010-215814

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a granular detergent composition having improved storage stability of inorganic peroxide under the coexistence of zeolite and a method for producing the same.

As a result of intensive investigations, the inventors of the present invention have found that by lowering the proportion of zeolite subjected to the spray drying process in the zeolite blended with the granular detergent (i.e., increasing the proportion of zeolite not subjected to the spray drying process) .

The present invention is based on the above knowledge and has the following form.

[1] A granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

(Y) containing particles (X) containing the surfactant (a) and no inorganic peroxide (b) and the inorganic peroxide (b)

Wherein the particles (X) comprise spray dried particles obtained by spray-drying a slurry containing a part of the zeolite (c)

The content of the zeolite (c) is 5 to 15% by mass,

Wherein the mass ratio (c1 / c2) of the zeolite (c1) to the zeolite (c2) other than the zeolite (c1) in the slurry of the zeolite (c) is 0.7 or less.

[2] A method for producing a granular detergent composition containing a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

(X) containing the surfactant (a) and not containing the inorganic peroxide (b) from the spray-dried particles by spray-drying a slurry containing a part of the zeolite (c) And

Mixing the particles (Y) containing the inorganic peroxide (b) with the particles (X)

The amount of the zeolite (c) to be used is 5 to 15% by mass based on the total mass of the granular detergent composition to be produced,

That is, the present invention relates to the following.

[1 '] A granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

The granular detergent composition comprises

(X) which comprises spray-dried particles obtained by spray-drying a slurry containing the surfactant (a) and a part of the zeolite (c), and which does not contain the inorganic peroxide (b)

(Y) comprising the inorganic peroxide (b);

The content of the zeolite (c) is 5 to 15 mass% with respect to the total mass of the granular detergent composition;

The zeolite (c) comprises a zeolite (c1) blended with the slurry and a zeolite (c2) other than the zeolite (c1), and the mass ratio c1 / c2 of the zeolite (c1) to the zeolite 0.0 > 0.7 < / RTI >

A method for producing a granular detergent composition containing [2 '] a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

The above-

A step of obtaining the particles (X)

A mixing step of mixing the particles (Y) containing the inorganic peroxide (b) and the particles (X)

The step of obtaining the particles (X)

Spray-drying a slurry containing a part of the zeolite (c) to obtain spray-dried particles,

(X) containing the surfactant (a) but not containing the inorganic peroxide (b) from the obtained spray dried particles,

(Effects of the Invention)

According to the present invention, it is possible to provide a granular detergent composition having improved storage stability of inorganic peroxide under the coexistence of zeolite and a method for producing the granular detergent composition.

(Granular detergent composition)

One aspect of the granular detergent composition according to the first aspect of the present invention is that the surfactant (a) (hereinafter referred to as component (a)) and the inorganic peroxide (b) (hereinafter referred to as component (b)) and the zeolite ) (Hereinafter referred to as component (c)),

Wherein said granular detergent composition contains particles (X) comprising said component (a) and no component (b) and particles (Y) comprising said component (b)

The particles (X) include spray-dried particles obtained by spray-drying a slurry containing a part of component (c)

The content of the component (c) is 5 to 15 mass% with respect to the total mass of the granular detergent composition,

The mass ratio (c1 / c2) of the zeolite (c1) to the zeolite (c2) other than the zeolite (c1) in the slurry of the component (c) is more than 0 and not more than 0.7.

Another aspect of the granular detergent composition, which is the first aspect of the present invention,

A granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

Wherein the granular detergent composition comprises spray dried particles obtained by spray drying a slurry containing the surfactant (a) and a part of the zeolite (c), and the particle X containing no inorganic peroxide (b) Wow,

(Y) comprising the inorganic peroxide (b);

&Lt; Components constituting the granular detergent composition >

The components constituting the granular detergent composition according to the first embodiment of the present invention include at least the following components (a), (b) and (c). The granular detergent composition may further contain components other than the components (a) to (c), if necessary.

&Quot; Component (a) "

The surfactant of component (a) is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

The anionic surfactant is not particularly limited as long as it is an anionic surfactant used in a granular detergent, and examples thereof include the following anionic surfactants (1) to (12).

(1) alpha -sulfo fatty acid alkyl ester salt.

The kind of the? -sulfo fatty acid alkyl ester salt is not particularly limited, and any of the? -sulfo fatty acid alkyl ester salt used in a general granular detergent composition can be suitably used. The? -sulfo fatty acid alkyl ester salt represented by the following formula (11) Alkyl ester salts are preferable.

R ¹¹ -CH (SO ₃ M) -COOR ¹² (11)

In the formula (11), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms or a straight or branched chain alkenyl group having 8 to 20 carbon atoms, preferably a straight chain or branched chain having 14 to 16 carbon atoms Chain alkyl group.

R ¹² is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group, an ethyl group, and a propyl group are preferable because the washing power is further improved, and a methyl group is particularly preferable.

M represents a counter ion, for example, an alkali metal salt such as sodium or potassium; Amine salts such as monoethanolamine, diethanolamine and triethanolamine; Ammonium salts and the like. Among them, an ion forming an alkali metal salt is preferable.

As the? -sulfo fatty acid alkyl ester salt, for example,? -sulfo fatty acid methyl ester sodium salt (MES) is preferable.

(2) a linear or branched alkylbenzene sulfonic acid salt (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.

(3) An alkanesulfonate having 10 to 20 carbon atoms.

(4)? -Olefin sulfonic acid salts (AOS) having 10 to 20 carbon atoms.

(5) an alkylsulfate having 10 to 20 carbon atoms or an alkenylsulfate (AS) having 10 to 20 carbon atoms.

(6) an alkylene oxide having 2 to 4 carbon atoms, or an ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) ether sulfates (AES) having a straight chain or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms (i.e., having an average addition molar number of 0.5 to 10).

(7) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) phenyl ether sulfates having a straight or branched chain alkyl group (or alkenyl group) having 10 to 20 carbon atoms (i.e. having an average addition molar number of 3 to 30).

(8) an alkylene oxide having 2 to 4 carbon atoms, or an ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) ether carboxylate having a straight or branched chain alkyl group (or alkenyl group) having 10 to 20 carbon atoms (i.e., having an average addition mole number of 0.5 to 10).

(9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.

(10) long chain monoalkyl, dialkyl or sesquioalkyl phosphates.

(11) polyoxyethylene monoalkyl, dialkyl or sesquioalkyl phosphates.

(12) High fatty acid salts having 10 to 20 carbon atoms (soap).

These anionic surfactants include alkali metal salts such as sodium salt and potassium salt; Amine salts; Ammonium salts and the like.

These anionic surfactants may be used alone, or two or more thereof may be used in combination.

The nonionic surfactant is not particularly limited as long as it is a nonionic surfactant conventionally used in the granular cleansing agent, and examples thereof include the following nonionic surfactants.

(1) an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18, more preferably 10 to 16, particularly preferably 12 to 14 carbon atoms, an alkylene oxide having 2 to 4 carbon atoms, Preferably 3 to 20 mol, more preferably 5 to 20 mol, particularly preferably 12 to 20 mol, most preferably 14 to 18 mol (that is, the average addition mole number is 3 to 30 mol , Preferably from 3 to 20 moles, more preferably from 5 to 20 moles, particularly preferably from 12 to 20 moles, and most preferably from 14 to 18 moles, of the polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.

Examples of the aliphatic alcohol used herein include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. The aliphatic alcohol is preferably a primary alcohol.

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

(3) Fatty acid alkyl ester alkoxylates to which an alkylene oxide is added between ester bonds of a long chain fatty acid alkyl ester.

(4) Polyoxyethylene sorbitan fatty acid ester.

(5) Polyoxyethylene sorbit fatty acid esters.

(6) Polyoxyethylene fatty acid ester.

(7) Polyoxyethylene hardened castor oil.

(8) Glycerin fatty acid ester.

The fatty acid alkyl ester alkoxylate of the above (3) includes, for example, those represented by the following general formula (31).

R ⁹ CO (OA) _q R ¹⁰ (31)

In formula (31), R ⁹ CO is a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18, more preferably 10 to 16, particularly preferably 12 to 14 fatty acid residues.

OA is an addition unit of an alkylene oxide having 2 to 4 carbon atoms (oxyalkylene group), preferably an alkylene oxide having 2 to 3 carbon atoms, more preferably ethylene oxide, propylene oxide and the like.

q represents an average addition mole number of the alkylene oxide, and is 3 to 30, preferably 5 to 20. Q may be an integer or may include a prime number.

R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.

These nonionic surfactants may be used singly or in combination of two or more.

Among the above nonionic surfactants, the nonionic surfactant of the above (1) is preferable. Particularly, an aliphatic alcohol having 12 to 16 carbon atoms and an alkylene oxide having 2 to 4 carbon atoms on an average of 5 to 20, preferably 12 to 20 (Or an alkenyl having an average addition mole number of 5 to 20 moles, preferably 12 to 20 moles, more preferably 14 to 18 moles), more preferably 14 to 18 moles, ) Ether is preferable.

Further, it is preferable to use a polyoxyethylene alkyl (or alkenyl) ether, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having an HLB of 9 to 16 at a melting point of 50 ° C or lower, a fatty acid methyl Esters ethoxylate, fatty acid methyl esters in which ethylene oxide and propylene oxide are added to fatty acid methyl esters, and ethoxy propoxylate are suitably used.

The term " HLB of a nonionic surfactant " in the present specification means a value obtained by the Griffin method (Yoshida, Shindo, Ohgaki, Yanamaka publication, "New Edition Surfactant Handbook" See page 234).

The "melting point" in the present specification means a value measured by the melting point measurement method described in JIS K0064-1992 "Method of measuring melting point and melting range of a chemical product".

As the cationic surfactant, for example, the following cationic surfactants can be mentioned.

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

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

(3) Tree long long chain alkyl mono short chain alkyl type quaternary ammonium salt.

The term " long chain alkyl " means an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.

The "short chain alkyl" includes substituents such as a phenyl group, a benzyl group, a hydroxyl group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, alkyl groups having 1 to 4, preferably 1 to 2, carbon atoms; Benzyl group; A hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; Preferred examples of the short-chain alkyl include 2 to 4, preferably 2 to 3, polyoxyalkylene groups.

Examples of the amphoteric surfactant include imidazoline amphoteric surfactants and amide betaine amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl betaine may be mentioned as preferred amphoteric surfactants.

The content of the component (a) in the granular detergent composition according to the first embodiment of the present invention is preferably 5 to 30 mass%, more preferably 5 to 15 mass%, and more preferably 7 to 11 mass%, based on the total mass of the granular detergent composition % Is particularly preferable. If it is 5% by mass or more, sufficient cleaning performance can be obtained as a granular detergent. If it is 30 mass% or less, the fluidity of the particles after humidity storage is good.

&Quot; Component (b) "

Component (b) is an inorganic peroxide. The component (b) mainly functions as a bleaching component.

As the component (b), inorganic peroxides conventionally used in granular detergents and the like can be used, and examples thereof include percarbonates such as sodium percarbonate particles; And perborates such as sodium borate and sodium perborate trihydrate. Of these, sodium percarbonate is preferable from the viewpoints of solubility in use and stability in storage.

The content of the component (b) in the granular detergent composition according to the first embodiment of the present invention is preferably 3 to 20 mass%, more preferably 3 to 15 mass%, and more preferably 7 to 15 mass%, based on the total mass of the granular detergent composition % Is particularly preferable. If it is 3% by mass or more, the effect of the component (b) (such as improvement of cleaning power against bleaching, sterilization, stain contamination, etc.) is sufficiently obtained. If the amount exceeds 20% by mass, the amount of other cleaning components may be decreased and the cleaning power may decrease.

&Quot; Component (c) "

The component (c) is zeolite. The term " zeolite " is a generic term for aluminosilicate. The zeolite in the present invention is preferably aluminosilicate which is crystalline in terms of cation exchange ability and is a structural body. Examples of the crystalline aluminosilicate zeolite include A type, X type, Y type and P type zeolite, and in the present invention, any zeolite can be used.

The content of the component (c) in the granular detergent composition according to the first embodiment of the present invention is preferably 5 to 15% by mass, and more preferably 8 to 15% by mass with respect to the total mass of the granular detergent composition.

When the content of the component (c) is 15 mass% or less, the stability of the component (b) is good. In addition, it is difficult for fine particles to be generated and fluidity is hard to deteriorate. Further, no significant turbidity of the washing liquid is observed at the time of washing, and the rinsing property is improved.

When the content of the component (c) is 5 mass% or more, the effect of the component (c) (that is, the improvement of the cleaning performance by capturing the Ca ions present in the washing liquid at the time of washing, the infiltration of the surfactant, Suppression of solidification, improvement of fluidity of the particle group, etc.).

In the granular detergent composition according to the first embodiment of the present invention, a part of the component (c) (that is, the zeolite (c1) described below) is blended with water and other components as required to form a slurry, And becomes spray-dried particles. The spray-dried particles are added to the granular detergent composition of the first embodiment of the present invention as it is or by adding water and other components as necessary to the spray-dried particles, kneading and pulverizing them.

That is, in the granular detergent composition according to the first embodiment of the present invention, the zeolite (c1) (that is, the zeolite undergoing the spray drying process) blended with the slurry as the component (c) and the zeolite (c2) other than the zeolite (c1) (I.e., zeolites that do not undergo a spray drying process).

That is, the component (c) is composed of the zeolite (c1) blended with the slurry and the zeolite (c2) other than the zeolite (c1).

The entire amount of the zeolite (c1) is contained in the particle (X).

The zeolite (c2) may be blended into the granular detergent composition as long as it is not subjected to the spray drying process. For example, zeolite (c2) may be added to the spray-dried particles by adding zeolite (c2) together with a surfactant or water and performing wet granulation such as kneading or pulverization. Zeolite (c2) may be used as the milling aid at the time of pulverization. The powdery zeolite (c2) may be dry-mixed with the particles (X), the particles (Y) and the like to be present as independent particles.

In the granular detergent composition according to the first embodiment of the present invention, the mass ratio of zeolite (c1) to zeolite (c2) (i.e., c1 / c2) is 0.7 or less, preferably 0.5 or less, more preferably 0.4 or less. Conventionally, in order to ensure the stability of component (b), the amount of zeolite to be added to the slurry tends to be kept in order to ensure the stability of the slurry while reducing the amount of zeolite as a whole, and c1 / c2 tends to increase have. However, according to the study by the present inventors, the stability of the component (b) improves by unexpectedly decreasing c1 / c2 to 0.7 or less.

The lower limit of c1 / c2 is not particularly limited in terms of the stability of the component (b) and may be more than 0, but if the proportion of the zeolite (c1) is too low, the fluidity of the particles (X) .

In other words, as c1 / c2, it is more than 0 and not more than 0.7, preferably not less than 0.2 and not more than 0.7, more preferably not less than 0.2 and not more than 0.5, and particularly preferably not less than 0.2 and not more than 0.4.

The content of the zeolite (c2) in the granular detergent composition according to the first embodiment of the present invention is preferably 3 mass% or more and less than 15 mass%, more preferably 5 mass% or less and 10 mass% or less, based on the total mass of the granular detergent composition desirable. If the content of the zeolite (c2) is less than 15% by mass, fine powder of the zeolite is hardly generated in the granular detergent composition, the fluidity is hardly reduced, and the stability of the component (b) improves. When the content of the zeolite (c2) is less than 3 mass%, the content of the zeolite (c1) is relatively small and the content of the component (c) , Inhibition of solidification of the surfactant, improvement of fluidity, etc.) may not be sufficiently obtained.

«Optional ingredients»

The granular detergent composition according to the first embodiment of the present invention may further contain components other than the components (a) to (c) within the range that does not impair the effect of the present invention. As the other components, various components conventionally used in the granular detergent may be used. For example, the components other than the component (c) may be selected from other cleaning builders, organic peracid precursors, metal salts, sequestering agents, An enzyme, an enzyme stabilizer, a re-contamination inhibitor, an anti-caking agent, a pH adjuster, and a binder.

[Other clean builders]

Other qualitative builders include inorganic builders other than component (c), organic builders, and the like.

Other inorganic builders include, 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 layered sodium silicate (for example, a crystalline alkali metal silicate such as "Na-SKS-6" (δ-Na ₂ O 揃 2SiO ₂ ) manufactured by Clariant Japan KK); Amorphous alkali metal silicates; Sulfates such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; Phosphates such as orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, and phthalates; And a complex of sodium carbonate and an amorphous alkali metal silicate (for example, trade name " NABION 15 " produced by Rhodia).

Of these, sodium carbonate, sodium bicarbonate, potassium salt (potassium carbonate, potassium sulfate, etc.) and alkali metal chloride (potassium chloride, sodium chloride and the like) are preferable, and sodium bicarbonate is particularly preferable.

The content of other inorganic builders in the granular detergent composition is preferably 10 to 70 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 25 mass%, based on the total mass of the granular detergent composition.

Examples of the organic builder include hydroxycarboxylic acids such as hydroxyacetic acid, tartaric acid, citric acid, gluconic acid, and hydroxyiminodisuccinic acid, and salts thereof; Cyclic carboxylic acids such as pyromellitic acid, benzopicarboxylic acid, and cyclopentanetetracarboxylic acid and salts thereof; Ether carboxylic acids such as carboxymethyl tartrate, carboxymethyl oxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate, and salts thereof; Polyacetal carboxylic acids such as polyacrylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer and polyglyoxylic acid, and salts thereof; Acrylic acid polymers or copolymers such as hydroxy acrylic acid polymers, polysaccharide-acrylic acid copolymers and their salts; Polymers or copolymers of maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, and aspartic acid; and salts thereof; Polysaccharide derivatives such as polysaccharide oxides such as starch, cellulose, amylose and pectin, and the like.

Among them, hydroxycarboxylic acid and its salt, polyacetal carboxylic acid and its salt (for example, polyacetal carboxylic acid and its salt described in JP-A 54-52196) are preferable. As the hydroxycarboxylic acid and its salt, citric acid, citric acid salt, hydroxyiminodisuccinic acid salt and the like are preferable, and citric acid and citric acid salt are more preferable. The salt of the polyacetal carboxylic acid is preferably a polyacrylic acid salt, a salt of an acrylic acid-maleic acid copolymer, a polyglyoxylic acid, or the like, a salt of an acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, Polyacrylic acid salts having a weight average molecular weight of 800 to 1,000,000 (preferably 5,000 to 200,000), and the like are more preferable.

[Organic Acid Precursor]

The organic peracid precursor functions as a bleach activator.

As the organic peracid precursor, conventionally known organic peracid precursors are used, and examples thereof include decanoyloxybenzoic acid, dodecanoyloxybenzenesulfonic acid, sodium dodecanoyloxybenzenesulfonate, and sodium nonanoyloxybenzenesulfonate. The organic peracid precursors may be used singly or in combination of two or more.

The organic peracid precursor can be compounded as particles containing an organic peracid precursor (hereinafter referred to as " organic peracid precursor particle "). The organic peracid precursor particles can be produced by a known production method. Examples of the production method include an extrusion granulation method and a granulation method using a briquetting machine. Specifically, the organic peroxide precursor particles can be obtained by the following production method.

And the powder of the organic peracid precursor and the surfactant is dispersed while heating and melting the binder material which is solid at room temperature, such as polyethylene glycol (weight average molecular weight 3000-20000, preferably 4000-6000). Thereafter, it is extruded by an extruder or the like to form a noodle phase having a diameter of about 1 mm, and further pulverized to a length of about 0.5 to 3 mm to obtain organic peracid precursor particles. The organic peroxide precursor particles thus obtained can be suitably used from the viewpoint of preventing classification in the high-volume-density particulate detergent composition.

As the surfactant, olefinsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylsulfuric acid ester salts and the like are preferable, and? -Olefin sulfonic acid salts having an alkyl chain length of 14 are more preferable.

[Metal salt]

As the metal salt, conventionally known metal salts are used, and examples thereof include manganese compounds such as manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, and manganese acetylacetonate; Copper compounds such as copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, ammonium chloride copper, copper gluconate, copper tin oxide and copper perchlorate; Zinc compounds such as zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc ammonium chloride, zinc gluconate, zinc tartrate and zinc perchlorate. The metal salts may be used singly or in combination of two or more kinds.

Of these, manganese sulfate, manganese chloride, copper sulfate, zinc chloride, zinc gluconate, zinc sulfate and zinc chloride are preferable from the viewpoints of handling property, cost, and feedability of raw materials, and copper sulfate and zinc sulfate are more preferable.

[Metal ion sequestrant]

As the metal ion sequestering agent, conventionally known metal ion sequestering agents are used. Examples of the sequestering agents include metal ion sequestrants such as nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt, beta -alanine diacetate salt, aspartic acid diacetate salt, methylglycine diacetate salt and iminodisuccinic acid salt Aminocarboxylic acid salts; Aminocarboxylic acid type sequestration agents such as serin diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, and hydroxyaminocarboxylate such as dihydroxyethyl glycine salt; 1,1-diphosphonic acid, 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, hydroxymethanesphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi Organic phosphonic acid derivatives such as hexamethylenediamine tetra (methylene phosphonic acid) and diethylenetriamine penta (methylene phosphonic acid), or salts thereof; Organic acids such as diglycolic acid, tartaric acid, oxalic acid and gluconic acid, and salts thereof. The metal ion sequestering agent may be used singly or in combination of two or more species.

Of these, aminocarboxylic acid salts are preferable from the viewpoint of cleaning effect, and methylglycine diacetate salts are more preferable.

Particularly, the use of the metal salt blocking agent in the form of an aminocarboxylate salt is preferred in view of increasing the activity of the component (b).

[Spices]

As the fragrance, a conventionally known fragrance is used, and for example, a mixture (perfume composition) comprising a fragrance component, a solvent, a fragrance stabilizer and the like can be used. As such a fragrance, for example, the fragrance described in JP-A-2002-146399 and JP-A-2003-89800 can be used. The perfume may be used singly or in combination of two or more kinds.

The content of the perfume in the granular detergent composition is preferably 0.01 to 0.5 mass% with respect to the total mass of the granular detergent composition.

[Coloring matter]

As the coloring matter, any of a dye and a pigment can be used. From the viewpoint of storage stability, a pigment is preferable, and a compound having oxidation resistance such as an oxide is particularly preferable. Examples of such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, stearic acid, persulfate, cyanine blue, and cyanine green. The coloring matter may be used alone, or two or more kinds thereof may be used in combination.

[Fluorescent Whitening Agent]

Examples of the fluorescent whitening agent include 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) Fluorescent whitening agents such as a 2- (styrylphenyl) naphthothiazole derivative, a 4,4'-bis (triazol-2-yl) stilbene derivative and a bis- (triazinylaminostilbene) have. As the fluorescent whitening agent, one kind may be used alone, or two or more kinds may be used in combination.

The content of the fluorescent whitening agent in the granular detergent composition is preferably 0.01 to 0.5 mass% with respect to the total mass of the granular detergent composition.

[enzyme]

Examples of enzymes include hydroazines, oxydoryldactase, lyases, transferases and isomerases, which are classified according to the reactivity of enzymes. In the present invention, any of the enzymes can be applied. Among them, protease, esterase, lipase, nuclease, cellulase, amyrase, pectinase and the like are preferable. The enzymes may be used alone, or two or more enzymes may be used in combination.

The content of the enzyme in the granular detergent composition is preferably 0.1 to 1.0% by mass based on the total mass of the granular detergent composition.

[Enzyme stabilizer]

As the enzyme stabilizer, for example, a calcium salt, a magnesium salt, a polyol, formic acid, a boron compound and the like can be added. The enzyme stabilizer may be used alone, or two or more thereof may be used in combination.

[Re-Contamination Agent]

Examples of the re-contamination preventive agent include cellulose derivatives such as carboxymethyl cellulose and hydroxypropylmethyl cellulose. The anti-fouling agent may be used alone, or two or more thereof may be used in combination.

The content of the antifouling agent in the granular detergent composition is preferably from 0.1 to 2.0% by mass based on the total mass of the granular detergent composition.

[Caking agent]

Examples of the anti-caking agent include paratoluene sulfonic acid salt, xylene sulfonic acid salt, acetic acid salt, sulfosuccinic acid salt, talc, fine powder silica, clay, magnesium oxide and the like. The anti-caking agent may be used alone, or two or more kinds thereof may be used in combination.

[pH adjusting agent]

Examples of the pH adjuster include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkali agents such as sodium hydroxide and potassium hydroxide; alkali metal hydrogen phosphate salts such as potassium dihydrogenphosphate; and lactic acid, , Gluconic acid or an acidic agent such as polycarboxylic acid, carbonic acid, sulfuric acid, hydrochloric acid and the like. The pH adjuster may be used alone, or two or more thereof may be used in combination.

The granular detergent composition preferably has a pH of 8 or more, more preferably 9 to 11, at 20 占 폚 of the 1 mass% aqueous solution of the granular detergent composition from the viewpoint of enhancing the cleaning power.

The pH value is defined as a value at 20 占 폚 unless otherwise specified. That is, even if the pH value is outside the range defined in the present specification, if the pH value is within the range defined in this specification when the pH value is corrected at 20 ° C, they are included in the scope of the present invention.

[bookbinder]

As the binder, conventionally known binders can be used, and examples thereof include polyethylene glycol, polypropylene glycol and the like.

&Lt; Particles constituting the granular detergent composition >

The granular detergent composition is an aggregate of a plurality of particles independently present.

The granular detergent composition of the present invention contains at least the following particles (X) and particles (Y) as different particles. If necessary, particles other than the particles (X) and (Y) may be further contained.

&Quot; Particles (X) "

Particles (X) are particles that contain component (a) and do not contain component (b).

As the component (a) contained in the particles (X), the above-described various surfactants can be used. Anionic surfactants and nonionic surfactants are preferable from the viewpoint of enhancing the washing power, and anionic surfactants are more preferable.

The component (a) contained in the particles (X) may be one kind or two or more kinds.

The content of the component (a) in the particles (X) is determined in consideration of the kind thereof, and is preferably 5 to 40 mass%, more preferably 5 to 30 mass%, based on the total mass of the particles (X) , And particularly preferably from 5 to 15 mass%.

Particles (X) further include a part of component (c).

At least a part of the component (c) contained in the particles (X) is zeolite (c1). That is, the particles X include spray dried particles obtained by spray drying a slurry containing a part of component (c), and the component (c) contained in the spray dried particles is zeolite (c1). The particle (X) contains the entire amount of the zeolite (c1) in the component (c). The particles X may further include a part or all of the zeolite (c2), or may not contain them.

That is, one side of the particle X is a particle which contains a component (a) and a part of the component (c) and does not contain the component (b) ) Component contains the entire amount of the zeolite (c1), and may contain part or all of the zeolite (c2).

In view of the effect of the present invention, it is preferable that at least a part of the zeolite (c2) is present on the surface of the particle (X). The presence of the zeolite (c2) on the surface of the particles (X) improves the stability of the component (b) and the flowability of the granular detergent composition.

The particle X in which the zeolite (c2) exists on the surface can be obtained, for example, by using the zeolite (c2) as the milling aid when the particle (X) is produced by crushing and assembling. Most of the zeolite (c2) used as the milling aid covers the surface of the granulated particles.

The content of the component (c) in the particle (X) is not particularly limited and is determined in consideration of, for example, the content of the particles (X) in the granular detergent composition. For example, the content is preferably 3 to 15 mass% By mass, and more preferably 5 to 15% by mass. When the content of the component (c) in the particles X is 3% by mass or more, the stability of the component (b) and the fluidity of the particles (X) themselves improve. When the content is 15% by mass or less, the stability of the component (b) improves.

The particles (X) may further contain other components (optional components) other than the components (a) to (c). As the other component, any of the above-mentioned components may be appropriately selected as the optional component.

The particles X are preferably other components and contain other cleansing builders. Other cleansing builders may be inorganic builders other than component (c), organic builders, or both.

The content of other cleansing builders in the particles X is determined in consideration of the kind thereof and is preferably 10 to 70 mass%, more preferably 30 to 60 mass%, based on the total mass of the particles (X) Do. If the lower limit value is not less than the lower limit value, the mixing effect of the other cleaning builders is sufficiently obtained. If the upper limit is exceeded, the content of the surfactant may be decreased and the detergent may be deteriorated.

Among other cleansing builders, the content of the organic builder is determined in consideration of the kind thereof, and is preferably 1 to 10 mass%, more preferably 3 to 5 mass%, based on the total mass of the particles (X) .

The particles (X) include spray dried particles obtained by spray drying the slurry. The spray dried particles include at least zeolite (c1) among the components constituting the particles (X) (that is, the components (a), (c) and optional components).

(X1): a granulated particle obtained by spray-drying a slurry containing a part of raw materials constituting the particle (X) and granulating the spray-dried particles obtained with the remaining raw materials together, (X2) And spray-dried particles obtained by spray-drying a slurry containing all of the components constituting the spray-dried particles.

Among these, the particles (X) are not particularly limited as long as the particles have a high bulk density and are less likely to be handled with less dust, and that the components can be stably compounded by blending the components with low heat resistance later without spray drying X1) are preferred.

The particles (X) can be produced by conventionally known production methods. The method of producing the particles X will be described later in detail.

The bulk density of the particles X is not particularly limited, but is preferably 0.7 g / cm 3 or more, more preferably 0.7 to 1.5 g / cm 3, and even more preferably 0.7 to 1.2 g / cm 3. When the amount is 0.7 g / cm 3 or more, the powder is less likely to be handled with ease, and when it is 1.5 g / cm 3 or less, the solubility in water is good.

The " bulk density " in the present specification means a value measured in accordance with JIS K3362.

The average particle diameter of the particles (X) is not particularly limited, but is preferably 200 to 1500 占 퐉, more preferably 250 to 1000 占 퐉, and still more preferably 300 to 700 占 퐉. When the thickness is 200 m or more, solidification of the granular detergent composition hardly occurs, and when it is 1500 m or less, solubility in water is good.

The " average particle size " in the present specification means a value calculated from the particle size distribution by sieving in accordance with the test of the particle size described in the Japanese Pharmacopoeia.

That is, the average particle size can be measured by a classification operation using nine-stage sieves and trays having an eye size of 1680 탆, 1410 탆, 1190 탆, 1000 탆, 710 탆, 500 탆, 350 탆, 250 탆 and 149 탆 . In the classification operation, a sieve body having a large eye size was sequentially stacked on a tray, a sample of 100 g / s was placed from a 1680 탆 sieve body at the top, and a lid was covered with a low taper body stirrer (manufactured by Iida-Seisakusho Japan Corporation, Tapping: 156 times / minute, and rolling: 290 times / minute), and after vibrating for 10 minutes, the sample remaining on each sieve and the tray is collected every sieve to measure the mass of the sample. When the mass frequency of the trays and the respective bodies is accumulated, the eye size of the first sieve having the mass frequency of integration of 50% or more is referred to as " a 占 퐉 & (50% by mass) according to the following formula (I), assuming that the integrated value of the mass frequency from the tray to the a mu m body is " c% ", and the mass frequency of the a mu m body is & Particle diameter) is determined to be the average particle diameter of the sample.

The particles (X) may be used singly or in combination of two or more.

The content of the particles (X) in the granular detergent composition according to the first embodiment of the present invention is preferably 50 to 90 mass%, more preferably 50 to 80 mass%, based on the total mass of the granular detergent composition. If it exceeds 90% by mass, the amount of the zeolite (c2) in the granular detergent composition may be insufficient, and the effect of improving the stability of the component (b) may become insufficient. If it is less than 50% by mass, the granular detergent composition may have insufficient cleaning power.

&Lt; Particle (X) / zeolite (c2) >

In the granular detergent composition according to the first embodiment of the present invention, the mass ratio (i.e., the particle X / zeolite c2) of the particles X to the zeolite (c2) contained in the granular detergent composition is from 5 to 25 , More preferably from 5 to 15 carbon atoms. When the amount of the particles (X) / zeolite (c2) is 25 or less, the effect of improving the stability of the component (b) and the flowability of the granular detergent composition is sufficiently obtained. When the particle (X) / zeolite (c2) is less than 5, the stability of the component (b) may decrease.

&Quot; Particles (Y) "

The particles (Y) are particles containing the component (b). The particles (Y) may contain the component (a).

Examples of the particles (Y) include particles of percarbonate such as sodium percarbonate, particles of perborate such as sodium perborate, sodium perborate and trihydrate, and the like. Among them, sodium percarbonate particles are preferable from the viewpoints of solubility in use and stability upon storage, and coated sodium percarbonate particles (i.e., coating and sodium carbonate particles) are more preferable. These coatings and sodium carbonate particles are superior in fluidity as compared to sodium percarbonate particles whose surface is smooth and uncoated.

The coating and the sodium carbonate particles are preferably sodium percarbonate particles coated with at least one component selected from the group consisting of silicic acid, silicate and boric acid, and borate, and sodium percarbonate particles coated with a combination of a surfactant such as LAS and an inorganic compound . Specifically, as disclosed in Japanese Patent No. 2918991, sodium percarbonate particles coated by spraying at least one component selected from the group consisting of an aqueous solution of silicic acid, an alkali metal silicate salt and boric acid, and an aqueous alkali metal borate solution; Sodium percarbonate particles coated with at least one component selected from the group consisting of an aromatic hydrocarbon sulfonic acid such as Japanese Patent No. 2871298, an alkali silicate salt having an average particle size of 10 to 500 m, a carbonate, a bicarbonate and a sulfate; And sodium percarbonate particles coated with a water-insoluble organic compound such as paraffin or wax. For non-hazardous materials, powder blend with various inorganic substances such as sodium carbonate, sodium bicarbonate, etc. may be used.

Further, as the particles (Y), sodium percarbonate particles coated with sodium percarbonate, sodium percarbonate particles, aromatic hydrocarbon sulfonic acid and alkali silicate, carbonate, bicarbonate and sulfate coated with silicic acid and sodium borate are more preferable.

As coatings and sodium carbonate particles, in addition to those disclosed in Japanese Patent Application Laid-open Nos. 59-196399 and 4526698 (all sodium carbonate is coated with a borate salt), Japanese Patent Application Laid-Open Nos. 4-31498, 6-40709, And coatings and sodium carbonate particles produced by the method disclosed in Japanese Patent Publication No. 7-118003 and Japanese Patent No. 2871298.

The bulk density of the particles (Y) is not particularly limited, but is preferably 0.7 g / cm 3 or more, more preferably 0.7 to 1.5 g / cm 3. When the amount is 0.7 g / cm 3 or more, the powder is less likely to be handled with ease, and when it is 1.5 g / cm 3 or less, the solubility in water is good.

The average particle diameter of the particles (Y) is not particularly limited, but is preferably 200 to 1000 占 퐉, more preferably 500 to 1000 占 퐉. When the thickness is 200 μm or more, stability and fluidity at the time of long-term storage are good, and when it is 1000 μm or less, solubility in water is good.

Further, because of improvement in solubility and stability, the particles having a particle diameter of less than 125 mu m and the particles having a particle diameter of 1400 mu m are preferably not more than 10 mass% with respect to the total mass of the particles (Y), and more preferably they are not included.

The particles (Y) may be used singly or in combination of two or more.

The content of the particles (Y) in the granular detergent composition according to one embodiment of the present invention is preferably 3 to 20 mass%, more preferably 3 to 15 mass%, based on the total mass of the granular detergent composition. When the content is 3% by mass or more, the effect such as improvement of washing power against bleaching, sterilization, stain contamination and the like is sufficiently obtained, and the fluidity is also good. If the amount exceeds 20% by mass, the amount of other cleaning components may be decreased and the cleaning power may decrease.

«Other particles»

The granular detergent composition according to one embodiment of the present invention may be a granular detergent composition composed of the particles (X) and the particles (Y), and may further contain particles other than the particles (X) and (Y) as necessary.

Examples of the other particles include particles of zeolite (c2), particles of any of the above-mentioned components (for example, inorganic builders), coarse particles containing at least two of them, .

The granular detergent composition which is one embodiment of the present invention can be produced by a granular detergent composition manufacturing method which is one embodiment of the present invention described later.

The bulk density of the granular detergent composition according to one embodiment of the present invention is not particularly limited, but is preferably 0.7 g / cm 3 or more, more preferably 0.7 to 1.6 g / cm 3, and even more preferably 0.7 to 1.2 g / cm 3. When the amount is 0.7 g / cm 3 or more, handling is easy because the amount of dust is small, and when it is 1.6 g / cm 3 or less, solubility in water is good.

The average particle diameter of the granular detergent composition according to one embodiment of the present invention is not particularly limited, but is preferably 200 to 1200 占 퐉, more preferably 250 to 900 占 퐉, and still more preferably 300 to 700 占 퐉. When the thickness is 200 m or more, dusting at the time of use is suppressed, and when it is 1200 m or less, the solubility in water is excellent.

The water content in the granular detergent composition according to one embodiment of the present invention is preferably from 3 to 8 mass%, more preferably from 3 to 7 mass%, based on the total mass of the granular detergent composition. If it exceeds 8% by mass, there is a fear that the stability of the component (b) is lowered and the flowability of the granular detergent composition is lowered. If it is less than 3% by mass, there is a fear of lowering of solubility in water and deterioration of oscillation property.

Refers to a value measured under conditions of a sample surface temperature of 130 占 폚 for 20 minutes by an infrared moisture meter (e.g., Kett Electric Laboratory, Kett moisture meter).

(Method for producing granular detergent composition)

One aspect of the process for producing a granular detergent composition according to the second aspect of the present invention is a process for producing a granular detergent composition containing a component (a), a component (b) and a component (c)

(Hereinafter referred to as a particle (X) production process) of obtaining a spray-dried particle by spray-drying a slurry containing a part of the component (c) and obtaining the particle (X) from the spray-

(Hereinafter referred to as a mixing step) of mixing the particles (Y) and the particles (X)

The amount of the component (c) used is 5 to 15% by mass based on the total mass of the granular detergent composition to be produced,

The mass ratio (c1 / c2) of the zeolite (c1) blended with the slurry to the zeolite (c2) other than the zeolite (c1) in the component (c) is more than 0 and 0.7 or less.

Another aspect of the method of making the granular detergent composition, which is the second aspect of the present invention,

A method for producing a granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)

The production method comprises a step of obtaining particles (X), a step of mixing the particles (Y) containing the inorganic peroxide (b) and the particles (X)

The step of obtaining the particles (X)

A step of spray-drying a slurry containing a part of the zeolite (c) to obtain spray-dried particles; and a step of spray-drying the slurry containing particles of the zeolite (c) X), < / RTI >

Details of the components (a) to (c), the particles (X) and the particles (Y) are as described above.

The amount of the component (a) used is preferably 5 to 15% by mass based on the total mass of the granular detergent composition to be produced.

The amount of the component (b) used is preferably 3 to 20% by mass based on the total mass of the granular detergent composition to be produced.

(c) is preferably in an amount of 5 to 15 mass% with respect to the total mass of the granular detergent composition to be produced.

The amount of the optional component to be used is preferably from 10 to 40% by mass based on the total mass of the granular detergent composition to be produced.

&Lt; Particle (X) Manufacturing Process >

The particles (X) can be produced by conventionally known production methods.

For example, when the particle X is the granulated particle of the above-mentioned (X1), a part of the raw material constituting the particle X (that is, the component (a), the component (c) (Slurry preparation step), the slurry is dried by a spray dryer (spray drying step), and the obtained spray dried particles are mixed with the remaining raw materials which have not been used for the adjustment of the slurry Assemble (assembly process). Thereafter, the granulated particles may be selected and adjusted to a desired average particle size and particle size distribution as necessary (a felling step).

When the particles (X) are spray dried particles of the above (X2), all of the raw materials constituting the particles (X) are dispersed and dissolved in water in the slurry preparing step to prepare slurries. I do. Accordingly, the obtained spray-dried particles can be used as the particles (X).

That is, one aspect of the method for producing the particles (X) is that a part of the raw materials (that is, the components (a), (c), and optional components) constituting the particles X are dispersed in water simultaneously or sequentially A slurry preparing step of preparing a slurry by dissolution; A spray drying step of spray drying the slurry; Drying the spray-dried particles obtained by the spray drying, together with the remaining raw materials not used in the slurry adjusting step; And a felling step of selecting the assembled granules according to desire and adjusting them to a desired average particle size and particle size distribution.

Another aspect of the method for producing the particles (X) includes: a slurry adjusting step of preparing a slurry by dispersing and dissolving all the raw materials constituting the particles (X) in water; And a spray-drying step of spray-drying using the slurry.

Hereinafter, a method for producing the particles (X) in the case where the particles (X) are the granulated particles of the above (X1) will be described in more detail.

«Slurry preparation process»

At least a part of component (c) is blended in the slurry. The component (c) blended in the slurry is zeolite (c1).

The water content of the component (c) before blending with the slurry (that is, the water content in the component (c) when the granular detergent composition is produced) is preferably 5% or more and 10% or less. When the water content is 10% or less, the stability of the component (b) in the obtained granular detergent composition is good.

The term "water content of the component (c)" means a value measured under the conditions of a sample surface temperature of 130 ° C. for 20 minutes by an infrared moisture meter (for example, Kett Electric Laboratory, Kett moisture meter).

The water content of the slurry after the adjustment is preferably 30 to 50 mass% with respect to the total mass of the slurry.

The components (a) and optional components may all be incorporated in the slurry; May be blended with the spray-dried particles in the subsequent assembly process; Some of them may be blended in the slurry and the remaining components not blended in the slurry may be blended together with the spray-dried particles in the subsequent assembly process. The low heat resistance component is preferably blended with the spray dried particles in a subsequent assembly process.

«Spray drying process»

During the spray drying of the slurry, the hot gas is supplied into the spray drying tower of the spray dryer. The hot gas is supplied from, for example, the lower portion of the spray drying tower and discharged from the top of the tower of the spray drying tower.

The temperature of the hot gas supplied into the spray drying tower is preferably 170 to 300 DEG C, more preferably 200 to 280 DEG C. Within this range, the slurry can be sufficiently dried, and spray dried particles having a desired water content can be easily obtained.

The temperature of the gas discharged from the spray drying tower is preferably 70 to 125 캜, and more preferably 70 to 115 캜.

The moisture content in the spray dried particles obtained in the spray drying process is preferably 2 to 7% by mass, more preferably 3 to 7% by mass, based on the total mass of the spray dried particles. When the moisture content in the spray-dried particles is 7 mass%, the flowability of the spray-dried particles is good. When the moisture content in the spray-dried particles is less than 2%, there is a fear of lowering of solubility in water and oscillation.

The term "moisture content in spray-dried particles" means a value measured at 130 ° C. for 20 minutes by an infrared moisture meter (eg, Kett Electric Laboratory, Kett moisture meter).

«Assembly process»

In the assembling step, the obtained spray-dried particles are assembled together with the remaining raw materials that are not used in the slurry adjusting step (that is, raw materials that are not blended in the slurry of the raw material constituting the particles (X)).

The assembling process can be carried out by using conventionally known methods such as crushing, stirring, assembling, fluidized bed, and the like. For example, in the case of the pulverized granulation, the granulated particles (particles (X)) are obtained by kneading the spray-dried particles and the remaining raw materials not used in the slurry adjusting step and cutting them while extruding them to obtain a pellet- ) Can be obtained.

That is, one aspect of the assembling process is that kneading the spray-dried particles and the remaining raw materials not used in the slurry adjusting process, cutting the kneaded mixture while extruding it to obtain a molded article in pellet form, and pulverizing the molded article To obtain granulated particles (particles (X)).

At this time, the remaining raw material that is not used in the slurry adjusting step may contain component (c). The component (c) blended with the remaining raw materials not used in the slurry preparation step corresponds to zeolite (c2).

In the assembling step, component (c) may be used as a granulation aid. For example, in the case of pulverizing and assembling, a part of the component (c) may be used as a pulverizing auxiliary at the time of pulverization. Although the component (c) used as a granulation aid is distributed in some granulated particles, most of them cover the surface of granulated granules. The component (c) used as the granulation aid corresponds to the zeolite (c2).

The water content in the component (c) used as the granulation aid in the granulation process is preferably 5 mass% or more and 10 mass% or less with respect to the total mass of the component (C). When the water content is 10 mass% or less, the stability of the component (b) in the obtained granular detergent composition is good.

The water content in the component (c) used as the granulation auxiliary agent is preferably less than the water content in the granulated particles. The surface of the granulated particles having a relatively large amount of water to be volatilized is coated with the component (c) having a small water content, whereby the stability of the component (b) in the granular detergent composition to be obtained is further improved.

«Fractionation process»

As the felling step, for example, a plurality of sieve-shaped sieves are prepared, and stacked body units are stacked in the order of sieve-like sieves in the order of a small-sized sieve, granulated particles are put into the upper part of the sieve unit, And a method of vibrating and selecting the body unit. The granulated particles remaining on each of the sieves are recovered per sieve and the recovered granulated particles are mixed to obtain granulated granules having a desired average particle size or particle size distribution.

The obtained particles (X) are provided in the following mixing step.

The water content in the particles (X) is preferably from 4 to 9 mass%, more preferably from 5 to 8 mass%, based on the total mass of the particles (X). If the water content of the particles (X) exceeds 9 mass%, there is a fear that the stability of the component (b) is lowered and the fluidity is lowered after mixing with the particles (Y). When the water content of the particles (X) is less than 4% by mass, there is a fear that the solubility in water is lowered and the oscillation property is deteriorated.

In the mixing step, the particles (X) and particles (Y) obtained in the production process of the particles (X) are mixed with other particles as required.

As the particles (Y) and other particles, commercially available particles may be used, or particles produced by a known production method may be used.

The mixing method of each particle may be any method as long as the mixing method can be carried out so that at least the particles (X) and the particles (Y) are present as independent particles. For example, a conventionally known powder mixing device (for example, Or a V-type mixer), and mixing the particles (X) and the particles (Y). The order of introduction of the particles X and Y is not particularly limited and the particles X and the particles Y may be preliminarily charged into the mixing apparatus to mix them and the particles X and Y may be sequentially May be added to the mixing apparatus to be mixed. Further, in the case of mixing other particles, the other particles may be mixed beforehand with any one of the particles (X) and (Y), and the other particles together with the particles (X) It may be added by mixing. For example, in the case of mixing zeolite (c2) as another particle, even if the particles (X) and the particles (Y) are mixed first and the zeolite (c2) ) May be mixed and finally the particles (Y) may be mixed. However, mixing the particles (Y) and the zeolite (c2) at the beginning and mixing the particles (X) at the end is undesirable because of the decrease in the stability of the component (b).

That is, one aspect of the mixing process involves mixing particles X and particles Y obtained in the process of manufacturing the particles X and, optionally, other particles,

Said mixing may comprise premixing said other particles with said particles (X) or said particles (Y);

And mixing the particles (X), the particles (Y) and the other particles together.

When the other particles are zeolite (c2), the mixing may include mixing the particles (X) and the particles (Y) and then mixing the zeolite (c2);

Mixing the particles (X) and the zeolite (c2), followed by mixing the particles (Y);

The particles X and the zeolite c2 are mixed and then allowed to stand under a predetermined condition (for example, at a temperature of 20 DEG C and a relative humidity of 50% RH for not less than 5 minutes and not longer than 30 minutes) Y) may be mixed.

In addition, as long as the particles (X) and the particles (Y) can exist as independent particles, the particles (X) and the particles (Y) are mixed and then the liquid component May be added and mixed. Also, a method of feeding a fixed amount of each particle on a belt conveyor, or the like can be used.

From the viewpoint of the stability of the component (b), it is preferable that the particles (X) and the zeolite (c2) are mixed first and the particles (Y) are finally mixed in the mixing step. Particles (X) and zeolite (c2) are mixed and allowed to stand in a predetermined condition (for example, in an environment of 20 占 폚 and 50% RH for 5 minutes or more and 30 minutes or less) It is preferable to mix the components (a) and (b) because the effect of improving the stability of the component (b) is high.

A granular detergent composition is obtained as described above.

In the method for producing a granular detergent composition according to one embodiment of the present invention, the amount of the component (c), that is, the amount of the zeolite (c2) added to the step after the preparation of the spray dried particles, is such that the value of the particle (X) / zeolite Is in the range of 5 to 25. The value of the particle X / zeolite (c2) is more preferably 5 to 15 as described above.

In the case of preparing the granular detergent composition by the above-mentioned slurry preparation process, spray drying process, and granulation process, and then passing the mixing process, the "process after preparation of spray dried particles" Means a subsequent process (assembling process, mixing process, etc.).

In the method for producing a granular detergent composition according to one embodiment of the present invention, it is preferable that at least a part of the zeolite (c2) is added in the granulation step, because the effect of improving the stability of the component (b) is excellent.

(A) component (that is, an aqueous solution in which the component (a) is dissolved in water)) which has been heated to not less than 50 ° C and not more than 65 ° C in the granulation step is impregnated with the spray- The bulk density of the spray-dried particles is largely changed. In this process, the water content increases and the number of free particles obtained in the granulation process increases. Further, since the aqueous solution of component (a) at 50 DEG C or more is used in a large amount (for example, 7 mass% or more), the temperature of the spray-dried particles is increased. Therefore, the free water is in a state where it is easy to catch. If zeolite (c2) is added to the spray-dried particles in this process, it is easy to capture free water and improve the stability of component (b) in the particulate detergent composition.

In the mixing step, a liquid component such as an aqueous solution of component (a) or a flavoring agent added at a temperature of 50 ° C or higher is added in the mixing step, but the addition amount thereof is small (for example, less than 5 mass%), The amount of water is very small. Further, the temperature at this time is not a high temperature. Therefore, the original free water capturing force is strong, and the effect of addition of zeolite (c2) in the mixing process is small as compared with the assembly process.

In the method for producing the granular detergent composition according to one embodiment of the present invention, from the viewpoint of the stability of the component (b), the moisture amount derived from the water added in the step after the preparation of the spray- It is preferable that the amount of water derived from the particles is smaller than the amount of water derived from the particles.

In the spray drying process, moisture other than the crystalline water, which is hardly volatilized, is volatilized in the water contained in the zeolite. Therefore, the moisture (that is, the crystal number) contained in the zeolite (c1) in the spray dried particles immediately after the production is hardly volatilized and the influence on the stability of the component (b) is small. However, in the process after the preparation of the spray-dried particles, moisture added to the spray-dried particles (that is, water contained in the surfactant solution, water required for kneading, etc.) tends to volatilize and (b) easy. The stability of the component (b) is further improved by reducing the amount of water derived from the water added in the step after the preparation of the spray-dried particles (that is, the amount of water not derived from the spray-dried particles)

The amount of water derived from the water added in the process after the preparation of the spray-dried particles is expressed by the following equation: " Water content (mass%) in the entire particle X " (Mass%) of spray-dried particles in the particles (X) / value of 100 ".

(Method of using granular detergent composition)

The granular detergent composition of the first aspect of the present invention (i.e., the granular detergent composition obtained by the manufacturing method of the second aspect) can be used for washing the particulate matter.

As a washing method of the particulate detergent composition, for example, a cleaning liquid having a concentration of the granular detergent composition of 0.02 to 2% by mass with respect to the total mass of the cleaning liquid is used, and the material is washed in a washing machine, And the like, may be mentioned.

Examples of the material to be used include fabrics such as medical materials, fabrics, curtains, and sheets.

That is, one aspect of the method of using the granular detergent composition is

Adjusting a cleaning liquid having a concentration of the granular detergent composition of 0.02 to 2% by mass with respect to the total mass of the cleaning liquid in the washing machine; Injecting the laundry into the washing machine in which the washing liquid is adjusted, and washing the laundry with the washing machine; Rinsing the washed laundry in the washing liquid with water; And dewatering the rinse mass with the water by desirability.

Another aspect of the method of using the granular detergent composition is to adjust the cleaning liquid having a granular detergent composition concentration of 0.02 to 2 mass% based on the total mass of the cleaning liquid; Immersing the cleaning liquid in the adjusted cleaning liquid for a desired time; Rinsing the soaked food with water; And dewatering the rinse mass with the water by desirability.

(Action effect)

The granular detergent composition (granular detergent composition obtained by the production method of the second aspect) of the first aspect of the present invention can be obtained by setting the mass ratio (c1 / c2) of zeolite (c1) to zeolite (c2) the storage stability of the component (b) is improved under the coexistence of the component (c). Also, the fluidity is good. In addition, since the components (a) to (c) are contained, it is possible to clean the substrate well.

It is considered that the reason why the stability of the component (b) is improved by setting c1 / c2 to 0.7 or less is that the movement of adsorption and release of water in the component (c) is reduced. That is, since the zeolite (c1) undergoing the spray drying process is dried at a high temperature (for example, 200 ° C or higher), the amount of moisture that can be adsorbed is large. Therefore, when the granular detergent composition having a large proportion of the zeolite (c1) is stored at high temperature, much water is released, and the stability of the component (b) is lowered by this water. On the other hand, the zeolite (c2) not subjected to the spray drying process has a smaller amount of moisture that can be adsorbed than the zeolite (c1), so that the amount of water released during storage at a high temperature is small and the stability of the component . Therefore, by increasing the proportion of the zeolite (c2), it is considered that the influence of moisture on the component (b) is reduced and the stability is improved.

In another aspect of the present invention,

As a granular detergent composition containing a surfactant (a), an inorganic peroxide (b), a zeolite (c) and optionally an optional component,

Wherein said granular detergent composition comprises spray dried particles obtained by spray-drying a slurry comprising said surfactant (a) and a part of said zeolite (c) but not including said inorganic peroxide (b)

(Y) comprising the inorganic peroxide (b);

With respect to the total mass of the granular detergent composition

Wherein the content of the surfactant (a) is 5 to 30 mass%

Wherein the content of the inorganic peroxide (b) is 3 to 20% by mass,

, The content of the zeolite (c) is 5 to 15 mass%

The total content of the respective components is not more than 100% by mass,

Wherein the zeolite (c) comprises a zeolite (c1) blended in the slurry and the zeolite (c2) other than the zeolite (c1), and the mass ratio c1 / c2 of the zeolite (c1) 0.0 > 0.7 < / RTI > or less.

In another aspect of the present invention,

(Y) comprising the inorganic peroxide (b);

With respect to the total mass of the granular detergent composition

The content of the surfactant (a) is 7 to 11 mass%

The content of the inorganic peroxide (b) is 7 to 15% by mass,

, The content of the zeolite (c) is 8 to 15 mass%

The total content of the respective components is not more than 100% by mass,

In another aspect of the present invention,

Particles (Y) containing the inorganic peroxide (b)

(X) and particles other than the particles (Y) by a desired amount;

With respect to the total mass of the granular detergent composition

Wherein the content of the surfactant (a) is 5 to 30 mass%

Wherein the content of the inorganic peroxide (b) is 3 to 20% by mass,

, The content of the zeolite (c) is 5 to 15 mass%

The total content of the respective components is not more than 100% by mass,

With respect to the total mass of the granular detergent composition

, The content of the particles (X) is 50 to 90 mass%

, The content of the particles (Y) is 3 to 20 mass%, the total content of the particles is not more than 100 mass%

In another aspect of the present invention,

Particles (Y) containing the inorganic peroxide (b)

(X) and particles other than the particles (Y) by a desired amount;

The surfactant (a) is at least one component selected from the group consisting of an anionic surfactant and a nonionic surfactant,

The inorganic peroxide (b) is at least one component selected from the group consisting of sodium percarbonate particles, sodium perborate particles, and sodium perborate trihydrate,

The zeolite (c) is at least one component selected from the group consisting of an A-type zeolite, an X-type zeolite, a Y-type zeolite, and a P-type zeolite,

Wherein the optional component is at least one component selected from the group consisting of an inorganic builder, an organic builder, a fluorescent brightener, a re-contamination inhibitor, a metal salt, a sequestering agent, an organic peracid precursor,

With respect to the total mass of the granular detergent composition

Wherein the content of the surfactant (a), the content of the inorganic peroxide (b), the content of the zeolite (c) and the content of the arbitrary component contained in the desired content, the content of the particles (X) , And the contents of the other particles contained by the above desirability are the same as above,

And granular detergent compositions in which the mass ratio c1 / c2 of the zeolite (c1) to the zeolite (c2) is the same as described above.

As another mode of the present invention,

Particles (Y) containing the inorganic peroxide (b)

(X) and particles other than the particles (Y) by a desired amount;

Wherein the surfactant (a) is at least one selected from the group consisting of a sodium salt of a straight chain alkylbenzenesulfonic acid having 10 to 14 carbon atoms and a polyoxyethylene alkyl (having 12 to 14 carbon atoms) ether having an average addition mole number of ethylene oxide of 15 Lt; / RTI >

The inorganic peroxide (b) is a sodium percarbonate-containing particle,

The zeolite (c) is an A-type zeolite,

The optional components are selected from the group consisting of acrylic acid / maleic anhydride copolymer sodium salt, sodium carbonate, potassium carbonate, sodium sulfate, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, carboxymethylcellulose sodium, At least one component selected from the group consisting of trisodium glycine diacetate, citric acid, sodium 4-dodecanoyloxybenzenesulfonate, sodium bicarbonate, and enzymes,

With respect to the total mass of the granular detergent composition

In another aspect of the present invention,

A method for producing a granular detergent composition containing a surfactant (a), an inorganic peroxide (b), a zeolite (c) and optionally an optional component,

The above-

A step of obtaining the particles (X)

A mixing step of mixing the particles (Y) containing the inorganic peroxide (b), the particles (X) and particles other than the particles (X) and the particles (Y)

The step of obtaining the particles (X)

A slurry preparing step of preparing a slurry by simultaneously or successively dispersing and dissolving a part of the raw material constituting the particles (X) comprising the component (a), the component (c) ,

A spray drying step of spray drying the slurry,

Drying the spray-dried particles obtained by the spray drying, together with the remainder of the raw material constituting the particles (X) not used in the slurry adjusting step;

And a felling step of selecting the assembled granules and adjusting the granulated granules to a desired average particle size and particle size distribution,

The mixing process

Mixing the particles (Y) after mixing the particles (X) and the other particles; Simultaneously mixing the particles (X), the particles (Y) and the other particles; Or the particles X and the other particles are mixed and then left in a predetermined condition (for example, at an environment of 20 ° C. and 50% RH for 5 minutes or more) Mixing,

Wherein the zeolite (c) comprises a zeolite (c1) blended in the slurry and a zeolite (c2) other than the zeolite (c1), and the mass ratio c1 / c2 of the zeolite (c1) And a granular detergent composition having a value of more than 0 and not more than 0.7.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these.

The raw materials used in each of the following examples are shown below.

&Lt; Particle (Y) >

PC: (SPCC, manufactured by JINKE Co., Ltd., sodium percarbonate-containing particles, volume density 1.05 g / cm3, average particle diameter 870 m)

A type zeolite (produced by Thai Silicate Chemicals Co., Ltd., water content: 4%).

Using an infrared moisture meter, the measurement value (weight reduction amount) after 20 minutes at the sample surface temperature of 130 占 폚 was determined as the moisture content of the zeolite.

LAS-Na: A product obtained by neutralizing LAS-H (manufactured by Lion Corporation) with a 48 mass% aqueous solution of sodium hydroxide (trade name: LIPON LH-200 (liquid content: 96 mass% (% By mass as LAS-Na)).

C12 = 11.7 mass%, C14 = 0.4 mass%, C16 = 29.2 mass%, C18F0 (stearic acid) = 10 mass% 0.7% by mass, C18F1 (oleic acid) = 56.8% by mass, C18F2 (linoleic acid) = 1.2% by mass, molecular weight: 289, manufactured by Lion Corporation). In the above, "C" represents the number of carbon atoms.

LMAO: LMAO-90 (trade name, manufactured by Nippon Shokubai Co., Ltd.) [polyoxyethylene (EO15) alkyl (C12-14) ether]. (EO15) represents that the average addition mole number of ethylene oxide is 15, and (C12-14) represents that the alkyl group has 12 to 14 carbon atoms.

MA: Acrylic acid / maleic anhydride copolymer sodium salt, trade name = AQUALIC TL-400, 40 mass% aqueous solution, Nippon Shokubai Co., Ltd. making.

Sodium carbonate: Product name = granular ash, bulk density = 1.07 g / cm 3, Soda Ash Japan Co., Ltd. making.

Potassium carbonate (trade name) = potassium carbonate (powder), a bulk density of 1.30 g / cm 3, and Asahi Glass Co., Ltd. making.

Sodium sulfate: Product name = Neutral anhydrous gum, Bulk density = 1.52 g / cm 3, manufactured by Shikoku Chemicals Corporation.

Fluorescent brightener: 4,4'-bis- (2-sulfostyryl) -biphenyl salt, trade name = CBS-X, BASF Japan Ltd. making.

CMC: Carboxymethylcellulose sodium, trade name = CMC DAICEL 1170, manufactured by Daicel Corporation.

Zinc sulfate: ZnSO ₄ .1H ₂ O (zinc sulfate monohydrate, manufactured by Shinyo-Koki Co., Ltd.).

MGDA: trisodium methylglycine diacetate, trade name = TRILONM COMPACTATE (pure: 86%), BASF Japan Ltd. making.

Citric acid: product name = liquid citric acid, Fuso Chemical Co., Ltd. making.

OBS: Sodium 4-dodecanoyloxybenzenesulfonate. OBS was blended as a granulated product (OBS particle) synthesized in Production Example 1 below.

Sodium bicarbonate: Product name = SODIUM BICARBONATE FOOD GRADE COARSE GRANULAR, made by Penrice.

Enzyme: A mixture of EVERLASE 8T / CELLUCLEAN 4500T / LIPEX 50T = 5/3/2 (by weight), made by Novozymes.

&Lt; Preparation Example 1: Production method of OBS particles &

3000 g (15.3 mol) of sodium dehydrogenated 4-hydroxybenzenesulfonate (reagent manufactured by Kanto Chemical Co., Inc.) which had been dehydrated beforehand was added to 9000 g of N, N-dimethylformamide (manufactured by Kanto Chemical Co., And 3347 g (15.3 mol) of lauric acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) was added dropwise at 50 DEG C over 30 minutes while stirring with a stirrer. N, N-dimethylformamide was distilled off at 100 占 폚 in a reduced pressure state (0.5 to 1 mmHg (66.7 to 133.3 Pa)) 3 hours after completion of the dropwise addition. Washed with acetone (manufactured by Kanto Chemical Co., Inc., reagent), and then purified by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90 mass%.

70 parts by mass of synthesized sodium 4-dodecanoyloxybenzenesulfonate, 20 parts by mass of PEG (polyethylene glycol # 6000M (trade name), manufactured by Lion Corporation), 14 parts by mass of alpha -olefin sulfonic acid sodium powder (LIPOLAN PJ- (Manufactured by Hosokawa Micron Corporation) in an amount of 5 parts by mass in total at a ratio of 5 parts by mass, manufactured by Lion Corporation) was kneaded and extruded to obtain a pressed product of noodle having a diameter of 0.8 mm. The extruded product (60 ° C) and 5 parts by mass of the A type zeolite powder were supplied to a fitzmill DKA-3 type (trade name, manufactured by Hosokawa Micron Corporation) and pulverized to obtain a granulate having an average particle size of about 700 μm ).

&Lt; Examples 1 to 10 and Comparative Examples 1 to 3 >

A granular detergent composition was prepared in the following order.

«1. Preparation of spray-dried particles »

Spray-dried particles (A-1 particles to A-4 particles) having the compositions shown in Table 1 were prepared in the following order.

The composition shown in Table 1 is the mass% with respect to the total mass of the spray-dried particles.

Water was poured into a mixing tank equipped with a jacket equipped with a stirring device, and the temperature of water in the mixing tank was adjusted to 60 캜. To this, LAS-Na and soap were added, and the mixture was stirred for 10 minutes. Subsequently, MA agent was added. After stirring for 10 minutes, zeolite for spray drying (zeolite (c1)), sodium carbonate, potassium carbonate and alkali metal sulfate were added. After stirring for 20 minutes to prepare a spray drying slurry having a water content of 38% by mass based on the total mass of the slurry for spray drying, the slurry for spray drying was dried under the condition of a hot air temperature of 280 캜 using a countercurrent spray drying tower. Followed by spray drying to obtain spray dried particles.

With respect to the obtained spray-dried particles, a weight loss after 20 minutes at a sample surface temperature of 130 占 폚 was measured using an infrared moisture meter, and the measured value was regarded as the water content in the spray-dried particles.

«2. Production of Particles (X) »

The following particles (X-1-1 particles, X-1-2 particles, X-2 particles, X-3 particles) were obtained by using the obtained spray dried particles (A- Particles, X-4 particles) were prepared in the following order.

X-1-1 Particles: Particles composed of A-1 particles and α-sulfo fatty acid methyl ester Na (hereinafter referred to as "MES"), LMAO, water and zeolite (c2) 7% by mass).

X-1-2 Particles: A-1 particles, MES, LMAO, water, and zeolite (c2), with a water content of 5 mass% based on the total mass of the granulated particles.

X-2 Particles: A-2 particles, agglomerated particles consisting of MES, LMAO, water and zeolite (c2) (moisture content 7 mass% based on the total mass of the agglomerated particles).

X-3 Particles: A-3 particles, agglomerated particles consisting of MES, LMAO, water and zeolite (c2) (moisture content 6 mass% based on the total mass of the agglomerated particles).

X-4 Particles: A-4 particles, agglomerated particles consisting of MES, LMAO, water and zeolite (c2) (moisture content 7 mass% based on the total mass of the agglomerated particles).

When the granular detergent composition containing the particles (X) is produced at a blending amount described later, the content of the MES in the granular detergent composition is preferably 9 By mass. When the granular detergent composition containing the particles (X) is produced at a blending amount described later, the content of LMAO in the granular detergent composition is preferably 2 mass% based on the total mass of the granular detergent composition %.

(Preparation of MES mixed concentrate)

The fatty acid ester was sulfonated and neutralized with sodium hydroxide to obtain an MES slurry (MES slurry having a water content of 25 mass%) in which MES was dispersed in water. A portion of LMAO was added to the MES slurry, and the mixture was concentrated under reduced pressure in a thin film drier until the water content in the MES slurry reached 11 mass%, whereby a mixed concentrate of MES and LMAO (hereinafter referred to as MES mixed concentrate ).

The fatty acid ester used herein was a sodium salt of fatty acid methyl ester sulfonate having a carbon number of 16: carbon number of 18 = 80: 20 (mass ratio) (manufactured by Lion Corporation, AI (purity) = 70% by mass, the remainder being unreacted fatty acid methyl ester, Sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).

(Assembly process)

Then, the spray dried particles, MES mixed concentrate, LMAO and water were fed into a continuous kneader (KRC-S12 type, manufactured by Kurimoto, Ltd.) and kneaded under conditions of a kneader rotation speed of 135 rpm and jacket temperature of 60 캜, To obtain a kneaded product containing the active agent.

The kneaded product was extruded by a PELLETER DOUBLE (manufactured by Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm and cut with a cutter (the cutter circumferential speed was 5 m / s) A pellet-shaped molding was obtained.

Subsequently, the obtained pellet-shaped product was pulverized (manufactured by Hosokawa Micron Corporation, DKA-3) arranged in three tiers in series in the coexistence of zeolite (zeolite (c2) (Screen hole diameter: first stage / second stage / third stage = 12 mm / 6 mm / 3 mm, number of revolutions: first stage / second stage / third stage). Thus, the particles X (X-1-1 particles, X-1-2 particles, X-2 particles, X-3 particles or X-4 particles) were obtained.

The amount of zeolite used in the pulverization was the amount shown in Tables 2 and 3 with "zeolite (c2) used in the granulation process" f. The zeolite (c2) used in this granulation process is a ratio (mass%) to the total mass of the granular detergent composition.

With respect to the obtained particles (X), the weight loss after 20 minutes at a sample surface temperature of 130 占 폚 was measured using an infrared moisture meter, and the measured value was regarded as the water content in the particles (X). The amount (mass%) of water not derived from the spray-dried particles in the particles (X) was determined from the measured values and the moisture content in the spray-dried particles measured as described above by the following formula.

Moisture content (mass%) not derived from spray-dried particles = (water content in particles (X) -water content of spray-dried particles)

«3. Preparation of granular detergent composition (mixing step) »

The granular detergent composition was obtained by mixing the particles (X), the PC agent and the zeolite (zeolite (c2)) according to the following production method (1), (2) or (3) so as to have the composition shown in Tables 2 to 3. The recipe for each example is given in Tables 2 to 3.

[Manufacturing method (1)]

Particles (X) and zeolite were added to the vessel rotating cylindrical mixer and mixed at a rate of 15 kg / min. After that, a PC agent was added, and LMAO was added to the total mass of the granular detergent composition so that LMAO was 1 mass% And mixed for 2 minutes to obtain a granular detergent composition. Cylindrical container The rotary type cylindrical mixer was composed of a container having a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, an exit beam height of 0.15 m, a bladed inner blade having a height of 0.1 m and a length of 1.4 m, It is a mixer.

[Manufacturing method (2)]

The particles (X), the PC agent and the zeolite were simultaneously charged into a vessel rotating cylindrical mixer and mixed at a rate of 15 kg / min. Further, LMAO was added to the total mass of the granular detergent composition so that LMAO was 1 mass% Minute to obtain a granular detergent composition. The vessel rotary type cylindrical mixer used the same mixer as in the production method (1).

[Manufacturing method (3)]

Then, the particles (X) and zeolite were simultaneously charged into a vessel rotating cylindrical mixer and mixed at a rate of 15 kg / min. Immediately thereafter, LMAO was added so that LMAO was 1 mass% based on the total mass of the granular detergent composition, And left for 2 minutes in an environment of relative humidity of 50% RH. Subsequently, a PC agent was added and mixed for 2 minutes to obtain a granular detergent composition. The vessel rotary type cylindrical mixer used the same mixer as in the production method (1).

The obtained granular detergent composition was evaluated as follows. The results are shown in Tables 2 to 3.

&Quot; (b) Component Stability &

The obtained granular detergent composition was subjected to the following storage stability test.

A paper made of three layers of cardboard paper (basis weight: 350 g / m2), wax sand paper (basis weight: 30 g / m2) and kraft pulp paper (basis weight: 70 g / m2) A box having a height of 18.5 cm was made, and 1.0 kg of a granular detergent composition was placed in the box. The box containing the granular detergent composition was sealed and kept in a constant temperature and humidity room for 30 days. The constant temperature and humidity chamber was repeatedly operated at 45 DEG C for 8 hours at 75% RH and for 16 hours at 25 DEG C and 55% RH. After the storage for 30 days, the box containing the granular detergent composition was taken out from the constant temperature and humidity chamber and allowed to stand at 25 DEG C and 60% relative humidity for 6 hours.

After the completion of the storage stability test, the granular detergent composition was thoroughly mixed, and then the granular detergent composition was sampled in the following procedure to measure the residual ratio of sodium percarbonate.

[Measurement of residual rate of sodium percarbonate]

The box containing the granular detergent composition was kept stationary on the horizontal stand and 1 cup (about 50 g) of granular detergent composition was spilled from the center using a spoon. About 25 g of the granular detergent composition (sample) was weighed to 10 mg.

Approximately 25 g of the purified sample was placed in a 1 L beaker, 200 mL of 33% by mass acetic acid aqueous solution was added, and the mixture was dissolved by dissolving in a magnetic stirrer. Subsequently, 40 mL of a 10 mass% potassium iodide aqueous solution was added, and the obtained solution was titrated with 1 mol / L sodium thiosulfate solution. On the way, when the solution became colorless, 2 to 3 drops of saturated ammonium molybdate were added. When the solution became pale yellow, further titration was continued. Titration was terminated when the solution became colorless again. From the titration amount p (mL) of 1 mol / L sodium thiosulfate solution dropped from titration to titration, the effective oxygen content (%) was determined by the following formula.

Effective oxygen amount (%) = {f x p (1/2) x (1/1000) x 16} / g x 100

Wherein f is a factor of a 1 mol / L sodium thiosulfate solution, p is an appropriate amount (unit: mL) of a 1 mol / L sodium thiosulfate solution, and g is a mass of a sample (unit: g)

The remaining half of the sample, about 25 g, was also obtained by the above-mentioned method. The average value of these was regarded as the effective oxygen amount of the sample.

Separately, the amount of effective oxygen (%) made of PC used in the preparation of the granular detergent composition was measured. The effective oxygen amount produced by PC was calculated by measuring the effective oxygen amount (%) made by PC from the equation for obtaining the same effective oxygen amount as the above.

From these effective oxygen amounts, the residual ratio (%) of sodium percarbonate was determined by the following formula.

Percentage of sodium percarbonate remaining (%) = (Effective oxygen amount (%) of sample / Effective oxygen amount (%

«Liquidity»

After completion of the storage stability test, the box containing the granular detergent composition was stopped on the horizontal stand and 1 cup of spoon leveling (about 50 g) of the granular detergent composition was removed from the center using a spoon.

The amount of PC agent contained in the granular detergent composition was defined as " PC amount of use start ". Further, the granular detergent composition was continuously applied by 1 cup of spoon leveling so as not to float the same place continuously. The amount of PC agent contained in the granular detergent composition which was left just before the leveling 1 cup could not be removed with a spoon without tilting the box was defined as " the amount of PC just before the end of use ". The ratio of the difference between the " amount of PC at the start of use " and the amount of " PC immediately before the end of use " was calculated and the classification evaluation of the granular detergent composition was made.

The amount of PC agent contained in the sample was quantified by the following method.

From the granular detergent composition (sample), about 25 g was weighed to 10 mg, and the effective oxygen amount (%) was obtained in the same manner as above. The remaining half of the sample, about 25 g, was also obtained by the above-mentioned method. The average value of these was regarded as the effective oxygen amount of the sample.

From the effective oxygen amount, the residual ratio (%) of sodium percarbonate was calculated in the same manner as described above, and the amount of PC agent contained in each of the samples of "start of use" and "immediately before the end of use" The percent classification of PC grade was calculated and the fluidity of the granular detergent composition was evaluated based on the following evaluation criteria.

PC classification ratio (%) = amount of PC contained in the sample of use start / amount of PC contained in the sample just before the end of use × 100 (%)

〔Evaluation standard〕

A: Classification of PC grade is less than 5%.

B: PC classification ratio exceeding 5% and less than 10%.

C: Classification ratio of PC grade exceeds 10% and 15% or less.

D: The classification ratio of PC grade is more than 15% and less than 20%.

E: PC classification ratio exceeded 20%.

In Tables 2 to 3, the unit of the blending amount is mass% and the blending ratio is the mass ratio.

The ratio of the particle X to the zeolite c2 is calculated by dividing the particle X by the total amount of the zeolite used in the granulation process and the zeolite used in the mixing process (i.e., zeolite c2) (mass% (% By mass) "

The amount of water not derived from the spray-dried particles in the particle X is calculated from the amount of water (mass%) in the particles X and the amount of water (mass%) in the spray-dried particles immediately after the spray- (% By mass) of spray-dried particles / 100 value ".

Compared to Examples 1 to 8 and Comparative Examples 1 to 3 prepared in Production Method (1), the granular detergent compositions of Examples 1 to 8 had better stability of component (b) as compared with Comparative Examples 1 to 3. Particularly, the results of Examples 1 to 7 in which the amount of water not derived from the spray-dried particles in the particles (X) is smaller than the water content in the spray-dried particles used in the production of the particles (X) Further, the granular detergent compositions of Examples 1 to 8 were suppressed from classifying the particles during the storage stability test.

On the other hand, in Comparative Examples 1 and 2 in which the mass ratio c1 / c2 of the zeolite (c1) to the zeolite (c2) exceeds 0.7, the content of the component (c) in the granular detergent composition (zeolite (c1) + zeolite (c2) ) Was 19.8%, the stability of the component (b) in Comparative Example 3 was low. Particularly, in Comparative Examples 1 and 2, classification of the particles in the storage stability test was remarkable.

The results of Example 9 in which the respective particles were mixed according to Production Method (3) were particularly good when the compositions of Examples 9 and 10 were the same as those of Example 1 and only the production method was different.

&Lt; Examples 11 to 15 &

Granular detergent compositions having the compositions shown in Table 4 were prepared in the following order. The unit of the blending amount and water content in the table is mass%.

First, except that zinc sulfate, MGDA and citric acid were further blended in the spray-drying slurry, Preparation of spray-dried particles > Spray-dried particles were produced in the same manner as in &

Particles (X) were prepared in the same manner as in the above (assembly step) except that the obtained spray-dried particles were kneaded by adding a spray drying agent, a MES mixed concentrate, LMAO and a fluorescent whitening agent together with water.

The obtained particles (X), the zeolite, the PC agent, the sodium bicarbonate and the CMC were simultaneously introduced into the vessel rotating cylindrical mixer at a rate of 15 kg / min, and thereafter, an LMAO aqueous solution having a concentration of 1% by mass was sprayed , And left for 2 minutes in an environment of 20 ° C and a relative humidity of 50% RH. Subsequently, the enzyme and OBS were added and mixed for 2 minutes to obtain a granular detergent composition. The vessel rotation type cylindrical mixer used the same mixing apparatus as in the production method (1).

(Industrial availability)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a granular detergent composition having improved storage stability of inorganic peroxide under the coexistence of zeolite and a method for producing the granular detergent composition.

Claims

A granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)
The granular detergent composition comprises
(X) which comprises spray-dried particles obtained by spray-drying a slurry containing the surfactant (a) and a part of the zeolite (c), and which does not contain the inorganic peroxide (b)
(Y) comprising the inorganic peroxide (b);
The content of the zeolite (c) is 5 to 15 mass% with respect to the total mass of the granular detergent composition;
The zeolite (c) comprises a zeolite (c1) blended with the slurry and a zeolite (c2) other than the zeolite (c1)
Wherein the mass ratio c1 / c2 of the zeolite (c1) to the zeolite (c2) is greater than 0 and less than or equal to 0.7.

A method for producing a granular detergent composition comprising a surfactant (a), an inorganic peroxide (b) and a zeolite (c)
In the above manufacturing method,
A step of obtaining the particles (X)
A mixing step of mixing the particles (Y) containing the inorganic peroxide (b) and the particles (X)
The step of obtaining the particles (X)
Spray-drying a slurry containing a part of the zeolite (c) to obtain spray-dried particles,
(X) containing the surfactant (a) but not containing the inorganic peroxide (b) from the obtained spray-dried particles,
The amount of the zeolite (c) to be used is 5 to 15 mass% with respect to the total mass of the granular detergent composition to be produced,
The zeolite (c) comprises a zeolite (c1) blended with the slurry and a zeolite (c2) other than the zeolite (c1)
Wherein a mass ratio c1 / c2 of the zeolite (c1) to the zeolite (c2) is greater than 0 and less than or equal to 0.7.

The method according to claim 1,
With respect to the total mass of the granular detergent composition,
The content of the surfactant (a) is 5 to 30% by mass,
The content of the inorganic peroxide (b) is 3 to 20% by mass,
The total content of the respective components is not more than 100% by mass,
With respect to the total mass of the granular detergent composition,
The content of the particles (X) is 50 to 90% by mass,
Wherein the content of the particles (Y) is 3 to 20 mass%, and the total content of the respective particles does not exceed 100 mass%.