JP5211376B2 - Granular detergent composition for clothing - Google Patents

Description

  The present invention relates to a granular detergent composition suitable for textile products such as clothing. Specifically, the present invention relates to a granular detergent composition in which a textile product is hardly yellowed even after repeated washing.

“Welding” occurs in clothing and the like while repeatedly washing and using textile products such as clothing in daily life. Yellowing is caused by deterioration of sebum remaining in the fiber product, iron in tap water adsorbed on the fiber product, or fluorescent whitening agent remaining in the fiber product decomposed by ultraviolet rays, etc. It is thought to be due to various factors. Among them, it is widely known that yellowing due to sebum degradation is a particular problem (Patent Document 1).
As a yellowing suppression technique, use of a bleaching agent to reduce sebum accumulation in clothing (Patent Document 2), and a method of causing a coating agent to prevent contact with dirt on the fiber surface (Patent Document 3) There is. However, the yellowing suppression effect by these methods was not fully satisfactory.

JP 2001-139987 A JP 2005-29587 A JP 2003-301376 A

  Accordingly, an object of the present invention is to provide a granular detergent composition that prevents yellowing of a textile product even after repeated washing.

As a result of intensive studies by the present inventors, it was found that the above object can be achieved by using a specific anionic surfactant in combination and further adding a specific plant extract.
That is, the present invention
(A) α-sulfo fatty acid alkyl ester salt,
(B) a higher fatty acid salt having 10 to 20 carbon atoms, and
(C) Selected from the group consisting of γ-oryzanol, hornon extract, horsetail extract, hop extract, pine extract, lemon extract, rosemary extract, asparagus linen ali extract, oolong tea extract, hypericum extract, button extract, eucalyptus extract and sage extract One or more plant extracts,
A granular detergent composition is provided.

  According to the present invention, it is possible to effectively prevent the textile product from being yellowed even after repeated washing. According to the present invention, it is also possible to suppress odor generated due to yellowing.

(A) α-sulfo fatty acid ester salt The α-sulfo fatty acid alkyl ester salt used in the present invention is represented by the following formula (A-1). It is particularly effective for removing sebum dirt.

In the formula, R ¹ is a linear or branched, preferably linear alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 16 carbon atoms,
R ² is a linear or branched group having 1 to 6 carbon atoms, preferably a linear alkyl or alkenyl 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, for example, alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like, among which alkali metal salts, particularly sodium or potassium are preferred. .
If the carbon number of R ¹ is less than 6 or more than 20, the detergency may be inferior.
Particularly preferred as a) is a compound in which R ¹ is a linear or branched alkyl group or alkenyl group having 12 to 16 carbon atoms and R ² is a methyl group.

In the present invention, the α-sulfo fatty acid alkyl ester can be used singly or as a mixture of two or more. A mixture is preferred. In particular, in the above formula, R ¹ is a linear or branched alkyl group or alkenyl group having 14 carbon atoms and R ² is a methyl group, and in the above formula, R ¹ is a straight chain having 16 carbon atoms or A mixture with a compound which is a branched alkyl group or an alkenyl group and R ² is a methyl group, or in the above formula, R ¹ is a linear or branched alkyl group or alkenyl group having 12 carbon atoms There, a compound wherein R ² is a methyl group, R ¹ in the above formula is a straight-chain or branched alkyl group or alkenyl group having 14 carbon atoms is a mixture of compounds wherein R ² is a methyl group Is preferred.
The α-sulfo fatty acid alkyl ester salt used in the present invention can be produced by a known method, or a commercially available product can be used. The α-sulfo fatty acid ester salt includes an α-sulfo fatty acid salt as a by-product.
From the viewpoint of detergency, the α-sulfo fatty acid ester salt is preferably contained in an amount of 5 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the composition.

(B) Higher fatty acid salt having 10 to 20 carbon atoms The higher fatty acid salt used in the present invention exhibits an effect of preventing yellowing when used in combination with a plant extract. Specifically, 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 a sodium or potassium salt. can give. The fatty acid may be saturated or unsaturated. 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. A mixture of a saturated fatty acid and an unsaturated fatty acid having the same or different chain length may be used. A mixture of a saturated fatty acid having 12 to 18 carbon atoms and an unsaturated fatty acid having 18 carbon atoms is preferable. The higher fatty acid salt used in the present invention can be produced by a known method, or a commercially available product can be used.
Even if there are too many fatty acid salts, the solubility tends to deteriorate, which is not preferable. From the viewpoint of solubility, the content of the higher fatty acid salt having 10 to 20 carbon atoms is preferably less than 10% by mass, more preferably 1 to 9% by mass, based on the total mass of the composition. preferable.

(C) Plant extract The plant extract is an ethanol solution containing ethanol, propylene glycol, diethylene glycol, 1,3-butylene glycol, glycerin, and 0.5 to 3% urea as an extraction solvent from a specific plant described later. Obtained by extraction using a hydrophilic organic solvent selected from the group consisting of 1,3-butylene glycol solution containing 0.5 to 3% urea and a mixture thereof, water, or a mixture of hydrophilic solvent and water. It is done.
γ-Oryzanol can be obtained from the seed coat of rice Oryza sativa Linne (Gramineae) using n-hexane as an extraction solvent or by a critical extraction method using carbon dioxide. It consists mainly of ferulic acid ester of triterpene alcohol. The dried product contains 95.0% or more of cycloartenyl ferulate when quantified. Specific examples of commercially available products of γ-oryzanol of 0.5% or less as the ignition residue include Oriza Gamma V, Oriza Gamma Milky, etc. from Oriza Oil Chemical Co., Ltd.

Ougon extract is obtained from the roots excluding the pericarp of Scutellaria baicalensis Georgi (Labiatae). A preferred extraction solvent is water, ethanol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercially available products of Ogon Extract include Ougon Falcos Ougon Extract Powder, Ogon Liquid B, Ogon Liquid SE, Maruzen Pharmaceutical Ougon Extract-J, Ougon Extract-BG-JC, Ogon Extract SQ, Ogon Extract BG-50 from Koei Kogyo Co., Ltd.
Horsetail extract is obtained from the whole plant of Horsetail Equisetum arvense Linne (Equisetaceae). A preferred extraction solvent is water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof, or a 1% urea-containing ethanol solution or a 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercial products of Sugina extract include Falco Rex Sugina B, Falco Rex BX46, Falco Rex BX 50, Ichimaru Falcos Co., Ltd., Sugina Extract, Sugina Extract BG, Sugina Extract LA, Maruzen Pharmaceutical Co., Ltd. Koei Kogyo Co., Ltd. too much extract, mixed plant extract (1), mixed plant extract (11), mixed plant extract (13), mixed plant extract (15), mixed plant extract (21 ), Mixed plant extract (22) and the like.

The hop extract is obtained from female spikelets of hops Humulus lupulus Linne (Moraceae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercial hop extract products include Ichimaru Falcos' Hop Liquid, Falco Rex BX46, Falco Rex BX 52, Maruzen Pharmaceutical's Hop Extract, Hop Extract BG-JN, and Koei Kogyo Co., Ltd. ) Hop extract, hop extract HS, and the like.
Pine extract is obtained from the cone of Pinus sylvestris Linne (Pinaceae). Preferable extraction solvents are water, propylene glycol, 1,3-butylene glycol, glycerin or a mixture thereof, 1% urea-containing ethanol solution, 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercially available pine extract include Falco Rex Pine B, Falco Rex BX32, Falco Rex BX46, mixed plant extract (2) from Koei Kogyo Co., Ltd., etc.
Lemon extract is obtained from the fruit (raw) or fruit juice of lemon Citrus limon Burmann fil (Rutaceae). Preferred extraction solvents are water, propylene glycol, 1,3-butylene glycol, glycerin or a mixture thereof. Specific examples of lemon extract commercial products include Lemon Extra Liquid from Ichimaru Falcos, Falco Rex BX46, Falco Rex BX47, Falco Rex BX52, Lemon Extract BG-J from Maruzen Pharmaceutical Co., Ltd., Koei Kogyo ( Lemon extract, mixed plant extract (5) and the like.

Rosemary extract is obtained by extracting the leaves of Rosemary Rosmarinus officinalis L. with 80% ethanol, concentrating under reduced pressure, and dissolving the crystal part precipitated by centrifugation with 95% ethanol, dipropylene glycol or a mixture thereof. The resulting extract. As a specific example of a commercially available product of rosemary extract, Rosemary 80% ethanol extract of Toyoda Fragrance Co., Ltd. and the like can be mentioned.
The Asparagus Linea Aris extract is obtained from the whole plant of Aspalathus linearis (NLBurm.) R. Dahlgren (Leguminosae). A preferred extraction solvent is 1,3-butylene glycol. As a specific example of a commercially available product of Asparasas rinealis extract, there is Falco Rex Robos B (N) from Ichimaru Falcos Co., Ltd.
Oolong tea extract is obtained from leaves of the tea tree Thea sinensis Linne (Theaceae). A preferred extraction solvent is ethanol. Specific examples of commercially available oolong tea extract include Falco Rex Oolong E from Ichimaru Falcos Co., Ltd., Oolong Tea Extract from Maruzen Pharmaceutical Co., Ltd., and Oolong Tea Extract BG.

Hypericum extract is obtained from the above-ground part of Hypericum perforatum Linne or Hypericum erectum Thunberg (Guttiferae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol, diethylene glycol or a mixture thereof. Specific examples of commercially available hypericum extract include Falco Rex Hypericum B, Falco Rex Hypericum E, Falco Rex BX43, Falco Rex BX44, Falco Rex BX52, and Hypericum Extract from Maruzen Pharmaceutical Co., Ltd.-J , Hypericum extract-BG, Hypericum extract of Koei Kogyo Co., Ltd., mixed plant extract (3), mixed plant extract (6), mixed plant extract (21), mixed plant extract (22), etc. Is mentioned.
The button extract is obtained from the root bark of the button Paeonia suffruticosa Andrews (Paeonia moutan Sims) (Paeoniaceae). A preferred extraction solvent is ethanol. An extract showing 0.5 w / v% or less as an ignition residue. Specific examples of commercially available button extracts include Falco Rex Buttonpi B, Falcolex Buttonpi E, Falcolex HGL, Falcolex PSP, Phyto desensitizer ABBA, Phyto Blend TIPS, Maruzen Pharmaceutical Co., Ltd. And button pi extract from Koei Kogyo Co., Ltd.

Eucalyptus extract is obtained from leaves of Eucalyptus globules Labillardiere or other related plants (Myrtaceae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercially available eucalyptus extracts include Falco Rex Eucalyptus B from Ichimaru Falcos, Falco Rex Eucalyptus E, Eucalyptus Extract BG from Maruzen Pharmaceutical Co., Ltd., Eucalyptus Extract BG, Eucalyptus from Koei Kogyo Co., Ltd. An extract, Eucalyptus extract S, etc. are mentioned.
Sage extract is obtained from flowers, leaves or whole grass of sage Salvia officinalis Linne (Labiatae). A preferred extraction solvent is water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof, 1% urea-containing ethanol solution, or 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercially available sage extracts include Falco Rex Sage B, Falco Rex Sage E, Falco Rex BX47, Falco Rex BX 52 from Ichimaru Falcos, Organic Sage Extract BG-50 from Koei Kogyo Co., Ltd., and Salvia Extract, Salvia extract HS, mixed plant extract (5), mixed plant extract (11), mixed plant extract (13), mixed plant extract (21), mixed plant extract (22), etc. It is done.
These plant extracts are preferably blended in the composition in an amount of 0.001 to 5% by weight, more preferably 0.1 to 5% by weight. If it exceeds 5% by weight, the original fragrance of the fragrance may be adversely affected.

[Optional ingredients]
<Surfactant>
The composition of this invention can further contain the component normally mix | blended with the granular detergent composition for garments. Examples of such components include the following.

<Anionic surfactant>
The composition of the present invention may further contain the following anionic surfactant in addition to the above (A) and (B).
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) 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.
(6) 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.
(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 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.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) 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.

<Nonionic surfactant>
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms 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. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether (3) Fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (I) in which alkylene oxide is added between ester bonds of long chain fatty acid alkyl ester
R1CO (OA) nOR2 (I)
(In the formula, R 1 CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably 2 to 3 carbon atoms. N represents the average number of moles of alkylene oxide added and is generally a number of 3 to 30, preferably 5 to 20. R2 is a lower group which may have a substituent of 1 to 3 carbon atoms ( C1-4 represents an alkyl group.)
(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 the nonionic surfactants described above, the nonionic surfactant (1) described above is preferable, and in particular, an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 12 to 16 carbon atoms. Added polyoxyalkylene alkyl (or alkenyl) ethers are preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, A fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester is preferably used. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, the HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka Co-ed., “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). Year, page 234).
The melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.

<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 26 carbon atoms, preferably 14 to 18 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 polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

<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 the composition of the present invention further contains the above surfactant, the total amount of the surfactant contained in the composition of the present invention is preferably 10 to 30% by mass, and 15 to 30% by mass. Is more preferable. In such a range, a sufficient cleaning effect and yellowing suppression effect are exhibited.

<Detergency Builder>
Detergency builders include inorganic builders and organic builders.
Examples of inorganic builders 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 [eg, manufactured by Clariant Japan Ltd. Crystalline alkali metal silicates such as “Na-SKS-6” (δ-Na ₂ O · 2SiO ₂ )], 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 complex (e.g., Rhod a trade name "NABION15"), 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 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. Commercially available products manufactured by HAIXING CHEMICAL CO., LTD OF DONGYING CITY, trade name ZEOLITE 4A; manufactured by FUJIAN RISHENG CL, LTD, trade name 4A ZEOLITE; Product name 4A Zeolite, manufactured by Shanxi Yuchi Changli High-Tech Co., Ltd. Product name 4A ZEOLITE, manufactured by ALUMINUM CORPORATION OF CHINA., Ltd. Huiying Chemical Products Co., Ltd Product name 4A Zeolite; Thai Silicate Chemicals Co., Ltd. Product name Zeolite 4A Type; Cosmo (COSMO FINE CHEMICALS CO., LTD.) Product name COLITE-P; PQ Chemicals Limited Product name VALFOR 100 Zeolite NaA;
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 weight, particularly preferably 5 to 15% by weight.

  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, cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; A salt of polyacetal carboxylic acid such as polyacrylic acid, salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of acrylic acid-maleic anhydride copolymer, polyglyoxylic acid; Acrylic acid polymers, polysaccharide-acrylic acid copolymers such as acrylic acid polymers or copolymer salts; maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, etc. Or a salt of the polymer; polysaccharide oxides such as starch, cellulose, amylose, and pectin; and polysaccharide derivatives such as carboxymethyl cellulose.

Among the above organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer salt, acrylic acid-maleic anhydride copolymer salt, polyacetal Carboxylic acid salts are preferred. 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-54-52196) are suitable.
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 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 to 80% by mass and more preferably 20 to 75% by mass from the viewpoint of imparting sufficient cleaning performance.

<Bleaching agent>
As the bleaching agent, oxygen-based bleaching agents such as percarbonate such as hydrogen peroxide and sodium percarbonate, and chlorine-based bleaching agents such as sodium hypochlorite and thiourea dioxide can be used. Of these, oxygen bleaches are preferred, percarbonates are more preferred, and sodium percarbonate is most preferred. Commercial products of sodium percarbonate include SPC-D, SPC-HGD (manufactured by Mitsubishi Gas Chemical Co., Inc.); PC-NK (manufactured by Nippon Peroxide Co., Ltd.); SPCC (Zheijing Jinke Chemicals Co., Ltd.). Sodium Percarbonate (Zhejiang DC Chemical Co., Ltd.) is a suitable example.
The blending amount of the bleaching agent in the granular detergent composition is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less. If the above range is exceeded, the bleaching effect may not increase any more, and if it is less than the above range, a sufficient bleaching effect may not be obtained.

<Enzyme>
Enzymes are classified according to the reactivity of the enzyme, and include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.
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. Commercially available products include sabinase, alcalase, polarzyme, cannase, everase, deozyme (above, trade name; manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Maxacal, Maxapem (above, trade name; Genencor) A protease K-14 or K-16 (protease described in JP-A-5-25492), and the like.
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, Lipex (trade name; manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).
Examples of cellulases include commercially available cellzymes (trade names, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, 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, CMCase II, alkaline cellulase E-II, and alkaline cellulase E -III (cellulase described in JP-A-63-264699) and the like.
Examples of amylase include commercially available Termamyl and Duramil (manufactured by Novozymes).
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.

<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. 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.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001 to 1% by mass.

<Fragrance>
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) which consists 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.

<Polymers>
In the granular detergent composition of the present invention, as a binder or a powder physical property modifier used when densifying the granular detergent composition particles, or for imparting a recontamination preventing effect on hydrophobic fine particles (dirt). , Blending polyethylene glycol having an average molecular weight of 200 to 200,000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, a cellulose derivative such as polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl methyl cellulose (HPMC), etc. Can do.
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.
Among the above polymers, HPMC is preferable and HPMC having a weight average molecular weight of 20,000 or more is more preferable from the viewpoint of imparting flexibility to an object to be washed and preventing recontamination.
Such polymers can be used singly or in appropriate combination of two or more.
As for content of the said polymers in a granular detergent composition, 0.05-5 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, 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 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>
From the viewpoint of cleaning performance, the granular detergent composition of the present invention preferably has a pH of 8 or more in a 1% by mass aqueous solution of the granular detergent composition, and the pH in the 1% by mass aqueous solution is 9 to 11. More preferred. When the pH is 8 or more, the cleaning effect is easily exhibited.
The pH of the granular detergent composition is usually adjusted with an alkali agent. As the pH adjuster, in addition to the alkali agent described in the detergency builder, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, water Examples thereof include sodium oxide and potassium hydroxide. 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 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.
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.
<Surface treatment water-soluble inorganic compound particles>
As the surface-treated water-soluble inorganic compound particles, for example, the surface-treated water-soluble inorganic compound particles described on pages 3 to 25 of WO 2004/094313 are suitably used.

[Method for producing granular detergent composition]
The manufacturing method of the granular detergent composition of this invention is not restrict | limited in particular, It can manufacture with the manufacturing method generally used. The case where the granular detergent composition is in a powder form will be described as an example. For example, a method of dispersing and dissolving a surfactant and other raw materials in water and spray drying, a method of dissolving a plant extract in a perfume and spray drying Alternatively, it can be produced by a kneading, extruding, stirring granulation, rolling granulation, or the like, subjected to kneading, granulation, compression molding, or the like, and further pulverized if necessary.

The components used to prepare the granular detergent compositions of the examples and comparative examples are shown below.
(A) α-sulfo fatty acid ester salt A fatty acid ester obtained by transesterifying palm oil with methyl alcohol is fractionated, and a C16 fatty acid ester fraction and a C18 fatty acid ester fraction are mixed at a mass ratio of 8: 2. In a flow-down type thin film reactor, sulfonated with SO ₃ gas diluted with nitrogen gas at a reaction molar ratio (SO ₃ / fatty acid ester) = 1.2 and reaction temperature of 80 ° C., α-sulfo fatty acid methyl ester (Hereinafter referred to as “MES”).
Next, 30 parts by weight of methanol was introduced to 100 parts by weight of the resulting α-sulfo fatty acid methyl ester, 8.6 parts by weight of 35% hydrogen peroxide was introduced, and bleaching was performed at 80 ° C. for 60 minutes. It was.
The bleached α-sulfo fatty acid methyl ester was neutralized with an aqueous sodium hydroxide solution at a neutralization temperature of 40 to 70 ° C. so that pH = 7.
Excess methanol was then removed under reduced pressure to give an aqueous slurry of MES-Na. The MES-Na content is 66% by mass and the water content is 27% by mass. The remainder contains a small amount of by-product α-sulfo fatty acid disodium salt, unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide and the like.

(B) C10-20 higher fatty acid salt C12-18 fatty acid sodium (manufactured by Lion Corporation, pure: 67% by mass, titer: 40-45 ° 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; 289).

(C) Plant extract / γ-Oryzanol: Oriza Gamma V, oriza gamma V (100% as oryzanol)
・ Ogon Extract: Ichimaru Falcos Co., Ltd., Ogon Liquid SE (contains 1.69% as Ogon Extract)
・ Sugina Extract: Made by Ichimaru Falcos Co., Ltd., Falco Rex Sugina B (contains 1.0% as Sugina extract)
・ Hop extract: Ichimaru Falcos, Hop Liquid (contains 1.5% as hop extract)
-Pine extract: manufactured by Ichimaru Falcos Co., Ltd., Falco Rex pine B (contains 0.64% as pine cone extract or pine extract)
・ Lemon extract: Ichimaru Falcos Co., Ltd., Lemon Extra Liquid (Contains 0.65% as a lemon extract or lemon fruit extract)
・ Rosemary extract: Made by Toyoda Fragrance Co., Ltd., Rosemary 80% ethanol extract (1.0% rosemary extract)

-Asparagus linen extract: Made by Ichimaru Falcos, Falco Rex Rooibos B (N) (containing 0.5% as rooibos extract)
・ Oolong tea extract: Ichimaru Falcos Co., Ltd., Falco Rex Oolong E (contains 2.56% as Oolong tea extract)
Hypericum extract: manufactured by Ichimaru Falcos Co., Ltd., Falco Rex Hypericum E (contains 0.86% as Hypericum extract)
-Button extract: manufactured by Ichimaru Falcos, Falco Rex Buttonpi E (contains 1.1% as a button extract)
-Eucalyptus extract: Ichimaru Falcos Co., Ltd., Falco Rex Eucalyptus E (containing 0.59% as eucalyptus extract or eucalyptus leaf extract)
-Sage extract: manufactured by Ichimaru Falcos, Falco Rex Sage E (contains 0.85% as sage extract or sage leaf extract)
It was used.
The blending amount (% by mass) in the table represents the concentration as an extract.

[Optional ingredients]
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure content 96% by mass)] was prepared during the preparation of the surfactant composition. What mixed the compound neutralized with 48 mass% sodium hydroxide aqueous solution and the compound neutralized with 48 mass% potassium hydroxide aqueous solution instead of neutralizing with the said sodium hydroxide by 2: 1 mass ratio. The compounding quantity in a table | surface shows the value (mass%) as these mixtures.
Nonionic surfactant: polyoxyethylene alkyl ether (ECOROL 26 (trade name, manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) average 15-mole ethylene oxide adduct (pure content: 90% by mass))
・ Zeolite: A-type zeolite ・ Silton B (trade name, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass)
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 4
0 mass% aqueous solution)
・ Sodium percarbonate: Coated sodium percarbonate (Mitsubishi Gas Chemical Co., Ltd., product name SPC-D)
Carbonic acid K: potassium carbonate (powder) (Asahi Glass Co., Ltd .; average particle size 490 μm, bulk density 1.30 g / cm ³ )
・ Sulfuric acid Na: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Enzyme: Sabinase 12T (manufactured by Novozymes)
-Fluorescent agent: Chinopearl CBS-X (trade name, Ciba Specialty Chemicals) / Chinopearl AMS-GX (trade name, Ciba Specialty Chemicals) = 3/1 (mass ratio)-Fragrance: JP 2002-146399 A Fragrance composition A shown in Table 11 to Table 18
-Carbonic acid Na: granular ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ )

・ Surface treatment sodium carbonate particles:
85.5 parts by weight of sodium carbonate (granular ash manufactured by Asahi Glass Co., Ltd.) was added to a pro-shear mixer (Daihei Koki Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling rate 30 (Volume%), stirring was started at a main shaft of 150 rpm (chopper rotation speed: 1015 rpm, blade tip speed (peripheral speed): 6.9 m / s) 10 seconds after stirring was started, sodium salt of acrylic acid / maleic acid copolymer 7.5 parts by weight (Aquaric TL-400 manufactured by Nippon Shokubai Co., Ltd., 40% solid content aqueous solution) was added by spraying with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees for 180 seconds, and granulation and coating operations were performed.
Subsequently, 7 parts by weight of lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees while continuing to stir the plow shear mixer. Stirring was continued for 30 seconds to obtain particles.
Next, the obtained particles are filled into a fluidized bed (Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is sent into the fluidized bed, The cooling operation was performed to obtain particles cooled to 20 ° C. The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state. The obtained particles were classified using a sieve having an opening of 2,000 μm to obtain surface-treated sodium carbonate particles having an average particle diameter of 350 μm and a bulk density of 1.14 g / mL passing through a sieve having an opening of 2,000 μm.

[Method for producing granular detergent composition]
According to the composition shown in Table 1 and Table 2, the granular detergent composition was manufactured in the following process.
However, Examples 2-6 and 8-13 are reference examples .
(Manufacturing process 1)
First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this was added a surfactant (excluding MES and nonionic surfactant) (the mixing stage was referred to as “raw material input 1”) and stirred for 10 minutes. Subsequently, MA agent, sodium sulfate, and fluorescent agent were added. Further, after stirring for 10 minutes, a part of zeolite (2.0% by mass equivalent (for surfactant-containing particles, hereinafter the same)) for addition during kneading, 3.2% by mass equivalent of grinding aid And 1.5 wt% of each surface coating zeolite was removed.), Na carbonate and K carbonate were added. Furthermore, after stirring for 20 minutes to prepare a slurry for spray drying with a water content of 38% by mass, the amount of air is adjusted using a countercurrent spray drying tower at a hot air temperature of 280 ° C. Particles were obtained.

(Manufacturing process 2)
A nonionic surfactant (25% by mass with respect to MES) is added to the aqueous slurry of MES (the mixing stage is referred to as “raw material input 2”), and a thin-film dryer is used until the water content becomes 11% by mass. The mixture was concentrated under reduced pressure to obtain a mixed concentrate of MES and nonionic surfactant.
(Manufacturing process 3)
The above-mentioned spray-dried particles, the above mixed concentrate, 2.0 mass% equivalent amount of zeolite, 0.5 mass% equivalent amount of the remaining nonionic surfactant and water except for spray addition were added to a continuous kneader (Kurimoto Co., Ltd.). (Made by Kakosho, KRC-S4 type) (this mixing stage is referred to as “raw material input 3”), kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C., and kneaded with surfactant I got a thing. This surfactant-containing kneaded product was cut with a cutter while extruding it with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed was 5 m). / S), a pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.

Next, 3.2% by mass of particulate zeolite (average particle size: 180 μm) as a grinding aid is added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) Below, it grind | pulverized using the Fitzmill (Hosokawa Micron Co., Ltd. product, DKA-3) arrange | positioned in series 3 steps (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, Number of rotations: 1st stage / 2nd stage / 3rd stage is 4700 rpm) Finally, with a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum inner wall surface of the container 131.7 L, a clearance between the inner wall surface of 20 mm, and a height of 45 mm baffle plates) Addition of 1.5% by mass of finely divided zeolite under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm and 25 ° C., and a fragrance containing a plant extract obtained by mixing a fragrance and a plant extract in advance and equivalent to 0.5% by mass While spraying an amount of nonionic surfactant, it was rolled for 1 minute and surface modified to prepare a granular detergent composition.
In accordance with the composition shown in Table 1 and Table 2, sodium percarbonate, surfactant particles, surface-treated inorganic particles, and enzyme were placed in a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, container 131.7 L inside drum) Example of comparison with rolling and mixing for 1 minute under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C. An example detergent composition was obtained.

[Evaluation of yellowing prevention effect]
(1) Preparation of dirt cloth Squalene was used as sebum. Squalene dissolved in a solvent (toluene) was added to a cotton cloth (5 cm × 5 cm) so as to be 5.0% owf, and it was left to dry at room temperature.
(2) Evaluation in cleaning system Five soil cloths were put into a Terg-O-Tometer machine (manufactured by U.S. Testing Co.), and each granular detergent composition was used so that the concentration became 667 ppm, and 120 rpm Then, after stirring for 10 minutes, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation, product number: CW-C30A1-H1) and dehydrated for 1 minute. Thereafter, rinsing was performed for 3 minutes, followed by dehydration for 1 minute and natural drying. The tap water used was adjusted to 25 ° C.
After washing treatment, it was air-dried, and the soiled cloth was allowed to stand at 100 ° C. for 24 hours to promote yellowing.

(3) Yellowing degree evaluation method The b value was measured according to JIS Z 8729 according to the CIE L * a * b * color system, using a dirty cloth before and after yellowing promotion. For measurement of b value, Spectro Color Meter SE2000 of Nippon Denshoku Industries Co., Ltd. was used. The b value is a parameter belonging to the L * a * b * (Elster Aster Baster) color system, and the yellow becomes stronger as it goes in the positive direction, and the blue becomes stronger as it goes in the negative direction. The difference in b value of the soiled cloth before and after yellowing acceleration was taken and evaluated according to the following criteria. ○ If it is above, it shall have yellowing suppression effect.
<Evaluation criteria>
◎◎: Less than Δ1 (no yellowing was observed)
◎: More than Δ1 and less than Δ2 (Slight yellowing change was observed compared to pre-deteriorated clothing, but there is virtually no problem)
○: Δ2 or more and less than Δ4 (Although a slight yellowing change was observed compared to pre-deteriorated clothing, there was virtually no problem)
×: Δ4 or more (a significant change in yellowing was observed compared to pre-deteriorated clothing)

Claims (6)

(A) α-sulfo fatty acid alkyl ester salt,
(B) a higher fatty acid salt having 10 to 20 carbon atoms, and
(C) one or more plant extracts selected from the group consisting of γ-oryzanol containing 95.0% by mass or more of cycloartenyl ferulate and 80% by volume of rosemary ethanol extract ,
A granular detergent composition comprising: The granular detergent composition according to claim 1, further comprising a surfactant other than (A) and (B), wherein the total amount of the surfactant in the composition is 10 to 30% by mass . The granular detergent composition of Claim 1 or 2 which contains a plant extract 0.001-5 mass% on the basis of the whole quantity of a composition. The granular detergent composition according to any one of claims 1 to 3 , wherein (A) is a compound represented by the following formula (A-1).

(In the formula, R ¹ is a linear or branched alkyl or alkenyl group having 12 to 16 carbon atoms, R ² is a methyl group, and M represents a counter ion.) The granular detergent composition according to any one of claims 1 to 4 , wherein (B) is a higher fatty acid salt having 12 to 18 carbon atoms. ( C) is γ-oryzanol containing 95.0% by mass or more of cycloartenyl ferulate or γ-oryzanol containing 95.0% by mass or more of cycloartenyl ferulate and 80% by volume of rosemary ethanol extract The granular detergent composition according to any one of claims 1 to 5, which is a combination .