JP5347156B2 - High bulk density granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-bulk density granular detergent composition simultaneously having excellent detergency, resoiling-preventing property, solubility and foam-inhibiting property. <P>SOLUTION: The high-bulk density granular detergent composition contains (A) an &alpha;-sulfofatty acid alkyl ester salt, (B) an alkyl or alkenyl sulfate salt, and/or an alkyl or alkenyl ether sulfonate salt, (C) an alkylbenzenesulfonic acid salt, and (D) a protease and/or a cellulase, wherein the parts [A], [B] and [C] by masses of the formulated components (A), (B) and (C) respectively satisfy the relation of 1&le;[A]/([B]+[C])&le;2, and the total content of the surfactants based on the whole composition is 10-20 mass%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a high bulk density granular detergent composition having excellent detergency, recontamination prevention, solubility and foam suppression.

Due to the recent increase in environmental awareness, high bulk density detergents that can suppress the amount used have become mainstream. At the same time, with the increase in the size of washing machines and the spread of drum-type washing machines, water-saving laundry that uses a small amount of water for laundry is also becoming popular. Due to these trends, various conditions regarding washing have also changed, and as a result, obtaining sufficient detergency, recontamination prevention, solubility, etc. has become a challenge, and various studies have previously been conducted to solve this problem. (Patent Documents 1 and 2).
In particular, in a drum type washing machine, the detergent concentration is high, so foam tends to form. As a result, foam overflows from the washing machine. If too much foam is formed, the washing liquid is discharged from the washing machine. Therefore, there is a problem that the original cleaning power cannot be obtained, and furthermore, there is a problem of wasting time and electric power for rinsing, and therefore, a detergent having foam suppression properties in addition to cleaning power, anti-contamination property and solubility. Is required. However, in reality, it is difficult to obtain a high bulk density granular detergent that satisfies the above conditions at a high level at the same time.

JP-A-4-213399 JP-A-5-171199

  An object of the present invention is to provide a high bulk density granular detergent having excellent detergency, recontamination preventing property, solubility and foam suppression property at the same time.

  The inventors of the present application have found that the above-mentioned problems can be solved by blending a surfactant under predetermined conditions and preparing a high bulk density granular detergent composition containing protease and / or cellulase, and complete the present invention. It came to.

That is, the present invention
(A) α-sulfo fatty acid alkyl ester salt,
(B) alkyl or alkenyl sulfate and / or alkyl or alkenyl ether sulfate,
(C) an alkylbenzene sulfonate, and
(D) A high bulk density granular detergent composition comprising protease and / or cellulase,
The blending parts [A], [B] and [C] of the components (A), (B) and (C) are 1 ≦ [A] / ([B] + [C]) ≦ 2.
Satisfy the relationship
Provided is a composition comprising a total of 10 to 20% by weight of surfactants based on the total composition.

  According to the present invention, a high bulk density granular detergent composition having both a detergency and a recontamination preventive property as well as a solubility and a foam suppression property can be obtained.

  The high bulk density granular detergent composition of the present invention comprises a surfactant. As a kind of surfactant, it has the following component (A), (B) and (C) as an essential component.

Component (A) α-sulfo fatty acid alkyl ester salt Examples of the α-sulfo fatty acid alkyl ester salt include the following.
(i) A methyl, ethyl or propyl ester (α-SF or MES) salt of a saturated or unsaturated α-sulfo fatty acid having 10 to 22 carbon atoms.
Examples of suitable α-sulfo fatty acid alkyl ester salts are shown below.

In the formula (A-1), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. In R ¹² , the carbon number is 1 to 6, and preferably 1 to 3. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable.
M represents a counter ion and includes, for example, alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts, among which alkali metal salts are preferred.
The α-sulfo fatty acid ester salt contains an α-sulfo fatty acid salt as a by-product.
Particularly preferred are those in which R ¹¹ is a linear or branched alkyl group or alkenyl group having 14 to 16 carbon atoms, and R ¹² is a methyl group.

  The amount of component (A) in the high bulk density granular detergent composition of the present invention is preferably 5 to 12% by mass based on the total composition. By setting it as 5 mass% or more, while being able to acquire sufficient detergency and the recontamination prevention effect, the fall of the effect | action of the enzyme mentioned later can be suppressed. Moreover, the deterioration of solubility can be prevented by setting it as 12 mass% or less.

Component (B) alkyl or alkenyl sulfate (AS) and / or alkyl or alkenyl ether sulfate (AES)
Although it does not specifically limit as a component (B) which can be used for the high bulk density granular detergent composition of this invention, For example, a C10-C20 alkyl sulfate (AS) or alkenyl sulfate, C10-C20 direct An alkyl (or alkenyl) ether sulfate (AES) obtained by adding an average of 1 to 5 moles of ethylene oxide to an alkyl (or alkenyl) having a chain or branched chain alkyl (or alkenyl) group can be used.
As a compounding quantity of a component (B), 1-3 mass% is preferable on the basis of the whole composition. By setting it as 1 mass% or more, it becomes possible to suppress the fall of the recontamination prevention effect, and it becomes possible to suppress a bubble generation | occurrence | production by setting it as 3 mass% or less.

Component (C) Alkylbenzene sulfonate (LAS or ABS)
Examples of the component (C) alkylbenzene sulfonate that can be used in the present invention include linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms. For example, C14-14 is preferable.
By blending component (C), a solubility improving effect and a detergency improving effect can be obtained. Moreover, as a compounding quantity of a component (C), 5-9 mass% is preferable on the basis of the whole composition. By setting it as 5 mass% or more, sufficient detergency and re-contamination prevention property are obtained, and by setting it as 9 mass% or more, deterioration of solubility can be suppressed.

In the high bulk density granular detergent composition of the present invention, the blending parts [A], [B] and [C] of the components (A), (B) and (C) are 1 ≦ [A] / ([[ B] + [C]) ≦ 2, preferably 1 ≦ [A] / ([B] + [C]) ≦ 1.4. By setting the value of [A] / ([B] + [C]) to 1 or more, it becomes possible to suppress a decrease in enzyme activity, and by setting it to 2 or less, a decrease in solubility is suppressed. It becomes possible to do.
Component (A) has good enzyme stability but is difficult to dissolve, and components (B) and (C) tend to decrease the activity of the enzyme. As a result of examining the blending conditions of the components (A), (B) and (C), the detergency of the detergent composition is determined by setting the value of [A] / ([B] + [C]) to the above-mentioned range. The present inventors have found that an excellent effect can be obtained with respect to recontamination prevention, solubility and foam suppression.

  The high bulk density granular detergent composition of the present invention may contain other surfactants described later in addition to the essential components (A), (B) and (C) described above as surfactants. In the high bulk density granular detergent composition of the present invention, the total amount of components (A), (B), (C), and any other surfactants is 10-20% by weight, based on the total composition, Preferably it is 12-20 mass%, More preferably, it is 15-20 mass%. 20 mass% or less is preferable from the surface of foam suppression and environmental consideration, and sufficient detergency and recontamination prevention property are obtained by setting it as 10 mass% or more.

  In the high bulk density granular detergent composition of the present invention, the value of [A] / ([B] + [C]) is 1 to 1.4, and the interface is based on the total composition. It is particularly preferable to contain 15 to 20% by mass of activators in total.

  Furthermore, in the high bulk density granular detergent composition of the present invention, the total amount of components (A), (B) and (C) based on the total surfactant is preferably 80 to 100% by mass, more preferably 85. It is -98 mass%, Most preferably, it is 90-95 mass%. By setting it as the above range, the cleaning power and the recontamination prevention property are improved.

Examples of surfactants other than (A), (B) and (C) that can be used in the present invention include the following.
<Anionic surfactant>
The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) C-C20 soot-olefin sulfonate (AOS)
(2) Alkanesulfonate having 10 to 20 carbon atoms (3) Ethylene oxide or propylene having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Alkyl ether carboxylate or alkenyl ether carboxylate to which oxide, butylene oxide or a mixture thereof is added (4) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms (5) Soap As the soap that can be used in the invention, the fatty acid has an average carbon number of 10 to 20, preferably an alkali metal salt or alkaline earth metal salt of a higher fatty acid having 12 to 18 carbon atoms, preferably an alkali metal salt, more preferably sodium or A potassium salt is mentioned. The alkyl group of the fatty acid is preferably primary. Either a single chain length or a mixture of two or more types can be suitably used.
In the present invention, when soap is dispensed, it is preferably blended in an amount of 0.2 to 2% by mass, more preferably 0.5 to 1.5% by mass, for example 1% by mass, based on the total composition.

  Among the above, as the anionic surfactant used in the high bulk density granular detergent composition of the present invention, AOS and soap are preferable. In a preferred embodiment, the high bulk density granular detergent composition of the present invention has a surface activity. In addition to components (A), (B) and (C), soap is included as an agent.

<Nonionic surfactant>
Examples of nonionic surfactants that can be used in the present invention include the following.
(1) Polyoxyalkylene alkyl ether or polyoxy obtained by adding an average of 3 to 30 moles, preferably 3 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms Alkylene alkenyl ether.
Among these, preferable examples include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols, and primary alcohols are preferred. The alkyl group or alkenyl group may be linear or branched.
(2) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkenyl phenyl ether (3) Alkyl oxide added between ester bonds of long chain fatty acid alkyl ester, for example, fatty acid alkyl ester alkoxy represented by the following general formula (I) Rate R ¹ CO (OA) N'OR ² (I)
(Wherein R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OA represents an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (for example, ethylene oxide, N ′ represents the average number of moles of alkylene oxide added, and is generally 3 to 30, preferably 5 to 20. R ² represents 1 to C carbon atoms. 3 represents a lower (1 to 4 carbon) alkyl group optionally having 3 substituents.)
(4) Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbit fatty acid ester (6) Polyoxyethylene fatty acid ester (7) Polyoxyethylene hydrogenated castor oil (8) Glycerin fatty acid ester Among the above nonionic surfactants The nonionic surfactant of (1) is preferable, and among them, a polyoxyalkylene alkyl ether or polyoxyalkylene obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms Alkenyl ethers are particularly preferred.
Also, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester and ethylene having a melting point of 50 ° C. or less and HLB of 9 to 16 A fatty acid methyl ester ethoxylate to which an oxide is added, a fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
The above-mentioned “HLB” is a value obtained by the method of GRIFFIN (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991, p. 234). reference).
The “melting point” is a value measured by the melting point measurement method described in JIS K 0064-1992 “Measuring method of melting point and melting range of chemical product”.

<Cationic surfactant>
Examples of the cationic surfactant that can be used in the present invention include the following.
(1) Di long chain alkyl dishort chain alkyl type quaternary ammonium salt (2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt (3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt The above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
Further, the “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

<Amphoteric surfactant>
Examples of amphoteric surfactants that can be used in the present invention include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

By blending component (D) protease and / or cellulase component (D), an effect of preventing recontamination and an effect of improving detergency can be obtained.
Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like.
Examples of commercially available products include sabinase, alcalase, everase, cannase, everase, deozyme, and porozyme (trade name; manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); And the like, KAP (manufactured by Kao Corporation), and proteases K-14 and K-16 described in JP-A-5-25492.
Examples of cellulases include commercially available cellzymes and carezymes (trade names, manufactured by Novozymes); KAC500 (manufactured by Kao Corporation), alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, and alkaline cellulase K. -539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMC Examples include ase II, alkaline cellulase E-II, and alkaline cellulase E-III (the cellulase described in JP-A-63-264699).
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
The enzyme is preferably granulated as a separate stable particle and used in a dry blended state with a detergent dough (particle). As a method for granulating the enzyme-containing particle, JP-A-53-6484 is disclosed. JP-A-60-262900, JP-A-62-257990, JP-A-1-112983, JP-T-3-503775, JP-A-4-503369, JP-A-2000-178593. And the method described in the Japanese Patent Publication.
The average particle size of the enzyme-containing particles is preferably 200 to 1,000 μm, more preferably 300 to 700 μm, from the viewpoints of solubility and storage stability.
When the content of the enzyme is preferably 0.1 to 2% by mass and less than 0.1% by mass, a sufficient effect cannot be obtained. Is not preferable.

The average particle size of the high bulk density granular detergent composition of the present invention is 200 to 1000 μm, preferably 250 to 700 μm, more preferably 300 to 600 μm.
The bulk density of the high bulk density granular detergent composition of the present invention is preferably 650 g / L or more, more preferably 700 to 1000 g / L.
It is preferable that the average particle diameter and the bulk density are in such ranges because handling properties, solubility and usability are good.

  Moreover, the manufacturing method of the high bulk density granular detergent composition of this invention is not restrict | limited in particular, It can manufacture with the manufacturing method generally used. For example, when the high bulk density granular detergent composition is in powder form, for example, a method of dispersing and dissolving a surfactant and other raw materials in water and spray drying, kneading / extrusion, stirring granulation, It can be produced by a method such as rolling, granulation, compression molding, etc., using a device such as rolling granulation, and further pulverizing if necessary.

Other components In addition to the above components, the granular detergent composition of the present invention may further contain the following optional components as necessary.
<Detergency Builder>
Detergency builders include inorganic builders and organic builders.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate; crystalline layered sodium silicate [eg, trade name “Na-SKS-6” (δ -Na ₂ O · 2SiO ₂₎ crystalline alkali metal silicates, etc.], an amorphous alkali metal silicate; sodium sulfate, sulfates such as potassium sulfate; sodium chloride, alkali metal chlorides such as potassium chloride; orthophosphoric acid Phosphate such as salt, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; crystalline aluminosilicate, amorphous aluminosilicate, sodium carbonate and amorphous alkali metal silicate Examples include composites (for example, trade name “NABION15” of Rhodia).
Among the inorganic builders, sodium carbonate, aluminosilicate, or potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as those having the effect of improving solubility.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability.
As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be suitably blended, and the average primary particle size is preferably 0.1 to 10 μm. The content of the crystalline aluminosilicate in the granular detergent composition is preferably 1 to 40% by mass, particularly preferably 2 to 30% by mass from the viewpoint of powder physical properties such as cleaning performance and fluidity.
When mix | blending potassium carbonate, the content is from a point of the effect of a solubility improvement, Preferably it is 1-15 mass% in a granular detergent composition, More preferably, it is 2-12 mass%, More preferably, it is 5-5. 12% by mass.
When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably, in the granular detergent composition in terms of the effect of improving solubility. It is 3-7 mass%.
When blending the crystalline alkali metal silicate, the content thereof is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, and further preferably from the viewpoint of cleaning performance in the granular detergent composition. Is 3 to 20% by mass, particularly preferably 5 to 15% by mass.

Examples of the organic builder include an organic high molecular builder and an organic low molecular builder. As an organic polymer builder, polymers or copolymers of acrylic acid polymer compounds, polyacetal carboxylates, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, Examples include polyethylene glycol, polyvinyl alcohol, carboxymethylcellulose (CMC), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), methylcellulose (MC), cellulose derivatives such as cationized cellulose, and cellulose such as powdered cellulose. As the acrylic acid-based polymer compound, an acrylic acid polymer and an acrylic acid / maleic anhydride copolymer are preferable. In particular, a salt of an acrylic acid / maleic anhydride copolymer having a weight average molecular weight of 1000 to 80000, acrylic acid Polymer salts are preferred. In particular, sodium or potassium salt of acrylic acid / maleic anhydride copolymer is preferred. As the polyacetal carboxylate, a polyacetal carboxylate such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000, preferably 5000 to 200000 described in JP-A No. 54-52196 is suitable. As the polyethylene glycol, an average molecular weight of 200 to 200,000 is suitable. The water-soluble polymer compound preferably has a weight average molecular weight of 1,000 to 1,000,000, more preferably 1,000 to 100,000.
In addition, a copolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol, a terpolymer, or the like can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
The organic polymer builder can be used singly or in appropriate combination of two or more.
Examples of the organic low molecular weight builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, Hydroxyaminocarboxylates such as hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid Cyclocarboxylates such as salts, benzopolycarboxylates, cyclopentanetetracarboxylates; ether carboxylic acids such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate Etc. The.
Among these organic low molecular weight builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, and hydroxyiminodisuccinate are preferable.
As for content of an organic builder, 1-20 mass% is preferable in a granular detergent composition, More preferably, it is 1-10 mass%, Most preferably, it is 2-5 mass%.
The said detergency builder can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among the above detergency builders, the detergency and stain dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a polymer or polyacetal carboxylate in combination with an inorganic builder such as zeolite.
The content of the detergency builder in the granular detergent composition is preferably 10 to 80% by mass and more preferably 20 to 75% by mass from the viewpoint of imparting sufficient cleaning performance.

<Bleaching agent>
As a bleaching agent, an inorganic peroxide that generates hydrogen peroxide when dissolved in water can be used. Usually, one or both of sodium percarbonate and sodium perborate are used. In particular, sodium percarbonate is preferred from the viewpoint of stability over time. When moisture or other detergent components come into contact with the surface of the inorganic peroxide particles, the inorganic peroxide may be decomposed. Therefore, it is preferable to perform a treatment such as coating to prevent this. As the particles in the form of coating, oxygen-based bleach particles that have already been proposed can be used. Examples thereof include bleaching particles described in Japanese Patent No. 2918991. The bleaching agent particles are a granulated product obtained by spraying and drying sodium borate particles maintained in a fluidized state separately with a boric acid aqueous solution and an alkali metal silicate aqueous solution. In addition to the above, a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent.
Further, a bleach activator or a bleach activation catalyst can be used.
As the bleach activator, a known compound can be used, but an organic peracid precursor is preferable.
Examples of the organic peracid precursor include tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzoic acid having 8 to 12 carbon atoms, and salts thereof, among which 4-decanoyloxy Benzoic acid, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred, and 4-decanoyloxybenzoic acid and sodium 4-nonanoyloxybenzenesulfonate are particularly preferable in terms of bleaching effect. More preferred. These may be used alone or in combination of two or more. Particles containing the bleach activator can be produced by a known production method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquetting machine.
Specifically, the organic peracid precursor particles are prepared by heating and melting a solid binder material at room temperature such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000. And a surfactant powder such as olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, etc., are branched and extruded to produce a noodle-shaped organic peracid precursor granule having a diameter of about 1 mm, and then long It is preferable to blend by lightly pulverizing to about 0.5 to 3 mm. As the surfactant powder, an α-olefin sulfonate having an alkyl chain length of 14 is preferred.
A known compound can be used as the bleach activating catalyst. Specific examples include transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum via nitrogen atoms, oxygen atoms, etc. As the transition metal contained, cobalt, manganese, etc. are preferable, and manganese is particularly preferable. In particular, the bleach activating catalyst described in JP-A No. 2004-189893 is preferable.
Particles containing the bleach activating catalyst can be produced by a known granulation method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquette machine.

<Fluorescent brightener>
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like.
The above-mentioned optical brighteners can be used alone or in combination of two or more.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001 to 1% by mass.
Specific examples of commercially available products include Whiteex SA, Whitetex SKC (above, product; manufactured by Sumitomo Chemical Co., Ltd.); Chino Pearl AMS-GX, Chino Pearl DBS-X, and Chino Pearl CBS-X (above, trade name: Ciba Specialty Chemicals); Lemonite CBUS-3B (above, trade name: manufactured by Khyati Chemicals) and the like are preferable. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable.

<Enzyme>
You may further use enzymes other than (D) component. Of these, esterase, lipase, nuclease, amylase, pectinase and the like are preferable.
Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Specific examples of the lipase include commercially available lipases such as lipolase, lipolase ultra, Lipex (trade name; manufactured by Novozymes), and liposome (trade name, manufactured by Showa Denko KK).
Examples of amylases include commercially available stainzymes, termamyls, duramils (manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

<Enzyme stabilizer>
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. Of these, sodium tetraborate, calcium chloride and the like are preferable.
An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.
As for content of the enzyme stabilizer in a granular detergent composition, 0.05-2 mass% is preferable.

<Anti-caking agent>
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.
<Antifoaming agent>
Examples of the antifoaming agent include conventionally known ones such as silicone / silica-based ones. Moreover, you may use this antifoamer as the following antifoamer granulated material.
[Method for producing antifoam granulated product]
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component and mixed. To obtain a homogeneous mixture. Next, after mixing 50 mass% of the obtained homogeneous mixture, polyethylene glycol (PEG-6000, melting point 58 ° C.) 25 mass%, and neutral anhydrous sodium sulfate 25 mass% at 70-80 ° C., an extrusion granulator ( Granulate by model EXKS-1, manufactured by Fuji Paudal Co., Ltd. to obtain a defoamer granulated product (see JP-A-3-186307).

<Reducing agent>
Examples of the reducing agent include sodium sulfite and potassium sulfite.
<Metal ion scavenger>
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing the adsorption of metal ions to the fiber (object to be washed).
As metal ion scavengers, in addition to those included in the detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) -H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic Acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) ) Organic phosphonic acid Conductor or a salt thereof; diglycolic acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the metal ion scavenger in the granular detergent composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. If it is 0.1 mass% or more, the effect which capture | acquires the metal ion in tap water will improve. On the other hand, if it is 5 mass% or less, the effect of capturing metal ions is sufficiently obtained.

<PH adjuster>
The pH of the granular detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the granular detergent composition is preferably 8 or more, and the 1 mass It is more preferable that pH in a 9% aqueous solution is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the granular detergent composition, the pH is usually adjusted with an alkaline agent. In addition to the alkaline agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.
Moreover, in order to prevent that the pH of a granular detergent composition becomes high too much, it can also adjust to the said pH range using an acid etc.
Examples of such acids include the metal ion scavengers, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, Hydrochloric acid or the like can be used.
Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

<Fragrance>
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) consisting of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.
As such a fragrance, for example, those described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
0.001-2 mass% is preferable and, as for content of the fragrance | flavor in a granular detergent composition, 0.01-1 mass% is more preferable.
<Dye>
In the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the granular detergent composition. Of these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable.
Examples of such a dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.

  According to the composition shown in Table 1, a high bulk density granular detergent composition was prepared by the preparation method shown below. Subsequently, the prepared high bulk density granular detergent composition was used for washing, and evaluation of detergency, recontamination preventing property, solubility, and foam suppression was performed. In the following examples, unless otherwise specified, “%” of the composition indicates mass%.

Manufacturing method First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, soap and a fluorescent agent were added and stirred for 10 minutes. Subsequently, after adding sodium carbonate and sodium sulfite, the MA agent was added and further stirred for 10 minutes, and then a part of the zeolite was added and stirred for 10 minutes. Furthermore, the slurry for spray drying was prepared by stirring for 30 minutes.
The temperature of the obtained slurry for spray drying was 50 ° C. This slurry was spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles having a moisture content of 3%, a bulk density of 0.50 g / cm ³ and an average particle size of 250 μm.
Separately, an anionic surfactant acid precursor (MES acid / LAS acid), an anionic surfactant (AS / AES) and metaxylene sulfonic acid were mixed at a temperature of 80 ° C., and the water content was 10%. A surfactant composition was prepared.
Then, the obtained spray-dried particles were put into a Roedige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped excavator and having a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume). The stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started while flowing 80 ° C. warm water through the jacket at a flow rate of 10 L / min. By adding the surfactant composition prepared above over 2 minutes and then stirring for 5 minutes, a part (equivalent to 10%) of the powder A-type zeolite was added and stirred for 2 minutes. Particles were obtained.
The obtained particles and a part of powder A-type zeolite (2% equivalent amount) are mixed with a V blender, sprayed with PEG and fragrance at 60 ° C., and surfactant-containing particles (average particle size 300 μm, bulk density 0 .78 g / cm ³ ) was obtained.

Preparation method of bleach activator granulated product (NOBS) First, synthesis of bleach activator 4-nonanoyloxybenzene sulfonate sodium as a raw material, 4-hydroxybenzene sulfonate sodium (Kanto Chemical Co., Ltd. reagent), N, N-dimethylformamide (a reagent manufactured by Kanto Chemical Co., Inc.), nonanoic acid chloride (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and acetone (a reagent manufactured by Kanto Chemical Co., Ltd.) were used in the following manner.
3000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 2918 g (15.3 mol) of nonanoic acid chloride was stirred at 50 ° C. for 30 minutes while stirring with a stirrer. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, the crystals were purified by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-nonanoyloxybenzenesulfonate. The yield was 91%.
70 parts by mass of sodium 4-nonanoyloxybenzenesulfonate synthesized by the above method, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)), sodium α-olefin sulfonate having 14 carbon atoms Powder product (trade name: Liporan PJ-400 (manufactured by Lion Corporation)) was put into Hosokawa Micron's Extrude Ohmic EM-6 (trade name) so that the total amount was 5000 g at a ratio of 5 parts by mass, By kneading and extruding, a noodle-like extruded product having a diameter of 0.8 mmφ was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 (trade name) manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent, and pulverized to obtain an average particle size of about A 700 μm bleach activator granulate (NOBS) was obtained.

  Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Surfactant-containing particles, bleach activator granules, sodium percarbonate, enzyme, and sodium sulfate were mixed for 5 minutes under the conditions of volume%, rotational speed 22 rpm, and 25 ° C. to obtain a granular detergent composition.

[Method for evaluating solubility]
The high bulk density granular detergent composition was passed through a JIS sieve (using # 32 and # 42), and the particle size was adjusted to 355 to 500 μm. 20 g of the detergent composition was weighed, and this amount was defined as “detergent mass before adding water”. 20 g of the detergent composition having a uniform particle diameter is placed on a pulsator of a two-tank washing machine (CW-C30A1-H manufactured by Mitsubishi Electric Corporation), and 30 L of tap water at 5 ° C. is placed in the detergent composition. After being put in over 3 minutes so as not to be directly applied to the water, it was stirred with a “weak water flow” for 2 minutes and then drained, and the waste water was collected in a container. The waste water is filtered through a JIS sieve having an aperture of 74 μm, and the detergent residue remaining on the sieve and the detergent residue in the washing machine are collected and air-dried at room temperature, and the mass is measured to obtain “detergent residue mass”. did. The dissolution rate was determined by the following equation from the “detergent mass before adding water” and the “detergent residue mass” thus obtained.
Dissolution rate (%) = [(detergent mass before adding water-detergent residue mass) / (detergent mass before adding water)] × 100
The following evaluation criteria were set for the dissolution rate, and the dissolution rate of each surfactant-containing particle was evaluated. The results are shown in Tables 2 and 3. ◎◎, ◎ and ○ were accepted.
<Evaluation criteria>
◎: Dissolution rate is 90% or more ◎: Dissolution rate is 80% or more and less than 90% ○: Dissolution rate is 70% or more and less than 80% △: Dissolution rate is 50% or more and less than 70% ×: Dissolution rate is less than 50%

[Evaluation method for re-contamination prevention]
Five sheets of 5 × 5 cm cotton cloth (BVD skin shirt: G0134TS was cut) were prepared as a recontamination prevention determination cloth for each detergent composition. Ten sheets of 5 × 5 cm EMPA101 (EMPA) were prepared as detergent cloths per detergent composition. U. S. Put the surfactant-containing particles of Examples or Comparative Examples, 5 cotton fabrics and 10 soiled fabrics in the Teg-o-meter of Testing, and adjust the bath ratio by chopping BVD skin shirt G0134TS. Adjusted to 30 times. The operation of washing at 120 rpm and 25 ° C. for 10 minutes, rinsing under the same conditions and dehydrating for 1 minute was repeated three times.
For washing, 900 ml having a detergent concentration of 0.073% was used, and 3 ° DH hard water (30 mg / L in terms of calcium chloride) was used as water. Measure the reflectance of the re-contamination prevention cloth using a reflectance meter (Nippon Denshoku Industries Co., Ltd., colorimetric chromaticity meter model 1001DP), and determine the difference ΔR from the reflectance before cleaning. evaluated. When ΔR is 1 or more, visual identification is possible.
The following evaluation criteria were set for the anti-contamination property, and the anti-contamination property of each surfactant-containing particle was evaluated. The results are shown in Tables 2 and 3. ◎◎, ◎ and ○ were accepted.
<Evaluation criteria>
◎: ΔR is less than 1 ◎: ΔR is from 1 to less than 2 ○: ΔR is from 2 to less than 3 △: ΔR is from 3 to less than 4 ×: ΔR is 4 or more

[Evaluation of cleaning performance]
Using Teg-O-meter of Testing in the United States as a cleaning tester, put 10 wet artificial soiled fabrics (purchased from the Laundry Science Association) and cleaning knitted fabrics, add so that the detergent concentration is 0.067%, Washing was performed at 120 rpm and 20 ° C. for 10 minutes in accordance with the bath ratio of 30 times. The water used was 4 ° DH, the amount of the cleaning solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the evaluation cloth was dried, the washing rate was calculated according to the following formula, the evaluation criteria shown below were set, and 及 び and ○ were accepted. In the formula, R is a reflectance measured using a color meter Σ-9000 made by Nippon Denshoku. The reflectance was measured using a 460 nm filter. The evaluation of the washing rate was carried out by the average value of 10 test cloths.

<Evaluation criteria>
◎◎: 80% or more ◎: 75% or more and less than 80% ○: 70% or more and less than 75% △: 65% or more and less than 70% ×: Less than 65%

[Evaluation of foaming property]
The foaming performance when used as a detergent for a drum type washing machine was measured as follows. Using a drum-type washing machine (Sharp Co., Ltd. fully automatic drying washing machine ES-E61), 1 kg of a cotton skin shirt was washed with water having a detergent amount of 20 g, a water temperature of 15 ° C., and a Ca hardness of 4 ° DH for 25 minutes. The height from the lower end of the glass window of the drum washing machine to the upper end of the foam was measured as the foam height (cm). The following evaluation criteria were set for foaming, and ◎ and ○ were accepted.
<Evaluation criteria>
◎: Bubble height is less than 5 cm ○: Bubble height is from 5 cm to less than 15 cm Δ: Bubble height is from 15 cm to 25 cm
×: Bubble height is 25 cm or more

[Measurement of bulk density]
The bulk density was measured according to JISK3362-1998.

Details of each component in Table 1 are as follows.
MES: Fatty acid ester obtained by transesterification of palm oil with methyl alcohol is fractionated, C16 fatty acid ester fraction and C18 fatty acid ester fraction are mixed at a mass ratio of 5: 5, and the flow-down type thin film reactor is mixed. Then, sulfonation was performed with SO ₃ gas diluted with nitrogen gas under the conditions of a reaction molar ratio (SO ₃ / fatty acid ester) = 1.2 and a reaction temperature of 80 ° C. Subsequently, after introducing 30 parts by mass of methanol with respect to 100 parts by mass of α-sulfo fatty acid methyl ester, 8.6 parts by mass of 35% hydrogen peroxide was introduced, and bleaching was performed at 80 ° C. for 60 minutes. Excess methanol was then removed under reduced pressure to give an aqueous slurry of MES acid. The MES content is 66% by mass and the water content is 27% by mass. The compounding quantity in a table | surface shows the value (mass%) as MES-Na obtained by neutralizing this.

-LAS: linear alkyl (C10-C14) benzenesulfonic acid [manufactured by Lion Corporation, Lipon LH-200 (LAS-H pure content 96 mass%)]. The compounding quantity in a table | surface shows the value (mass%) as LAS-Na obtained by neutralizing this.

AS-Na: sodium lauryl sulfate ester (manufactured by Lion Corporation, trade name: SANNOL LM-1100NT).
・ AES: Polyoxyethylene alkyl ether sulfate (EO3)
Ethylene oxide average 3 mol adduct prepared by Japanese Patent Application No. 2005-325807 (P2005-325807)

・ Protease: Sabinase 12T (Novozymes)
・ Cellulase: Cellzyme 0.7T (manufactured by Novozymes)

Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67% by mass, titer: 40 to 45 ° C .; fatty acid composition: C12 11.7% by mass, C14 0.4% by mass, C16 29 2% by mass, C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight: 289).
Zeolite: A-type zeolite Silton B (trade name, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass).

・ PEG: Polyethylene glycol (trade name: PEG # 1000K, manufactured by Lion Corporation)
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by mass aqueous solution).
PC (sodium percarbonate): manufactured by Mitsubishi Gas Chemical Co., Ltd., SPC-D, effective oxygen amount 13.2%, average particle size 760 μm
-Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.).
-Carbonic acid Na: granular ash (Asahi Glass Co., Ltd. average particle diameter 320 micrometers, bulk density 1.07g / cm3).
-Nasulfite: Anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Perfume: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
Fluorescent agent: Chinopearl CBS-X (trade name, Ciba Specialty Chemicals) / Chinopearl AMS-GX (trade name, Ciba Specialty Chemicals) = 1/2 (mass ratio) mixture.
MXS: meta-xylene sulfonic acid (manufactured by Mitsubishi Gas Chemical Company, SXA-60)

Claims (4)

(A) α-sulfo fatty acid alkyl ester salt,
(B) alkyl or alkenyl sulfate and / or alkyl or alkenyl ether sulfate,
(C) alkylbenzene sulfonate ,
(D) protease and / or cellulase , and
Soap 0.2-2% by mass
A high bulk density granular detergent composition comprising:
The blending parts [A], [B] and [C] of the components (A), (B) and (C) are 1 ≦ [A] / ([B] + [C]) ≦ 1.4
Satisfy the relationship
A composition comprising 10 to 20% by mass of surfactants based on the total composition. Including 15 to 20% by weight of surfactants based on the total composition,
The high bulk density granular detergent composition according to claim 1.   Based on the total composition, the α-sulfo fatty acid alkyl ester salt of component (A) is 5 to 12% by mass, the alkyl or alkenyl sulfate of component (B), and / or the alkyl or alkenyl ether sulfate is 1 to The high bulk density granular detergent composition of Claim 1 or 2 which contains 5-9 mass% of alkylbenzene sulfonate of 3 mass% and a component (C).   The high bulk density granular detergent composition according to any one of claims 1 to 3, wherein the total amount of components (A), (B) and (C) based on all surfactants is 80 to 100% by mass.