JP2010180284A - Granular detergent composition and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular detergent composition which can impart a flavor lasting for a long period to a material to be washed even with a high bulk density; and a method for manufacturing the same. <P>SOLUTION: This granular detergent composition includes an oil-in-water emulsion, which contains an oil or fat component with a melting point of 40°C or above and a flavor, and a nonionic surfactant with an HLB of 13 or more, wherein this granular detergent composition has a bulk density of 0.6 kg/L or more. Preferably, this oil-in-water emulsion contains a nonionic surfactant and/or a cationic surfactant. The method for manufacturing this granular detergent composition includes preparing an oil-in-water emulsion containing an oil or fat component with a melting point of 40°C or above and a flavor, adjusting the surfactant-containing particles to a temperature of a melting point or below of the oil or fat component, thereafter spraying the oil-in-water emulsion onto the surfactant-containing particles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a granular detergent composition and a method for producing the same.

  Conventionally, in order to improve the product value of a detergent composition, a perfume has been blended. One of the purposes of blending a fragrance into a detergent composition is to mask the odor of a base mainly composed of a surfactant. Another object is to impart a scent to the object to be washed and ensure palatability. As a method of adding a fragrance to a detergent composition, a method of spraying a fragrance on surfactant-containing particles is generally known. However, spraying the fragrance directly onto the surfactant-containing particles may come into direct contact with other components in the surfactant-containing particles, which may adversely affect the quality of the fragrance. In addition, when the fragrance is simply sprayed on the surfactant-containing particles, the fragrance of the fragrance is released at an early stage, and there is a problem that the release of the fragrance in the detergent composition itself or the object to be washed is difficult to be sustained.

In recent years, in order to solve these problems, a so-called long lasting technique for maintaining the fragrance for a long period of time has been used for detergent compositions. Development of technology to sustain the release of the added fragrance for a long time is underway.
As a long lasting technique, for example, a detergent composition has been proposed in which a perfume carried on powdered nonionic cellulose is blended to improve the sustainability of the aroma (for example, Patent Document 1). In addition, as an invention utilizing microcapsules, a technique for controlling aroma release characteristics by adding a fragrance as an oil-in-water emulsion to spray-dried particles has been proposed (for example, Patent Document 2). Alternatively, a detergent composition in which an amino-containing polymer is added to delay the release of aroma has been proposed (for example, Patent Document 3).

JP 2008-156516 A Japanese Patent Laid-Open No. 5-19489 Special table 2002-520495 gazette

However, the detergent composition is required to impart a more durable fragrance to the object to be washed. In particular, in a granular detergent composition having a high bulk density, even when a microcapsule having an oil-in-water emulsion as a fragrance is blended, it has been difficult to impart a highly durable fragrance to an object to be washed.
Then, even if the bulk density is high, this invention aims at the granular detergent composition which can provide the fragrance lasting for a long time with respect to to-be-washed | cleaned material.

  The granular detergent composition of the present invention comprises an oil-in-water emulsion (hereinafter sometimes referred to as component (A)) containing an oil and fat component having a melting point of 40 ° C. or higher, and a nonionic surfactant having an HLB of 13 or higher. (Hereinafter, also referred to as component (B)), wherein the bulk density is 0.6 kg / L or more. The oil-in-water emulsion preferably contains a nonionic surfactant and / or a cationic surfactant.

  The method for producing the granular detergent composition of the present invention comprises preparing an oil-in-water emulsion containing an oil and fat component having a melting point of 40 ° C. or higher and a fragrance, and adjusting the surfactant-containing particles to a temperature not higher than the melting point of the oil and fat component. Then, the oil-in-water emulsion is sprayed onto the surfactant-containing particles.

  According to the granular detergent composition of the present invention, even if the bulk density is high, it is possible to impart a long-lasting fragrance to the object to be washed.

(Granular detergent composition)
The granular detergent composition of the present invention is a granular detergent composition containing an oil-in-water emulsion containing an oil and fat component having a melting point of 40 ° C or higher and a fragrance, and a nonionic surfactant having an HLB of 13 or higher, The bulk density is 0.6 kg / L or more.

  The bulk density of the granular detergent composition is 0.6 kg / L or more, preferably 0.7 kg / L or more, and more preferably 0.8 kg / L or more. This is because the effect of the present invention is remarkably exhibited in such a high bulk density granular detergent composition. The upper limit of the bulk density of the granular detergent composition can be determined in consideration of the detergency and solubility required for the granular detergent composition, for example, preferably determined within a range of 1.2 kg / L or less, 1.0 kg / L or less is more preferable. The bulk density is a value measured according to JIS K3362-1998.

[(A) component: oil-in-water emulsion]
The component (A) is an oil-in-water emulsion containing an oil and fat component (hereinafter referred to as (a1) component) having a melting point of 40 ° C. or higher and a fragrance (hereinafter referred to as component (a2)). The oil-in-water emulsion is a water-soluble liquid obtained by emulsifying and dispersing a mixture of the component (a1) and the component (a2) in water.
The blending amount of the component (A) in the granular detergent composition of the present invention can be determined in consideration of the quality required for the granular detergent composition, the type of the component (a2), and the like, for example, 0.01 to 2 mass. % Is preferable, and 0.1 to 1.0% by mass is more preferable. If it is in the above-mentioned range, it is because the aroma required for the granular detergent composition can be imparted and a highly durable aroma can be imparted to the object to be washed.

<(A1) component: Oil component having a melting point of 40 ° C. or higher>
The oil and fat component (a1) has a melting point of 40 ° C. or higher and a melting point of 50 ° C. or higher. When the melting point is less than 40 ° C., it becomes difficult to form an emulsion with the component (a2) in a room temperature environment, and the emulsion of the component (A) is easily broken during storage of the granular detergent composition. In addition, if the melting point of the component (a1) is 40 ° C. or higher, the component (A) is present in the solid state in the granular detergent composition, and the component (A) in the desired amount can be stably blended. is there.
In addition, melting | fusing point is a value measured according to the 2nd method of the melting | fusing point measuring method described in "Cosmetic raw material standard 2nd edition note-1984".

  The type of the fat component of the component (a1) can be determined according to the type of the component (a2), and examples thereof include higher alcohols, higher fatty acids, hardened fats and oils, among which higher alcohols and higher fatty acids are preferable. Higher alcohols are more preferred. When a higher alcohol is used as the component (a1), a crystalline oil film is formed in the component (A), so that a strong oil-in-water emulsion can be formed. In addition, it is because it becomes easy to control the particle diameter of the component (A).

The higher alcohol means an alcohol having a hydrocarbon chain having 8 or more carbon atoms. The hydrocarbon chain of the higher alcohol may be branched or linear and may have an unsaturated bond. The hydrocarbon chain of the higher alcohol preferably has 15 to 30 carbon atoms, more preferably 18 to 25 carbon atoms. Examples of such higher alcohols include 1-pentadecanol, 1-octadecanol, 1-docosanol, 1-behenyl alcohol, etc. Among them, linear 1-pentanol that can form a strong oil-in-water emulsion. Octadecanol and 1-docosanol are preferred.
The higher fatty acid means a fatty acid having 8 or more carbon atoms in the hydrocarbon chain. The hydrocarbon chain of the higher fatty acid may be branched or linear and may have an unsaturated bond. The hydrocarbon chain of the higher fatty acid preferably has 12 or more carbon atoms, more preferably 14 to 24 carbon atoms. Examples of such higher fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, and the like, among which palmitic acid, stearic acid, and behenic acid are preferable.

  The blending amount of the component (a1) in the component (A) can be determined in consideration of the type of the component (a2) and the type of the solvent, and can be determined in the range of 4 to 12% by mass, for example. Preferably, 6 to 10% by mass is more preferable. If it is less than 4% by mass, it becomes difficult to form and maintain an oil-in-water emulsion. Even if it exceeds 12% by mass, the effect of forming and maintaining an oil-in-water emulsion is saturated, and further improvement of the effect can be expected. This is because there is not.

<(A2) component: fragrance>
The fragrance | flavor which is (a2) component is a mixture (fragrance | flavor composition) which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc. The fragrance | flavor used for this invention will not be limited if it can mix | blend with a detergent. A list of fragrance ingredients that can be used as detergent fragrances can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. I and II, Stephen Arctander, Allured Pub. Co. (1994), “Synthetic perfume chemistry and product knowledge”, Motoichi Into, Chemical Industry Daily (1996), “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994), “Encyclopedia of Scent”, edited by Japan Fragrance Association, Asakura Shoten (1989), “Performerial Material Performance V.3.3”, Bolens Aroma Chemical Information Service (1996), “Flower oils”. , Danute Lajaujis Anonis, Allured Pub. Co. (1993). Further, for example, the fragrances described in JP-A Nos. 2002-146399 and 2003-89800 can be used.

  The blending amount of the component (a2) in the component (A) can be determined in consideration of the quality required for the granular detergent composition, the type of the component (a1), and the like, for example, in the range of 5 to 40% by mass. It is preferable to determine, and 10-30 mass% is more preferable. If it is within the above-mentioned range, it is possible to impart an appropriate aroma to the granular detergent composition and to stabilize the emulsion of component (A).

<Other components in component (A)>
In addition to water, which is a solvent for forming an emulsion, the component (A) can contain a lower alcohol, a nonionic surfactant, and a cationic surfactant as necessary.

≪Lower alcohol≫
A lower alcohol means an alcohol having a hydrocarbon chain having 7 or less carbon atoms. The lower alcohol to mix | blend is not specifically limited, Methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene glycol, glycerol, etc. are mentioned. This is because by adding such a lower alcohol to the component (A), the emulsified dispersion of the component (A) can be improved.
When mix | blending a lower alcohol with (A) component, it is preferable to mix | blend so that it may become 6-10 mass% in (A) component. If it is less than 6% by mass, the effect of improving emulsification dispersion is difficult to obtain, and if it exceeds 10% by mass, the strength of the oil-in-water emulsion tends to be reduced.

≪Nonionic surfactant≫
A nonionic surfactant is not specifically limited, For example, the following can be mentioned.
(1) An average of 10 to 100 moles of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 16 carbon atoms, preferably 30 -80 mol, more preferably 40-70 mol added 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 here include primary alcohols and secondary alcohols.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylates represented by, for example, the following general formula (I) in which an alkylene oxide is added between the ester bonds of a long-chain fatty acid alkyl ester.

R ¹ CO (OA) _m OR ² (I)

[In Formula (I), R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 alkylene oxide addition units, m represents the average number of moles of alkylene oxide added, and is generally 10 to 100, preferably 30 to 80. R ² represents an optionally substituted lower (1-4 carbon atoms) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]

(4) Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbite fatty acid ester (6) Polyoxyethylene fatty acid ester (7) Polyoxyethylene hydrogenated castor oil (8) Glycerin fatty acid ester

  Among these, as the nonionic surfactant, the nonionic surfactant of (1) described above is preferable, more preferably an ethylene oxide (EO) 40-70 mole adduct of an aliphatic alcohol having 12 to 16 carbon atoms, Isotridecyl ether EO 60 mol adduct is preferably used. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate. By blending such a nonionic surfactant with the component (A), the component (A) can have excellent oily-in-water emulsion particles and excellent perfume volatility control.

The HLB of the nonionic surfactant to be blended with the component (A) is not particularly limited, and can be determined in consideration of the types of the components (a1) and (a2).
When mix | blending a nonionic surfactant with (A) component, it is preferable to mix | blend so that it may become 2-6 mass% in (A) component. When it is less than the lower limit, the effect of the nonionic surfactant in the component (A) is difficult to obtain, and when the upper limit is exceeded, the melting point of the component (A) is lowered and the volatility control of the fragrance is insufficient. Tend to be.

≪Cationic surfactant≫
Examples of the cationic surfactant include the following.
(1) Dilong 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.
However, the above “long chain alkyl” represents an alkyl group having 12 to 30 carbon atoms, preferably 16 to 24 carbon atoms. 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 polyoxy having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms An alkylene group is mentioned as a suitable thing. Among such cationic surfactants, the above-described cationic surfactant (2) is preferable, and a mono long chain alkyl trishort chain alkyl type quaternary ammonium salt having a long chain alkyl group having 16 to 24 carbon atoms is more preferable. Preferred is behenyl (C22) trimethylammonium salt. By blending such a cationic surfactant with the component (A), the oil-in-water emulsion can be strengthened in the component (A) and the volatility of the perfume can be excellently controlled.
When mix | blending a cationic surfactant with (A) component, it is preferable to mix | blend so that it may become 2-6 mass% in (A) component. When it is less than the lower limit, the effect of the nonionic surfactant in the component (A) is difficult to obtain, and when the upper limit is exceeded, the melting point of the component (A) is lowered and the volatility control of the fragrance is insufficient. Tend to be.

[(B) component: nonionic surfactant having HLB of 13 or more]
The component (B) is a nonionic surfactant having an HLB of 13 or more. The kind of nonionic surfactant which is (B) component is not specifically limited, It is the same as the kind of nonionic surfactant which can be mix | blended in the (A) component mentioned above, and may be the same or different.
Among these, polyoxyalkylene alkyl (or alkenyl) ethers obtained by adding an average of 8 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms are preferable. Polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester ethoxylate in which ethylene oxide is added to fatty acid methyl ester, ethylene oxide in fatty acid methyl ester And fatty acid methyl ester ethoxypropoxylate to which propylene oxide is added. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate.

  (B) HLB of a component is 13 or more, 14 or more are preferable and 15-17 are more preferable. When the component (B) has an HLB of less than 13, the lipophilicity becomes high, and the oil content of the granular detergent composition is controlled, and the necessary amount of the component (A) is stably retained in the granular detergent composition. This is because it becomes difficult. In addition, the oil-in-water emulsion of the component (A) is broken, and the aroma is easily released in a short time. Although the upper limit of HLB of (B) component is not specifically limited, 20 or less is preferable and 17 or less is more preferable from a viewpoint of detergency. By containing such a component (B), the low oil absorbency of the high bulk density granular detergent composition can be prevented from further decreasing, and the retention amount of the component (A) can be improved by increasing the hydrophilicity. Because. In addition, it is because the cleaning property which was excellent in the granular detergent composition can be provided. The HLB in this paper is a value obtained by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho, 1991, p. 234).

  The blending amount of the component (B) in the granular detergent composition can be determined in consideration of the blending amount of the component (A) and the type of the component (B), and is preferably 3 to 8% by mass, for example. 6 mass% is more preferable. If it is 3 mass% or more, it becomes easy to mix | blend the desired quantity of (A) component with a granular detergent composition, and if it is 8 mass% or less, it is because the compounding balance with another component will be taken.

[Other ingredients]
The granular detergent composition of this invention can mix | blend detergent components, such as an anionic surfactant and a builder, in addition to (A) component and (B) component. Such a detergent component can be blended as a surfactant-containing particle granulated together with the component (B) or separately from the component (B).

<Anionic surfactant>
(1) A methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(2) Alkali metal salts or alkaline earth metal salts of higher fatty acids having an average number of carbon atoms of 10 to 20 fatty acids.
(3) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(4) Alkane sulfonate having 10 to 20 carbon atoms.
(5) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(6) C10-20 alkyl sulfate or alkenyl sulfate (AS).
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(9) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(10) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(11) Long chain monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.
By blending such an anionic surfactant into the granular detergent composition, it is possible to form a complex with the component (B) and stabilize the form of the oil-in-water emulsion of the component (A).

When mix | blending an anionic surfactant with a granular detergent composition, it is preferable to mix | blend 10-30 mass% in a granular detergent composition, and it is preferable to mix | blend 15-20 mass%. This is because the cleaning power is good within the above range.
In addition, when mix | blending an anionic surfactant with a granular detergent composition, the value (nonion) which remove | divided the compounding quantity (mass%) of the nonionic surfactant of (B) component by the compounding quantity (mass%) of an anionic surfactant / Anion blending ratio) is preferably less than 1.0, more preferably 0.6 or less, and even more preferably 0.3 or less. 1.0 or more, that is, when the blending amount of the component (B) is larger than the blending amount of the anionic surfactant, the contact frequency between the component (A) and the component (B) increases, and the emulsion of the component (A) May be destroyed. The nonionic / anionic compounding ratio is preferably 0.1 or more, and more preferably 0.3 or more, from the viewpoint of detergency of the granular detergent composition.

<Cationic surfactant>
In addition to the cationic surfactant added to the component (A), a cationic surfactant can be further added to the granular detergent composition. The cationic surfactant to be blended in the granular detergent composition is the same as the cationic surfactant that can be blended in the component (A). When a cationic surfactant is blended in the granular detergent composition, it is preferably blended in an amount of 0.5 to 10 mass%, more preferably 1 to 4 mass%, in the granular detergent composition.

<Amphoteric surfactant>
Examples of amphoteric surfactants 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. When mix | blending an amphoteric surfactant with a granular detergent composition, it is preferable to mix | blend 0.5-10 mass% in a granular detergent composition, and it is preferable to mix | blend 1-4 mass%.

<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; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate (for example, manufactured by Clariant Japan Ltd.) Trade name "Na-SKS-6" (δ-Na ₂ O · 2SiO ₂ ) and other crystalline alkali metal silicates; amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride Alkali metal chlorides such as potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; crystalline aluminosilicate, amorphous aluminosilicate , Sodium carbonate and amorphous alkali metal silicate composites (eg Rhodia) Such as NABION15 (trade name)), and the like.

  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 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 10 to 30% by mass, particularly preferably 14 to 20% by mass from the viewpoint of powder properties such as cleaning performance and fluidity.

  When mix | blending potassium carbonate, the content is from the point of the effect of a solubility improvement, Preferably it is 1-10 mass% in a granular detergent composition, More preferably, it is 3-7 mass%.

  When blending an alkali metal chloride, the content thereof is preferably 0.1 to 5% by mass, more preferably 2 to 4% by mass in the granular detergent composition from the viewpoint of the effect of improving the solubility. .

  When blending the crystalline alkali metal silicate, the content thereof is preferably 1 to 30% by mass, more preferably 5 to 20% by mass in the granular detergent composition from the viewpoint of cleaning performance.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, Examples thereof include polysaccharide oxides such as cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose.

  Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000-80000, polyacrylate, acrylic acid-maleic anhydride copolymer having a weight average molecular weight of 1000-80000 And polyacetal carboxylates such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) (for example, those described in JP-A No. 54-52196) are suitable.

As for content of an organic builder, 1-10 mass% is preferable in a granular detergent composition, More preferably, it is 1-5 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 salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.

The content of the detergency builder in the granular detergent composition is preferably 10% by mass or more, more preferably 20 to 80% by mass from the viewpoint of imparting sufficient cleaning performance.
There are various grades of detergency builders available in commercial products, but these grades do not limit the use of the present invention. For example, impurities mixed in the production of commercial products and quality stability It may contain a storage stabilizer and an antioxidant added for the purpose of conversion.

<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 said fluorescent brightening agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001 to 1% by mass.

  Commercially available products of fluorescent whitening agents include Whitetex SA, Whitetex SKC (trade name) manufactured by Sumitomo Chemical Co., Ltd .; Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS- manufactured by Ciba Japan Co., Ltd. X (above, trade name); Lemonite CBUS-3B (trade name) manufactured by Khyati Chemicals and the like are preferable. Of these, chinopearl CBS-X and chinopearl AMS-GX are more preferable.

<Polymers>
In the present invention, a weight average molecular weight of 200 is used as a binder or a powder physical property adjusting agent used when densifying the granular detergent composition, or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). Polyethylene glycol having a molecular weight of ˜200000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, cellulose derivatives such as polyvinyl alcohol, hydroxypropylmethylcellulose (HPMC), and the like can be blended.
Moreover, a copolymer or terpolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol 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.
There are various grades of commercially available polymers, but these grades do not limit the use of the present invention. For example, impurities mixed during the production of the commercial products and quality stabilization It may contain a storage stabilizer and an antioxidant added for the purpose.

<Enzyme stabilizer>
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. 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.

<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, citric 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 1 to 20% by mass, more preferably 2 to 10% by mass. If it is in the said range, the effect which capture | acquires the metal ion in tap water will improve.

<PH adjuster>
The pH of the granular detergent composition is not particularly limited, but from the viewpoint of cleaning performance, the pH of the granular detergent composition in a 1% by mass aqueous solution is preferably 8 or more, and in the 1% by mass aqueous solution, More preferably, the pH 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 alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, and the like. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like.
In order to prevent the pH of the granular detergent composition from becoming too high, the pH can be adjusted to the above pH range using an acid or the like. Examples of the acid include the metal ion scavenger, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, citric acid, sodium hydrogen carbonate. , Sulfuric acid, hydrochloric acid and the like can be used.
In addition, it is also 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.

(Production method)
In the method for producing the granular detergent composition of the present invention, an oil-in-water emulsion containing an oil and fat component (a1) having a melting point of 40 ° C. or higher and a fragrance (a2) is prepared (emulsification step). After adjusting to the temperature below melting | fusing point of the said fats and oils component (temperature adjustment process), the said oil-in-water emulsion is sprayed on the said surfactant containing particle | grain (spraying process).

[Emulsification process]
In the emulsification step, for example, the component (a1) is heated to a melting point or higher and melted, and the liquid component (a2) is added to the melted component (a1). Furthermore, after adding lower alcohol as needed, a mixed solution is prepared while heating. And the method of adding the said liquid mixture to the water previously adjusted to the temperature more than melting | fusing point of (a1) component, emulsifying, stirring, and preparing the oil-in-water emulsion is mentioned.

  The apparatus used for an emulsification process is not specifically limited, The existing apparatus can be used, for example, a jet agitator (Shimadasaki Co., Ltd. make, type SJ) etc. are mentioned.

  The temperature during emulsification is preferably determined in consideration of the type of component (a1) and the type of component (a2). For example, the temperature is determined in the range from the melting point of component (a1) to 100 ° C. It is preferable.

  The particle diameter of the prepared oil-in-water emulsion is not particularly limited, and is, for example, 0.1 to 100 μm, more preferably 10 to 50 μm. The particle diameter can be measured visually by contrast with a scale using an optical microscope. This is because a strong oil-in-water emulsion can be obtained in such a state.

[Temperature adjustment process]
In the temperature adjustment step, first, surfactant-containing particles containing detergent components and the like are produced. Next, the surfactant-containing particles are adjusted to a temperature equal to or lower than the melting point of the component (a1).
For convenience of explanation, particles containing the surfactant excluding the component (B) are sometimes referred to as “detergent particles”, but the detergent particles are a concept included in the surfactant-containing particles.

  The temperature of the surfactant-containing particles in the temperature adjusting step is not higher than the melting point of the component (a1), preferably 10 ° C. or lower, more preferably 15 ° C. or lower. By setting the surfactant-containing particles to a temperature equal to or lower than the melting point of (a1), when the component (A) is sprayed onto the surfactant-containing particles, the component (a1) melts and the emulsion of the component (A) is destroyed. This is because it can be prevented.

  The surfactant-containing particles can be produced by a known production method. For example, after a part of detergent components such as surfactant and optional component (A) is dispersed and dissolved in water to form a spray drying slurry, the spray drying slurry is spray dried to form spray dried particles. To do. The remainder of the detergent component is added to the spray-dried particles, and kneading, granulation, compression molding or the like is performed to obtain surfactant-containing particles. In addition, for example, the surfactant and optional components excluding component (A) are subjected to kneading, extrusion, stirring granulation, rolling granulation, etc., and subjected to kneading, granulation, compression molding, and the like. Accordingly, the surfactant-containing particles having a desired form can be obtained by pulverization or the like.

The component (B) can be included in the surfactant-containing particles by being used together with other surfactants and the like in an apparatus such as kneading / extrusion, stirring granulation, and rolling granulation. In addition, for example, after the detergent components other than the components (A) and (B) are subjected to kneading / extrusion, stirring granulation, tumbling granulation and the like to obtain detergent particles, The component B) may be added to the detergent particles by spraying or the like to form surfactant-containing particles. As the method for adding the component (B), any of the above methods can be used, and among them, the method of adding the component (B) by spraying it onto the detergent particles is preferable. Since the component (B) is present on the surface of the surfactant-containing particles by such an addition method, the component (A) is stably adsorbed to the surfactant-containing particles via the component (B). It is.
When the component (B) is sprayed onto the detergent particles, the component (B) is preferably sprayed as an aqueous liquid, and the water content in the aqueous liquid is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. 5-10 mass% is further more preferable. When the water content is less than the above lower limit, the nonionic surfactant of the component (B) acts directly on the component (A) to easily break the emulsion, so that the fragrance persistence may be insufficient. is there. When the above upper limit is exceeded, the blending ratio of the detergent components in the granular detergent composition is lowered, and there is a risk of inducing problems such as solidification during storage of the granular detergent composition.

The spray drying method is not particularly limited, and a known method can be used. For example, it can be produced using a spray drying tower. The spray drying tower may be a countercurrent type or a cocurrent type, and among them, a countercurrent type is preferable because thermal efficiency and spray-dried particles can be sufficiently dried. Examples of the atomizer for the slurry for spray drying include a pressure spray nozzle, a two-fluid spray nozzle, and a rotary disk type. Among them, it is preferable to use a pressure spray nozzle that can easily obtain a desired average particle diameter.
Here, the “pressure spray nozzle” includes all nozzles used when spraying and atomizing the slurry for spray-drying from the spray port of the nozzle by applying pressure. Among these, a nozzle having a structure in which the slurry for spray drying is guided from one or a plurality of inlets of the nozzle to the spiral chamber in the nozzle and sprayed from the spray port as a swirling flow in the spiral chamber is particularly preferable. As a pressure at the time of spraying, 2-4 MPa (gauge pressure) is preferable, More preferably, it is 2.5-3 MPa (gauge pressure).

When obtaining spray-dried particles, a high-temperature gas is supplied into the spray-drying tower at the time of spray-drying the slurry for spray-drying. This hot gas is supplied from, for example, the lower part of the spray drying tower and discharged from the top of the spray drying tower. The temperature of the high-temperature gas is preferably 170 to 300 ° C, and more preferably 200 to 280 ° C. If it is this range, the slurry for spray-drying can fully be dried, and the spray-drying particle | grains of desired moisture content can be obtained easily.
Moreover, it is preferable that the temperature of the gas discharged | emitted from a spray-drying tower is 70-125 degreeC normally, and it is more preferable that it is 70-115 degreeC.
In addition, when high temperature gas is supplied from the lower part of a spray-drying tower and discharged | emitted from the tower top of a spray-drying tower (countercurrent type), in order to suppress that the temperature of the spray-dried particle obtained becomes too high, it sprays. Cold air can be supplied from the bottom of the drying tower. At the same time, for example, inorganic fine particles (such as zeolite) are introduced from the lower part of the spray drying tower and brought into contact with the spray drying particles, thereby preventing the adhesion of the spray drying particles to the inner wall of the spray drying tower. It becomes easy to improve the fluidity of the spray-dried particles.

  The method of adjusting the temperature of the surfactant-containing particles is not particularly limited. For example, the temperature may be adjusted by allowing the particles to stand at room temperature for an arbitrary time, or air at an arbitrary temperature while flowing in a rotary drum. To adjust the temperature.

  As a method of spraying the component (B) on the detergent particles, a known method can be used. For example, the detergent particles are put into a horizontal cylindrical rolling mixer, and while rotating the cylinder, the component (B) is sprayed onto the detergent particles, and the surface active activity is achieved by attaching the component (B) to the surface of the detergent particles. Agent-containing particles can be obtained.

  The amount of water in the surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and 6 to 8% from the viewpoint of solubility and storage stability. Is most preferred.

The average particle size of the surfactant-containing particles is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 300 to 700 μm. This is because when the average particle size is within the above range, the solubility is excellent.
Although the bulk density of the surfactant-containing particles is not particularly limited, for example, it is preferably determined in the range of 0.6 to 1.2 kg / L, and more preferably 0.8 to 1.0 kg / L.

[Spraying process]
The spraying process is a process of spraying the component (A) onto the surfactant-containing particles whose temperature has been adjusted in the temperature adjusting process to obtain a granular detergent composition.
(A) The method of spraying a component is not specifically limited, A well-known method can be used. For example, the surfactant-containing particles are placed in a horizontal cylindrical rolling mixer, and while the cylinder is rotated, the component (A) is sprayed onto the surfactant-containing particles, and the surface of the surfactant-containing particles (A) The method of attaching a component and obtaining a granular detergent composition is mentioned. At this time, the zeolite for surface coating of the surfactant-containing particles can be flowed together with the surfactant-containing particles, and the component (A) can be sprayed. Minerals with high oil absorption performance, such as zeolite, have the characteristic of incorporating a large amount of component (A). Therefore, from the viewpoint of adding a large amount of component (A), it is preferable to use zeolite in combination in the spraying step.

  Or you may perform a spraying process together with the spraying to the detergent particle | grains of (B) component at the time of manufacturing surfactant-containing particle | grains in a temperature control process. That is, the granular detergent composition can be obtained by spraying the component (A) and the component (B) on the flowing detergent particles. At this time, the temperature of the detergent particles is set to be equal to or lower than the temperature of the melting point of the component (a1). The order of spraying the component (A) and the component (B) is not particularly limited, but from the viewpoint of the stability of the emulsion of the component (A), the component (B) is obtained by spraying the detergent particles. It is preferable to spray the component (A) on the surfactant-containing particles. When (A) component and (B) component are sprayed simultaneously on the detergent particles, or (B) component is sprayed after spraying (A) component, the contact frequency between (A) component and (B) component Becomes higher, and the emulsion of component (A) becomes fragile. When the emulsion of the component (A) is broken, the release of the fragrance is promoted and the fragrance persistence of the washing object is lowered. Therefore, it is preferable to spray the component (A) after spraying the component (B). By spraying the surfactant-containing particles in a state in which the component (B) is appropriately impregnated by this spraying sequence, the component (A) is moderately suppressed in contact frequency with the component (B). And adsorbing to the surfactant-containing particles while maintaining the formation of the emulsion.

When a perfume that is not in the form of an oil-in-water emulsion is added to a surfactant-containing particle, the surfactant-containing particle is generally alkaline. There is a risk. As described above, in the present invention, since the fragrance is added to the surfactant-containing particles as the component (A) which is an oil-in-water emulsion to form a granular detergent composition, the form of the oil-in-water emulsion is used as the wall material of the fragrance. It acts to prevent the perfume from coming into direct contact with the surfactant-containing particles. For this reason, the stable fragrance | flavor of a fragrance | flavor can be obtained.
In addition, by using an oil and fat component having a melting point of 40 ° C. or higher as the component (A), it is possible to control the release of the aroma and to impart a highly durable aroma to the object to be washed.
Furthermore, the surfactant-containing particles having a high bulk density have a dense structure and low oil absorption compared to particles having a low bulk density such as spray-dried particles. For this reason, even if it is going to add the fragrance | flavor made into the oil-in-water emulsion simply to surfactant-containing particle | grains with a high bulk density, this oil-in-water emulsion is hard to be adsorbed by the high bulk density detergent particles. In the present invention, by using an oil and fat component having a melting point of 40 ° C. or higher as the component (A), the component can be fixed even if the contact point with the surfactant-containing particles is minute. For this reason, a sufficient quantity of a fragrance | flavor can be mix | blended with a granular detergent composition. In addition, since it contains a non-ionic surfactant of HLB13 or higher having relatively low lipophilicity, a sufficient amount of the oil-in-water emulsion can be added in a stable state without breaking the emulsion of the oil-in-water emulsion.

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

(Raw material)
-Paste containing α-sulfo fatty acid alkyl ester salt (manufactured by Lion Corporation)
Composition: Fatty acid chain length; carbon number 16/18, mass ratio 8/2, active ingredient 63%, nonionic surfactant (nonionic surfactant A described later) 16%, impurities 8 such as di-salt and methyl sulfate %, Moisture 13%
・ Sodium carbonate: grain ash (manufactured by Soda Ash Japan)
・ Fluorescent agent: Chino Pearl CBS-X (Ciba Japan Co., Ltd.)
・ Potassium hydroxide: flake caustic potash (Asahi Glass Co., Ltd.)
-Linear alkylbenzene sulfonate potassium (LAS-K): Linear alkylbenzene sulfonic acid (LAS-H, manufactured by Lion Corporation, Lipon LH-200, AV value (potassium hydroxide required to neutralize 1 g of LAS-H) mg number) = 180.0) neutralized with a 48 mass% potassium hydroxide solution in a slurry for preparing spray-dried particles.
Acrylic acid / maleic acid copolymer salt (MA agent): AQUALIC TL-400 (manufactured by Nippon Shokubai Co., Ltd., pure 40% by mass aqueous solution)
Nonionic surfactant A (nonionic A): an average of 15 moles of ethylene oxide adduct of alcohol having an alkyl group having 12 to 16 carbon atoms (trade name; CO-1214, manufactured by Procter & Gamble Chemicals) (pure Min 90%, HLB; 15.1-15.6)
Nonionic surfactant B (nonionic B): an average of 10 moles of ethylene oxide adduct of alcohol having an alkyl group having 12 to 16 carbon atoms (trade name; CO-1214, manufactured by Procter & Gamble Chemicals) (pure Min 90%, HLB; 13.5-14.1)
Nonionic surfactant C (nonionic C): average 7 mol of ethylene oxide adduct of alcohol having 12 to 16 carbon atoms (trade name; CO-1214, manufactured by Procter & Gamble Chemicals) (pure Min 90%, HLB; 11.5-12.5)
・ A-type zeolite: Shilton B (Mizawazawa Chemical Co., Ltd., pure content 80%)
・ Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)
・ Sodium sulfate: neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Kasei Co., Ltd.)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12; 11.7%, C14; 0.4%, C16; 29 0.2%, C18F0 (stearic acid); 0.7%, C18F1 (oleic acid); 56.8%, C18F2 (linoleic acid); 1.2%, molecular weight: 289)
・ Enzyme: Protease (sabinase 12T) / Ripase (LIPEX100T) (trade name, manufactured by Novozymes Japan Ltd.) = 8.2 (mass ratio) ・ Oil component 1-octadecanol (stearyl alcohol) ..Melting point 58 ° C
1-docosanol (behenyl alcohol) mp 70.5 ° C
Stearic acid: Melting point 69.6 ° C
1-tetradecanol (myristyl alcohol): melting point 37.9 ° C.
1-dodecanol (lauryl alcohol): melting point 24 ° C.
・ Ethyl alcohol (95% synthetic alcohol, Nippon Synthetic Alcohol Co., Ltd.)
-Isotridecyl ether EO 60 mol adduct: EO3 mol adduct of isotridecyl alcohol (trade name; Rutensol TO3, manufactured by BASF Japan Ltd.) 57 mol of EO-C22 monoalkyl cation: behenyltrimethylammonium chloride (Product name: Arcard 22-80, manufactured by Lion Akzo Corporation)
Fragrance: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]

(Evaluation methods)
About the granular detergent composition obtained by the Example and the comparative example, the residual fragrance property was evaluated by the method shown below.
[Preprocessing]
Cotton towel (Toshin Co., Ltd., 220cm border soft FT) 1kg, two tub type washing machine (product name: CW-C30A1-H1 type, manufactured by Mitsubishi Electric Co., Ltd.) is used, and tap water at 50 ° C is used. Standard usage concentration of commercially available detergent top (manufactured by Lion Corporation) (detergent top 20 g, ie 667 mass ppm with respect to 30 L of tap water), bath ratio (ratio represented by mass of washing water / mass of washing object) After 30 times, the washing and dehydrating operation of “15 minutes washing, 5 minutes dehydration” was repeated twice, and then the “15 minutes running water rinsing, 5 minutes dehydration” rinsing and dehydration operations were repeated 5 times. Pretreatment was performed by hanging and drying at room temperature.
B. V. The same pretreatment was applied to 1 kg of D skin shirt (round neck short sleeve T-shirt, product number G0134TS).

[Cleaning treatment]
A fully automatic electric washing machine (product name: JW-Z23A, manufactured by Haier) 2 pre-treated cotton towels (71 g / sheet) and B. V. Three D-skin shirts (140 g / sheet) (total of 562 g, hereinafter collectively referred to as “clothes”) were introduced. Next, using tap water with a water temperature of 20 ° C., the bath ratio is 21 times (low water level: 12 L), and the concentration of the granular detergent composition is 833 mass ppm (10 g of granular detergent composition with respect to 12 L of tap water). The cloths were washed in the same bath according to a normal course of a washing machine. After the washing treatment, it was hung and dried in a room (a room adjusted to a temperature of 20 ° C. and a humidity of 40% RH) and dried overnight (about 12 hours).

[Evaluation of residual fragrance]
Cotton towels immediately after washing and drying (washing up), and cotton towels that have passed for one week in the room (temperature: 20 ° C, humidity: adjusted to 40% RH) after washing and drying A sensory test was conducted by 10 professional panelists according to the following 6-step odor intensity method, and the average value of the evaluations of 10 people was evaluated according to the following evaluation criteria (× to ◎). In Table 2, the numerical values described in the evaluation of residual fragrance are average values of 10 panelists.

<6-step odor intensity method>
5 points: intense odor 4 points: strong odor 3 points: odor that can be easily detected 2 points: weak odor that tells what odor it is 1 point: odor that can finally be detected 0 points: odorless

<Evaluation criteria>
◎: 2.5 points or more ○: 2 points or more and less than 2.5 points △: 1 or more and less than 2 points ×: less than 1 point

(Measurement of bulk density)
The bulk density of the spray-dried particles and the granular detergent composition was measured according to JIS K3362-1998.

(Measurement of average particle size)
The average particle size of the spray-dried particles and the granular detergent composition was measured by a classification operation using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked on a saucer in the order of a sieve with a large opening, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, a lid is put on and a low-tap sieve shaker (Iida Seisakusho, Tapping: 156 times / minute, Rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and tray was collected for each sieve.
By repeating this operation, 1410 to 1680 μm (1410 μm on), 1190 to 1410 μm (1190 μm on), 1000 to 1190 μm (1000 μm on), 710 to 1000 μm (710 μm on), 500 to 710 μm (500 μm on), 350 to 500 μm (350 μm on), 250 to 350 μm (250 μm on), 149 to 250 μm (149 μm on), dish to 149 μm (149 μm pass), each classified particle size sample was obtained, and mass frequency (%) was calculated.
Next, the opening of the first sieve with a calculated mass frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the integration of the mass frequency from the tray to the sieve of a μm is c %, And the weight frequency on the a μm sieve was d%, and the average particle diameter (mass 50%) was determined by the following formula (1).

(Production Example 1) Preparation of spray-dried particles According to Table 1, each component (excluding 2% by mass equivalent of zeolite A as a coating agent for spray-dried particles) was put into a reactor having a stirrer and a jacket, and was put into water. Dissolved and dispersed (agitator jacket temperature 75 ° C.) to prepare a slurry for spray drying having a solid content concentration of 60% by mass.
Next, using a counter-current drying tower, the spray-drying slurry is spray-dried under the following conditions, and a part of the A-type zeolite (2% by mass equivalent) is introduced into the lower part of the spray-drying tower as a coating agent for the spray-dried particles. As a result, spray-dried particles were obtained.
・ Spray dryer: counter-current type, tower diameter 2.0m, effective length 5.0m
・ Atomization method: Pressurized nozzle method ・ Spraying pressure: 30 kg / cm ²
・ Hot air inlet temperature: 250 ℃
-Hot air outlet temperature: 100 ° C
The average particle diameter of the obtained spray-dried particles was 300 μm, the bulk density was 0.3 kg / L, and the water content was 5% by mass.
The moisture content (mass%) in the spray-dried particles was measured with a Kett moisture meter (trade name, manufactured by Ketto Scientific Laboratory; infrared moisture meter). The measurement conditions were 170 ° C. and 20 minutes.

Example 1
[Production of component (A)]
As the component (a1), 1-docosanol was heated to a temperature higher than its melting point to form a liquid. To 50 g of liquid 1-docosanol, 100 g of liquid fragrance composition A was added as component (a2) to prepare a liquid mixture of 1-docosanol and fragrance composition. Furthermore, 50 g of ethyl alcohol and 25 g of isotridecyl ether EO 60 mol adduct were mixed as a mixture and heated to 70 ° C. to prepare a mixed solution. This mixed solution was emulsified and dispersed in 425 g of ion-exchanged water preheated to the melting point of 1-docosanol. For emulsification and dispersion, a jet agitator (Shimasaki Manufacturing Co., Ltd., type SJ) was used, and the mixture was stirred under the condition of a rotational speed of 1000 rpm. This emulsion was allowed to stand as it was and slowly cooled to room temperature to obtain component (A) of an oil-in-water emulsion.

[Manufacture of detergent particles]
71.1 parts by mass of the spray-dried particles obtained in Production Example 1, 15 parts by mass of α-sulfo fatty acid alkyl ester salt-containing paste, 2 parts by mass of nonion A, and 0.5 parts by mass of water were continuously kneaded (Kurimoto Corporation) And then kneaded (kneader rotational speed 135 rpm, water temperature in jacket: jacket inlet; 5 ° C., outlet; 25 ° C.) to prepare a dough-like product. The temperature of the resulting dough was 55 ± 15 ° C.
Next, the obtained dough-like product is put into a pelleter double (EXD-100 type, manufactured by Fuji Powder Co., Ltd.) and extruded from a die having a hole diameter of about 10 mm and a thickness of 10 mm, and simultaneously cut (perimeter of the cutter of the pelleter). Speed: 5 m / s), a pellet-shaped molded body (diameter: about 10 mm, length: 5-70 mm) was obtained.

Fitzmill (manufactured by Hosokawa Micron Corporation, manufactured by adding 6.5 parts by mass of A-type zeolite as a grinding aid to three-stage series in the presence of air blown to 89.8 parts by mass of the obtained pellet-shaped molded body. DKA-6 type) was used to obtain detergent particles. The grinding conditions were as follows. The obtained detergent particles had a temperature of 30 ± 10 ° C., an average particle size of 350 μm, and a bulk density of 0.85 kg / L.
・ Blower temperature: 15 ± 3 ℃
・ Blowing rate (gas / solid ratio): 2.8 ± 0.25 m ³ / kg
・ Screen diameter: 6mm, 4mm, 2mm from the top
・ Crusher rotation speed: 100% = 4700 rpm (circumferential speed about 60 m / s)
・ Processing speed: 230kg / h

[Production of granular detergent composition]
The obtained detergent particles 95.1 parts by mass, enzyme 1 part by mass and surface coat A-type zeolite 2.5 parts by mass were simultaneously charged into a container rotating cylindrical mixer and rotated into fluidized detergent particles. On the other hand, 1.2 parts by weight of nonion A as component (B) was sprayed to obtain surfactant-containing particles. While the surfactant-containing particles were fluidized in a container-rotating cylindrical mixer, 0.2 parts by mass of component (A) was sprayed onto the surfactant-containing particles to obtain a detergent composition (average particle size: 360 μm). , Bulk density: 0.85 kg / L). The temperature of the detergent particles and the surfactant-containing particles was 30 ± 10 ° C., that is, the temperature of the melting point of 1-docosanol as the component (a1). About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Example 2)
A granular detergent composition was obtained in the same manner as in Example 1 except that nonion A blended with the detergent particles and nonion A sprayed onto the surfactant-containing particles were changed to nonion B. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Example 3)
(A1) A granular detergent composition was obtained in the same manner as in Example 1 except that 1-octadecanol was used. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

Example 4
A granular detergent composition was obtained in the same manner as in Example 2 except that the component (a1) was changed to 1-octadecanol. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Example 5)
A granular detergent composition was obtained in the same manner as in Example 1 except that the 60 mol adduct of isotridecyl ether EO in the component (A) was changed to a C22 monoalkyl cation. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Example 6)
A granular detergent composition was obtained in the same manner as in Example 1 except that the 60 mol adduct of isotridecyl ether EO in the component (A) was not added. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Example 7)
A granular detergent composition was obtained in the same manner as in Example 1 except that the component (a1) was stearic acid. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Comparative Example 1)
A granular detergent composition was obtained in the same manner as in Example 1 except that Nonion A blended with the detergent particles and Nonion A sprayed onto the surfactant-containing particles were changed to Nonion C. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Comparative Example 2)
(A1) A granular detergent composition was obtained in the same manner as in Example 1 except that 1-tetradecanol was used as the component. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

(Comparative Example 3)
(A1) A granular detergent composition was obtained in the same manner as in Example 1 except that 1-dodecanol was used as the component. About the obtained granular detergent composition, residual fragrance property evaluation was performed and the result is shown in Table 2.

In Table 2, “◯” in the terms of the component (A) and the component (B) indicates that the component is added.
In each of Examples 1 to 7 and Comparative Examples 1 to 3, the remaining fragrance after washing was good. In addition, in Examples 1 to 7, the residual fragrance after one week of washing was ○ to ◎ (average value was 2.0 or more). Among them, Examples 1 and 3 in which Nonion A (EO 15 mol adduct, HLB 15.1 to 15.6) was used as the component (B) and a nonionic surfactant or a cationic surfactant was added to the component (A). In Nos. 5 and 7, the residual fragrance after one week of washing was excellent (average value of 2.5 or more), which was particularly good. On the other hand, in each of Comparative Examples 1 to 3, the residual fragrance after one week of washing was Δ (average value is 1 or more and less than 2). From this, it was found that the granular detergent composition of the present invention can impart a long-lasting fragrance to the object to be washed. In Examples 1 to 7, the scent quality was good after washing and after one week of washing.

Claims (3)

  A granular detergent composition comprising an oil-in-water emulsion containing an oil and fat component having a melting point of 40 ° C. or higher and a fragrance, and a nonionic surfactant having an HLB of 13 or higher, and having a bulk density of 0.6 kg / L or higher The granular detergent composition characterized by the above-mentioned.   The granular detergent composition according to claim 1, wherein the oil-in-water emulsion contains a nonionic surfactant and / or a cationic surfactant.   An oil-in-water emulsion containing an oil / fat component having a melting point of 40 ° C. or higher and a fragrance is prepared, and the surfactant-containing particles are adjusted to a temperature below the melting point of the oil / fat component, and then the oil-in-water emulsion is treated with the surface active agent. 3. The method for producing a granular detergent composition according to claim 1 or 2, wherein the agent-containing particles are sprayed.