JP2014062196A - Detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for clothing exhibiting effective detergency to particle contamination, and dramatically improving inhibition effects on odors due to drying in a room.SOLUTION: A detergent composition for clothing contains (A) a compound having, in a molecule, 2 or more groups selected from a group consisting of a quaternary ammonium group and an amino group, having one or more group selected from a group consisting of an alkyl group having 8 to 36 carbon atoms and an alkenyl group having 8 to 36 carbon atoms, and (B) α-sulfo fatty acid alkyl ester and/or a soap, and a mole fraction of (A)/(B) is 0.04 to 0.5.

Description

  The present invention relates to a cleaning composition suitable for use in textiles such as clothing. More specifically, the present invention relates to a cleaning composition for clothing that exhibits an effective cleaning power against particle dirt and dramatically improves the effect of suppressing room drying odor.

In consumer surveys, representative soot stains include sock stains and collar stains. Socks stains and dark spots on the collar are dirt that contains particles of metal and carbon (hereinafter referred to as particle stains) and are difficult to remove with just a washing machine. Therefore, although pre-washing (hand washing before washing in a washing machine, washing-up washing, etc.) is generally performed on these stains, it is very time-consuming and a solution has been demanded.
In addition, bacteria are listed as invisible stains. In recent years, room-drying behavior has become common due to lifestyle changes, and countermeasures against odors such as room-drying odors have become necessary. While the environment surrounding washing has become harsh, such as increasing the capacity of washing machines, stuffing washing, and lowering the bath ratio, there has been a problem that further improvement effects are required for room drying odor, and it is not sufficient at present .

  As disclosed in Patent Document 1, attempts have been made to clean dirt such as clothing by blending a cationic surfactant into a detergent for clothing. However, when a cationic surfactant is added to a laundry detergent, it generally forms a complex with the anionic surfactant as a cleaning component, not only detergency is reduced but also the effect of the cation is not exhibited. In addition, sufficient detergency against particle contamination and sufficient room drying odor control effect could not be obtained.

JP 2003-301195 A

  Therefore, an object of this invention is to provide the cleaning composition which shows the effective cleaning power with respect to particle | grain stain | pollution | contamination, and improves a room-drying odor suppression effect dramatically.

  The present inventors use a specific cationic surfactant and a specific anionic surfactant in combination to improve the dispersibility of particle dirt such as mud and dramatically improve the effect of suppressing room drying odor. I found out. In addition, after examining the manufacturing process, in the detergent composition, by making the specific cationic surfactant and the specific anionic surfactant into a complexed state, it is possible to reduce particle contamination. It was found that the detergency and the effect of suppressing room drying odor were further improved. The present invention has been completed based on such novel findings.

The present invention
(A) From the group which has 2 or more groups chosen from the group which consists of a quaternary ammonium group and an amino group in a molecule | numerator, and consists of a C8-C36 alkyl group and a C8-C36 alkenyl group A compound having one or more selected groups, and (B) an α-sulfo fatty acid alkyl ester and / or a soap,
And a cleaning composition for clothing having a molar ratio of (A) / (B) of 0.04 to 0.5.

  According to the cleaning composition for clothing of the present invention, it is possible to exert an effective cleaning power against particle dirt and to bring about an excellent effect of suppressing room drying odor. Such an effect of the present invention is obtained by using the components (A) and (B) described in detail below, and is unexpected from the prior art.

[(A) component]
The component (A) contained in the garment cleaning composition of the present invention has two or more, more preferably two or three selected from the group consisting of a quaternary ammonium group and a tertiary amino group in the molecule. Most preferably two groups and one or more, more preferably one or two, most preferably one group selected from the group consisting of an alkyl group having 8 to 36 carbon atoms and an alkenyl group having 8 to 36 carbon atoms It is a compound which has this. In particular, a compound of the following general formula (1) is preferable.
_{R 1 - [AP] n -} [BQ] m -CR 2 · aX - (1)
[In the formula, R ₁ and R ₂ may be the same or different, and both or any one of them may be separated by an ester group or an amide group, having 8 to 36 carbon atoms, preferably 10 to 24, Particularly preferred is an alkyl group or alkenyl group having 14 to 24 carbon atoms, and the other may be an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. A, B, and C may be the same or different and each represents a group represented by —N ⁺ (R ₃ ) (R ₄ ) — or —N (R ₅ ) —. Here, R ₃ , R ₄ and R ₅ may be the same or different, and are an alkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. P and Q may be the same or different, may be separated by an ester group, an ether group or an amide group, and may be an alkylene having 1 to 5 carbon atoms which may be substituted by a hydroxy group or an ether group It is a group. a is the same number as the number of groups represented by -N ⁺ (R ₃ ) (R ₄ )-in A, B and C. n is a number from 1 to 3, preferably 1 or 2, and m is a number from 0 to 2, preferably 0 or 1. X ⁻ is an anion, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. It is 1 or more types chosen from the group which consists of the aryl sulfonate ion which may be substituted by. ]

Preferred examples of such compounds include the following compounds.

In the above formulas (I) to (VI), R _{1 to} R ₅ and X ⁻ represent the same meaning as described above, R ₆ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, or an average degree of condensation of 1 to 20 The oxyethylene group. Y is a group selected from the group consisting of —COO—, —OCO—, —CONH—, —NHCO—, and —O—. l and k are the numbers of 1-5 which may be the same or different.
In the present invention, among the above compounds, compounds represented by the formula (I), (II), (IV), (V) are preferable, and compounds represented by the formula (II) or (V) are particularly preferable.

Further, in the present invention, both or any one of R ₁ and R ₂ , preferably any one is an alkyl group or alkenyl group having 14 to 24 carbon atoms separated by an ester group or an amide group or both. Desirably, especially
R ₇ -COZ-R ₈ - and R ₇ -ZCO-R ₈ -
[Wherein, R ₇ is an alkyl or alkenyl group having 13 to 19 carbon atoms, and R ₈ is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Z represents —O— or —NH—. ]
A group selected from the group consisting of

In addition, the compound which has a tertiary amino group among the compounds of (A) component can also use what neutralized the tertiary amino group with the acid agent before mix | blending with the cleaning composition for clothes. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid and fatty acid are preferable, and hydrochloric acid and sulfuric acid are particularly preferable.
Moreover, content of (A) component is 0.1-6 mass% with respect to the total mass of the cleaning composition for clothing of this invention, Preferably it is 0.5-3 mass%, More preferably, it is 1-2 mass %. If it is in the above-mentioned range, the cleaning power can be exerted in a well-balanced manner against not only particle dirt such as mud but also various kinds of dirt other than particle dirt such as mud.

  By using the component (A), the dispersibility of dirt and the effect of suppressing room-drying odor when used in combination with the component (B) are improved. The reason for improving the air-drying odor control effect is that the increase in the dispersibility of particle dirt such as mud improves the dispersion of protein and lipid dirt present in a complex state with particle dirt such as mud. Since cations remain on the subsequent cloth to exert an antibacterial effect, it is thought that the effect of suppressing room-drying odor is improved.

[Component (B)]
The component (B) contained in the garment cleaning composition of the present invention is α-sulfo fatty acid alkyl ester and / or soap. An α-sulfo fatty acid alkyl ester or soap can be used alone, or both can be used in combination. Preferred when used alone is an α-sulfo fatty acid alkyl ester.
As the α-sulfo fatty acid alkyl ester, a methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms can be preferably used. The fatty acid methyl ester sulfonate is also called MES. The α-sulfo fatty acid alkyl ester is represented by the following formula (VII).

In the above formula (VII), R ^a is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. R ^b is a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable. M represents a counter ion and includes, for example, alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts, among which alkali metal salts are preferred. More preferably, R ^a is a linear or branched alkyl or alkenyl group having 14 to 16 carbon atoms (16 to 18 carbon atoms in the fatty acid residue), and R ^b is a methyl group. is there.

  The kind of the soap used as the component (B) in the cleaning composition for clothing of the present invention is not particularly limited, and the soap used in a general granular detergent composition can be suitably used. A higher fatty acid salt having 10 to 20 carbon atoms is preferable, and a higher fatty acid salt having 11 to 17 carbon atoms is more preferable. Examples of the higher fatty acid constituting the soap include stearic acid, linoleic acid, and oleic acid. Examples of the soap include alkali metal salts or alkaline earth metal salts of the above fatty acids, preferably alkali metal salts, more preferably sodium or potassium salts.

Particularly preferably, the component (B) is a linear α-sulfo fatty acid alkyl ester and / or a linear soap. The linear α-sulfo fatty acid alkyl ester means that the structure excluding the sulfo group is linear.
Since the structure of the component (B) is a linear structure, the packing property with the component (A) is improved, and an anion-cation complex can be efficiently formed. Thereby, the dispersibility of particle dirts, such as mud, and the drying odor control effect improve more.

  In the garment cleaning composition of the present invention, α-sulfo fatty acid alkyl ester or soap can be used alone as component (B), and more preferably α-sulfo fatty acid alkyl ester and soap are used in combination. . The molar ratio of the α-sulfo fatty acid alkyl ester and the soap when used in combination is not limited, but is preferably 0.1 to 5.0, more preferably 0.5 to 3, and particularly preferably 1 to 2.5. If it is in the above-mentioned range, the dispersibility of particulate dirt such as mud and the effect of suppressing room-drying odor will be further improved.

The content of the component (B) is, for example, 1.5 to 15% by mass, preferably 4 to 12% by mass, and more preferably 5 to 10% by mass with respect to the total mass of the cleaning composition for clothing of the present invention. is there. If it is within the above-mentioned range, it exhibits good cleaning power in a well-balanced manner against not only particle dirt such as mud but also various dirt other than particle dirt such as mud, and also has good solubility and is used in combination with (A). This improves the dispersibility of dirt and the effect of suppressing room-drying odor.
Moreover, in the washing | cleaning composition for clothing of this invention, as described as an arbitrary component below, other anionic surfactants other than (B) component can be used together. However, from the viewpoint of performance, the component (B) is contained in the composition in an amount of 20 to 100% by mass, preferably 50 to 100% by mass, more preferably 70 to 90% by mass, based on the total anionic surfactant. %included.

  In the garment cleaning composition of the present invention, the molar ratio of (A) / (B) is 0.04 to 0.5, preferably 0.04 to 0.3, and more preferably 0.10 to 0.14. When the molar ratio of (A) / (B) is within the above-described range, excellent dispersibility of particle dirt such as mud and room drying odor suppression effect are brought about.

  The garment cleaning composition of the present invention may contain components other than the above components (A) and (B) as long as the effects of the present invention are not impaired. The other component is not particularly limited, and various additives that have been conventionally blended in a cleaning composition for clothing and the like can be blended. Examples of such additives include those shown below.

[Surfactant]
<Anionic surfactant>
Examples of the anionic surfactant other than the component (B) that can be used in the garment cleaning composition of the present invention include the following.
(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>
As a nonionic surfactant which can be mix | blended with the cleaning composition for clothing of this invention, the following can be mentioned, for example.
(1) Polyoxyalkylene alkyl ether or polyoxy obtained by adding an average of 3 to 30 moles, preferably 3 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms An alkylene alkenyl ether.
Among these, preferable examples include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols, and primary alcohols are preferred. The alkyl group or alkenyl group may be linear or branched.
(2) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkenyl phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (2) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ^c CO (OA) _{n ′} OR ^d (2)
[Wherein R ^c CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OA represents an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (for example, ethylene oxide, Propylene oxide or the like) is an addition unit (oxyalkylene group); n ′ is the average number of moles of alkylene oxide added, and is generally 3 to 30, preferably 5 to 20. R ^d represents a lower (1 to 4 carbon) 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 the nonionic surfactants described above, the nonionic surfactant (1) is preferable, and among them, polyoxyethylene having an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 12 to 16 carbon atoms. Alkylene alkyl ethers or polyoxyalkylene alkenyl ethers are particularly preferred.
Also, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester and ethylene having a melting point of 50 ° C. or less and HLB of 9 to 16 A fatty acid methyl ester ethoxylate to which an oxide is added, a fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
The above-mentioned “HLB” is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho, 1991, p. 234) reference).
Moreover, said "melting point" means the value measured by the melting | fusing point measuring method described in JISK0064-1992 "The melting | fusing point and melting range measuring method of a chemical product".

<Cationic surfactant>
As a cationic surfactant which can be mix | blended with the cleaning composition for clothing of this invention, the following can be mentioned, for example. However, the following description relates to optional components, and those corresponding to the component (A) are excluded.
(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.
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 polyoxy having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms An alkylene group is mentioned as a suitable thing.

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

[Detergency Builder]
Detergency builders are roughly classified into 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, and crystalline layered sodium silicate (for example, manufactured by Clariant Japan Co., Ltd.). Of 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, aluminosilicates and the like.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, zeolite can be suitably blended, and any of A type, X type, Y type, and P type can be used as the zeolite.

Among the above inorganic builder, sodium carbonate, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, and aluminosilicate are preferred, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, crystalline Alkali metal chlorides are particularly preferred.
When mix | blending potassium carbonate, 1-15 mass% is preferable from the point of the effect of a solubility improvement, and, as for content of potassium carbonate in a bleaching composition, 2-12 mass% is more preferable, 5-12 mass % Is more preferable.
When blending the crystalline alkali metal silicate, the content of the crystalline alkali metal silicate in the bleaching composition is preferably 0.5 to 40% by mass, and 1 to 25% by mass from the viewpoint of detergency. More preferably, 3-20 mass% is further more preferable, and 5-15 mass% is especially preferable.
When blending the alkali metal chloride, the content of the alkali metal chloride in the bleaching composition is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, from the viewpoint of improving the solubility. 3-7 mass% is further more preferable.
When blending the crystalline aluminosilicate, the content of the crystalline aluminosilicate in the bleaching composition is preferably 1 to 40% by mass in terms of powder properties such as detergency and fluidity. 30% by mass is particularly preferred.

  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, And polysaccharide derivatives such as polysaccharide oxides such as cellulose, amylose and pectin.

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

As a detergency builder, it can be used individually by 1 type or in combination of 2 or more types as appropriate. For the purpose of improving detergency and soil dispersibility in the washing liquid, it is preferable to use an organic builder such as polyacrylate and acrylic acid-maleic acid copolymer salt together with an inorganic builder such as zeolite.
The content of the detergency builder in the garment detergent composition of the present invention is preferably used in a range that does not impair the effects of the present invention in order to impart sufficient detergency.

[Fragrance]
A fragrance is a mixture (fragrance composition) comprising a fragrance component, a solvent, a fragrance stabilizer, and the like.
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 the cleaning composition for clothing of this invention, 0.01-1 mass% is more preferable.

[Dye]
In order to improve the appearance of the cleaning composition for clothing, various pigments can be blended.
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, pigments are preferred, and compounds having oxidation resistance such as oxides are particularly preferred. Such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like.
As the dye, one kind can be used alone, or two or more kinds can be used in appropriate combination.

[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). Examples thereof include fluorescent whitening agents such as phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.
Examples of commercially available fluorescent whitening agents include Whiteex SA, Whitetex SKC (above, trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba Specialty Chemicals), Lemonite CBUS-3B (trade name; manufactured by Khyati Chemicals), and the like. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are preferred.
As the fluorescent brightening agent, one kind can be used alone, or two or more kinds can be used in appropriate combination.
The content of the fluorescent brightener in the cleaning composition for clothing of the present invention is preferably 0.001 to 1% by mass.

[enzyme]
Enzymes that can be blended into the detergent composition for clothing include hydrolases, oxidoreductases, lyases, transferases, and isomerases, classified according to the reactivity of the enzyme. Is also applicable. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.
Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promerin, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. As commercial products of protease, sabinase, alcalase, cannase, everase, deozyme (above, trade name: manufactured by Novozymes); API21 (trade name: manufactured by Showa Denko KK); Maxacar, Maxapem (above, trade name: Genencor) Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.
Examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.

Examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposome (trade name; manufactured by Showa Denko KK).
As cellulase, cellzyme (trade name; 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 (and above) And cellulase described in JP-A-63-264699).
Examples of the amylase include commercially available stainzymes, termamyls, duramils (above, trade names: manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).
In the garment cleaning composition of the present invention, the content of the enzyme is preferably 0.3 to 2% by mass.

[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 and calcium chloride are preferred.
As an enzyme stabilizer, 1 type can be used individually or in combination of 2 or more types as appropriate.
As for content of the enzyme stabilizer in the cleaning composition for clothing of this invention, 0.05-2 mass% is preferable.

[Other polymers]
Polyethylene glycol having an average molecular weight of 200 to 200,000 or a weight average molecular weight of 1000, as a binder or a powder physical agent when densifying the surfactant-containing particles, and further imparting a recontamination preventing effect on hydrophobic fine particles. ˜100,000 acrylic acid and / or maleic acid polymers, cellulose derivatives such as polyvinyl alcohol and carboxymethyl cellulose can be blended.
Moreover, as a soil release agent, a copolymer or terpolymer of terephthalic acid and ethylene glycol and / or propylene glycol units can be blended.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above, polyethylene glycol having an average molecular weight of 1500 to 7000 is preferable.
These polymers can be used singly or in appropriate combination of two or more.
As for content of this polymer in the cleaning composition for clothing of this invention, 0.05-5 mass% is preferable.

[Anti-caking agent]
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like.
As a caking inhibitor, 1 type can be used individually or in combination of 2 or more types as appropriate.

[Defoaming agent]
Examples of the antifoaming agent include conventionally known antifoaming agents such as silicone / silica.
The antifoaming agent may be a defoaming agent granulated product produced using the method described in JP-A-3-186307, page 4, lower left column. Specifically, first, 20 g of Dow Corning silicone (compound type, PS antifoam) is added as a defoaming component to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nissho Chemical Co., Ltd., and mixed to obtain a homogeneous mixture. . Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of neutral anhydrous sodium sulfate were mixed at 70 to 80 ° C., and then extruded by Fuji Powder Co., Ltd. Granulate with a granulator (model EXKS-1) to obtain a granulated product.
As an antifoamer, it can be used individually by 1 type or in combination of 2 or more types as appropriate.

[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 adsorption of metal ions to fibers (objects to be cleaned).
In addition to those included in the detergency builder, the metal ion scavenger that can be blended in the garment detergent composition of the present invention includes aminopolyamines such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and glycolethylenediaminehexaacetic acid. Acetic acids: 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), diethylenetria Npenta (methylene phosphonic acid) organic phosphonic acid derivative or a salt thereof and the like; diglycolic acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
Consideration is required so that the content of the metal ion scavenger in the garment cleaning composition of the present invention is used within a range that does not impair the performance.

[PH adjuster]
The pH of the cleaning composition for clothing of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH of a 1% by weight aqueous solution of the cleaning composition for clothing is preferably 8 or more. The pH in the 1% by mass aqueous solution is more preferably 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the detergent composition for clothing, the pH is usually adjusted with an alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine And alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.

Moreover, in order to prevent the pH of the detergent composition for clothing from becoming too high, the pH can be adjusted to the above range using an acid or the like.
Examples of such acids include the metal ion scavengers, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, Hydrochloric acid or the like can be used.
Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

The manufacturing method of the washing | cleaning composition for clothing of this invention is not restrict | limited in particular, It can manufacture with the manufacturing method generally used. Examples of cases where the detergent composition is in powder form include, for example, a method in which a surfactant and other raw materials are dispersed / dissolved in water and spray-dried, kneading / extrusion, stirring granulation, rolling It can be manufactured by a method of subjecting it to granulation or the like, subjecting it to kneading, granulation, compression molding or the like, and further pulverizing as necessary.
Typical examples include the following methods.

Step (A)
Water is placed in a jacketed mixing tank equipped with a stirrer, and the temperature is adjusted to 60 ° C. To this, a surfactant excluding MES-Na and nonionic surfactant, such as soap, is added and stirred. Subsequently, MA agent (acrylic acid / maleic acid copolymer sodium salt) is added. After further stirring, a detergency builder such as zeolite, sodium carbonate, potassium carbonate, sodium sulfate is added. After further stirring to prepare a slurry for spray drying having a moisture content of 38%, spray drying is performed using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain spray-dried particles.
Process (B)
Spray kneaded particles obtained in step (A), MES-Na, and optional components such as zeolite, nonionic surfactant, fluorescent whitening agent and water are continuously kneaded (for example, manufactured by Kurimoto Steel Works, KRC-S4 type) and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a mixture containing a surfactant.
Process (C)
The mixture obtained in the step (B) was extruded with a pelleter double equipped with a die having a hole diameter of 10 mm (for example, EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.), etc. A pellet of about ˜30 mm is obtained.
Next, a grinding aid such as zeolite is added to the obtained pellets, and a grinding machine such as Fitzmill arranged in series in three stages in the presence of cold air (eg, 10 ° C., 15 m / s) (eg, Hosokawa Micron Corporation) (For example, screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage) All are 4700 rpm).
Post-processing step An optional component such as the powder obtained above and carboxymethylcellulose, coated sodium percarbonate particles, sodium sulfite, etc., is mixed into a horizontal cylindrical rolling mixer (for example, cylinder diameter 585 mm, cylinder length 490 mm, container 131.7 L Non-ionic surfactant with the addition of zeolite under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, 25 ° C., etc., with a drum inner wall surface having two baffle plates with a clearance of 20 mm and a height of 45 mm. While spraying the fragrance, it rolls and surface-modifies to obtain particles.
In order to color a part of the obtained particles, an aqueous dispersion of a pigment may be sprayed on the surface of the particles.
Filled with a horizontal cylindrical type rolling mixer (for example, a cylinder having a diameter of 585 mm, a cylinder length of 490 mm, a drum inner wall surface of a container 131.7 L and two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Under the conditions of a rate of 30% by volume, a rotational speed of 22 rpm, 25 ° C. and the like, the particles and enzyme obtained above are added and mixed to obtain a granular detergent composition.

  The component (A) may be blended in a slurry (blended in the step (A) in the above example), blended at the time of mixing (blended in the step (B) in the above example), or Spray blending (mixing in the post-processing step in the above example) in a horizontal cylindrical rolling mixer (Trommel) may be performed.

  In the garment cleaning composition of the present invention, the component (A) and the component (B) are preferably in a state of forming a complex. For example, in the manufacturing process of the cleaning composition for clothing of the present invention, the component (A) and the component (B) form a complex by mixing the component (A) at the time of slurry blending or kneading. be able to. Since the component (A) and the component (B) form a complex, the detergent particles can act on the soil as a complex immediately after dissolution. In addition, the effect of suppressing room-dried odor is further improved.

The method of using the cleaning composition for clothes of the present invention is not particularly limited. For example, when washing textile products such as clothes, it is used by putting it in a washing machine according to the amount of laundry, It can be used by dissolving in stored water. Laundry using the cleaning composition of the present invention may be performed in a short time or may be soaked. In addition, the object to be washed using the cleaning composition of the present invention is not particularly limited as compared with those in which a normal garment cleaning composition is a washing object. For example, clothes, towels, Examples thereof include textile products such as sheets.
The form of the garment cleaning composition of the present invention is not particularly limited, and is a form that can be taken by an ordinary garment cleaning composition. Preferably, the cleaning composition for clothing of the present invention is granular.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. According to the composition shown in the following Tables 3-5, the cleaning composition was prepared by the preparation method shown below. Subsequently, the prepared cleaning composition was used for washing, and the washing performance of the cloth to be washed and the suppression of the room drying odor were evaluated. In the following examples, unless otherwise specified, “%” of the composition indicates mass%.

Examples 1-15, Comparative Examples 1-9
The cleaning composition of each example shown to the following Tables 3-5 was manufactured using the component shown in the table | surface. In addition, the unit of the composition blending amount in the table indicates mass% based on the total mass of the cleaning composition. In addition, among the components in the table, zeolite and MA agent indicate blending amounts in terms of pure components, and components (A), (B), and others indicate blending amounts as (as is). . “Balance” of the amount of sodium carbonate means that the total amount is adjusted to 100% by mass. (A) / (B) (molar ratio) indicates a value expressed by a molar ratio of a pure component conversion ratio of the component (A) and the component (B). Similarly, the molar ratio of MES and soap is a value expressed by the molar ratio of the pure component conversion blending ratio of MES and soap. Below, it demonstrates about the description of the component shown in the table | surface, and the manufacturing method of a cleaning composition.

（Ａ−１）レジコートE-11： ＡＩ 50％ 分子量 457
A-1成分中、「牛脂アルキル」は、C12〜C18の混合物（C18が主体）である。
（Ａ−２）アーカードT-800： ＡＩ 50％ 分子量 351
（Ａ−３）化合物Ｘ：C32H70O12.2 ＡＩ 99％ 分子量 650 [(A) component]
Table 1 below shows the cationic substances as the component (A) used in the present invention.

(A-1) Regicoat E-11: AI 50% Molecular weight 457
In the A-1 component, “tallow alkyl” is a mixture of C12 to C18 (mainly C18).
(A-2) ARCARD T-800: AI 50% Molecular weight 351
(A-3) Compound X: C32H70O12.2 AI 99% Molecular weight 650

平均分子量６００のポリエチレングリコール１００ｇをクロロホルム５００ｇに溶解し、室温下で塩化チオニル４８ｇを添加した。一昼夜の撹拌・熟成を行った後、反応混合物を水２００ｇを用いて３回の水洗を行った。得られた有機相を濃縮してポリエチレングリコール二塩化物１０３ｇを得た。得られたポリエチレングリコール二塩化物５０ｇとイソプロパノール２００ｇおよび炭酸ナトリウム０．８ｇを１Ｌのオートクレーブに仕込み、トリメチルアミン９．５ｇを封入した後、９０℃で３時間の反応を行った。反応生成物をオートクレーブから取り出し濃縮を行い、最終生成物５６ｇを得た。これをVolhard法によりＣｌイオン％の定量を行ったところ９．３１％であった。また、最終生成物をナトリウムブチラートで処理した後、Volhard法により塩素の定量を行い、全Ｃｌ％を求めたところ９．３３％であった。（Ａ−３）成分でＣｌはＣｌイオンとして存在しているので、（Ａ−３）成分の全Ｃｌ％及びＣｌイオン％の理論値は共に９．３９％である。よって、上記の定量値と理論値から得られた最終生成物は（Ａ−３）成分であることを確認した。 ((A-3) Component Production Method)
The component (A-3) is a compound described in Patent Document 1, and is represented by the general formula (X). In the formula (X), R ¹ and R ³ are methyl groups, R ² is an ethylene group, and n is It is a compound having an average value of 12.2, and Y ⁻ is Cl ⁻ .

100 g of polyethylene glycol having an average molecular weight of 600 was dissolved in 500 g of chloroform, and 48 g of thionyl chloride was added at room temperature. After stirring and aging for a whole day and night, the reaction mixture was washed with water three times using 200 g of water. The obtained organic phase was concentrated to obtain 103 g of polyethylene glycol dichloride. 50 g of the obtained polyethylene glycol dichloride, 200 g of isopropanol and 0.8 g of sodium carbonate were charged into a 1 L autoclave, 9.5 g of trimethylamine was sealed, and the reaction was performed at 90 ° C. for 3 hours. The reaction product was removed from the autoclave and concentrated to obtain 56 g of the final product. This was determined to be 9.31% when the Cl ion% was quantified by the Volhard method. Further, after the final product was treated with sodium butyrate, chlorine was quantified by the Volhard method, and the total Cl% was determined to be 9.33%. Since Cl exists as a Cl ion in the component (A-3), the theoretical values of the total Cl% and the Cl ion% in the component (A-3) are both 9.39%. Therefore, it was confirmed that the final product obtained from the above quantitative value and theoretical value was the component (A-3).

（Ｂ−１）CH3(CH2)14CH(SO3Na)COOCH3) ＭＥＳ−Ｎａ： ＡＩ 66％ 分子量 387
（Ｂ−２）炭素数12〜18の脂肪酸ナトリウム（純分；67質量％、タイター；40〜45℃、脂肪酸組成；Ｃ12＝11．7質量％、Ｃ14＝0.4質量％、Ｃ16＝29．2質量％、Ｃ18Ｆ０（ステアリン酸）＝0.7質量％、Ｃ１８Ｆ１（オレイン酸）＝56．8質量％、Ｃ18Ｆ2（リノール酸）＝1.2質量％、ＡＩ 67％ 分子量 289 （特開2011-202149の実施例、「界面活性剤粒子の原料」に記載の石鹸）
（Ｂ−３）(CH3)13C6H4SO3Na ＬＡＳ： ＡＩ 50％ 分子量 375 （Ｃ12-14のため13として算出）
（Ｂ−４）CH3(CH2)10CH2S2Na ＡＩ 90％ 分子量 256
（Ｂ−５）ライポンＬＨ−900 ＡＩ 96％ 分子量 270 （Ｃ12-14のため 13として算出） [(B) component]
Table 2 below shows the anionic surfactant which is the component (B) used in the present invention.

(B-1) CH3 (CH2) 14CH (SO3Na) COOCH3) MES-Na: AI 66% Molecular weight 387
(B-2) Fatty acid sodium having 12 to 18 carbon atoms (pure content; 67% by mass, titer; 40 to 45 ° C., fatty acid composition; C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 % By mass, C18F0 (stearic acid) = 0.7% by mass, C18F1 (oleic acid) = 56.8% by mass, C18F2 (linoleic acid) = 1.2% by mass, AI 67% Molecular weight 289 (Examples of JP 2011-202149 A) Soap described in “Raw material for surfactant particles”)
(B-3) (CH3) 13C6H4SO3Na LAS: AI 50% Molecular weight 375 (Calculated as 13 for C12-14)
(B-4) CH3 (CH2) 10CH2S2Na AI 90% Molecular weight 256
(B-5) Lipon LH-900 AI 96% Molecular weight 270 (Calculated as 13 for C12-14)

(Method for producing component (B-1))
C14 fatty acid ester obtained by fractionating a fatty acid ester obtained by transesterifying palm oil with methyl alcohol was reacted with SO3 gas diluted with nitrogen gas in a flow-through type thin film reactor (SO3 / Fatty acid ester) = 1.2, sulfonation was performed under the conditions of a reaction temperature of 80 ° C. to obtain α-sulfo fatty acid methyl ester. Next, 30 parts by weight of methanol was introduced into 100 parts by weight of the obtained α-sulfo fatty acid methyl ester, and then 8.6 parts by weight of 35% hydrogen peroxide was introduced, and bleaching was performed at 80 ° C. for 60 minutes. . 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.

[Other ingredients (common ingredients)]
Carboxymethyl cellulose (CMC): trade name; CMC Daicel 1190, Daicel Industries, Ltd.
Nonionic surfactant: ECOROL26 (trade name, manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms), an 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 40% by mass aqueous solution).
-Nasulfite: Anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
-Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.).
Carbonic acid K: Potassium carbonate (powder) (Asahi Glass Co., Ltd .; average particle diameter 490 μm, bulk density 1.30 g / cm 3).
-Carbonic acid Na: granular ash (Asahi Glass Co., Ltd. average particle diameter 320 micrometers, bulk density 1.07g / cm3).
-Brightening agent: Mixture of Chino Pearl CBS-X (trade name, Ciba Specialty Chemicals) / Chino Pearl AMS-GX (trade name, Ciba Specialty Chemicals) = 3/1 (mass ratio).
Perfume: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 5/4 (mass ratio).
-Dye: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue).
-Percarbonate Na: Zhejiang Jinke Chemicals, trade name; SPCC (carbonic acid root 43.5% by mass, average particle size 870 μm, coated sodium percarbonate particles).

Bleach activator: Synthesis of sodium 4-dodecanoyloxybenzene sulfonate as a bleach activator, sodium 4-hydroxybenzene sulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (Kanto) as raw materials The following method was used, using a reagent manufactured by Kagaku Co., Ltd., lauric acid chloride (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and acetone (a reagent manufactured by Kanto Chemical Co., Inc.).
3,000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 3347 g (15.3 mol) of lauric acid chloride was stirred at 50 ° C. for 30 minutes while stirring with a stirrer. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, purification was performed by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90%. 70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate synthesized by the above method, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)), sodium a-olefin sulfonate having 14 carbon atoms Powder product (trade name: Liporan PJ-400 (manufactured by Lion Corporation)) was put into Hosokawa Micron's Extrude Ohmic EM-6 (trade name) so that the total amount was 5000 g at a ratio of 5 parts by mass, By kneading and extruding, a noodle-like extruded product having a diameter of 0.8 mmf was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 (trade name) manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent, and pulverized to obtain an average particle size of about A 700 μm bleach activator granulate was obtained.
Baking soda: sodium bicarbonate (Penrice, trade name; SODIUM BICARBONATE FOOD GRADE COARSE GRANULAR, bicarbonate root 72.6% by mass, average particle size 300 μm, content of particles less than 150 μm; 3% by mass, particles Does not include particles having a diameter of 600 μm or more).
・ Moisture: Ion exchange water

[Production method of cleaning composition]
The cleaning compositions of Examples 1 to 15 and Comparative Examples 1 to 9 shown in Tables 3 to 5 below were prepared by the following method according to the compositions shown in the table.
(Preparation of granular detergent composition)
Step (A)
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, a surfactant excluding MES-Na and nonionic surfactant was added and stirred for 10 minutes. Subsequently, MA agent (acrylic acid / maleic acid copolymer sodium salt) was added. After further stirring for 10 minutes, a part of the powder A-type zeolite (1.0% for addition during kneading, 5.0% for grinding aid, 1.5% from the addition amount described in Tables 3 to 5) The amount excluding each zeolite A for surface coating), sodium carbonate, potassium carbonate, and sodium sulfate were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray dried particles with cm ³ and 5% moisture were obtained.

Process (B)
Spray dried particles obtained in step (A), MES-Na, 1.0% powder A-type zeolite, remaining nonionic surfactant except 0.5% nonionic surfactant for spray addition, fluorescent whitening The water and the surfactant 6 were added to the continuous kneader (KRC-S4, KRC-S4 type) and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. % Mixture was obtained.

Process (C)
The mixture obtained in step (B) was cut with a cutter while extruding it using 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 having a length of about 5 to 30 mm was obtained.
Next, 5.0% of powder A-type zeolite as a grinding aid was added to the obtained pellets, and Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) was arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). , DKA-3) to obtain a powder (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3 All stages are 4700 rpm).

Post-treatment step The powder obtained in step (C), carboxymethylcellulose, coated sodium percarbonate particles, and sodium sulfite were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, container 131.7 L inside the drum). 1.5% powder A-type zeolite was added under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C. with a wall having two baffle plates with a clearance of 20 mm and a height of 45 mm. While spraying 0.5% nonionic surfactant and fragrance, the particles were obtained by rolling for 1 minute to modify the surface.
In order to color a part of the obtained particles, the particles are transferred on a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor has a height of 30 mm and a layer width of 300 mm) A 20% aqueous dispersion of the pigment was sprayed on the surface (average particle size 500 μm, bulk density 0.84 g / cm ³ ).
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Under the conditions of volume%, rotation speed 22 rpm, and 25 ° C., the particles and enzyme obtained above were added and mixed for 5 minutes to obtain a granular detergent composition.

Example 1 (Examples 2, 5-10 Comparative Examples 1 and 2)
In the kneading step of step (B), (A-1) Regiscoat E-11 was blended to produce a powder cleaning composition for clothing. In Example 1, “surfactant excluding MES-Na and nonionic surfactant” in step (A) is soap.

Example 3
When adding "surfactant excluding MES-Na and nonionic surfactant" in step (A), (A-1) Regiscoat E-11 was blended to produce a powder cleaning composition for clothing. .

Example 4
In addition to the nonionic surfactant and the fragrance in the post-treatment step, (A-1) Regiscoat E-11 was spray-blended to produce a powder cleaning composition for clothing.

Example 11
In the production method of Example 1, when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), a powder cleaning composition for clothing was similarly prepared except that no soap was added. Manufactured.

Example 12
A powder detergent composition for clothing was produced in the same manner except that MES-Na in the step (B) was not added in the production method of Example 1.

Example 13
In the production method of Example 1, when “surfactant excluding MES-Na and nonionic surfactant” in step (A) is added, it is similarly applied to clothing except that sodium alkylbenzenesulfonate is added in addition to soap. A powder detergent composition was prepared.

Example 14
In the production method of Example 1, when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), powder for clothing is similarly applied except that sodium dodecyl sulfate is added in addition to soap. A cleaning composition was prepared.

Example 15
Powder for clothing in the same manner as in the production method of Example 1, except that sodium percarbonate and sodium bicarbonate are added when adding carboxymethylcellulose and sodium sulfite in the post-treatment step, and bleaching activator is added when adding the enzyme. A cleaning composition was prepared.

Comparative Example 3
In the production method of Example 1, no soap is added when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), and MES-Na is not added in step (B). In the same manner, a powder cleaning composition for clothing was produced.

Comparative Example 4
In the production method of Example 1, a powder cleaning composition for clothing was produced in the same manner except that (A-1) Regiscoat E-11 was not blended in the kneading step of step (B).

Comparative Example 5
In the production method of Example 1, LAS is added without adding soap when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), and MES-Na in step (B) is added. A granular detergent composition was prepared in the same manner except that it was not added.

Comparative Example 6
In the production method of Example 1, sodium dodecyl sulfate was added without adding soap when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), and MES- in step (B) A granular detergent composition was prepared in the same manner except that Na was not added.

Comparative Example 7
In the production method of Example 1, when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), branched dodecylbenzene is added without adding soap, and MES- in step (B) is added. A granular detergent composition was prepared in the same manner except that Na was not added.

Comparative Example 8
In the production method of Example 1, soap is not added when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), and in the kneading step in step (B) (A-1 ) A detergent composition for clothing was produced in the same manner except that (A-2) Arcard T-800 was added instead of Regiscoat E-11.

Comparative Example 9
In the production method of Example 1, soap is not added when adding “surfactant excluding MES-Na and nonionic surfactant” in step (A), and in the kneading step in step (B) (A-1 ) A detergent composition for clothing was produced in the same manner except that (A-3) compound X was added instead of Regiscoat E-11.

[Mud cleaning power evaluation method]
1) Preparation method of mud-contaminated cloth Dissolve 50 g of original mud from Mikata in 1 L of ion exchange water, disperse with an ultrasonic cleaner for 20 minutes, and further with a homogenizer for 5 minutes and transfer to an evaporating dish. The cloth is dipped 20 times with cotton tweezers (11 × 16 cm) sandwiched between tweezers, repeatedly pulled up, dehydrated with a roller, and then dried with an electric dryer (105 ° C.) for 30 minutes. After drying, both sides of the contaminated cloth were polished 25 times with a sponge to make the mud particles uniform, cut into 4 cm square, and used as a mud-dirt contaminated cloth.
2) Cleaning method Prepared as above under the conditions of 3 ° DH hard water, bath volume 30 L, bath ratio 1:30, detergent (clothing detergent composition shown in Tables 3 to 5 below) concentration 833 ppm, temperature 25 ° C. Five mud-contaminated cloths were put in each, washed for 10 minutes with a targotometer, dehydrated for 1 minute, rinsed twice with water at 3 ° DH and 25 ° C. for 3 minutes, and dehydrated for 1 minute. Using the Z value measured by Nippon Denshoku color difference meter Z-90 as the reflectance, the mud dirt cleaning power of each cleaning composition was calculated by the following formula (1). In addition, the value of the detergency was shown as an average value of five contaminated cloths.
Dirt application cleaning power (%) = (reflectance of contaminated cloth−reflectivity of cleaning cloth) / (reflectance of contaminated cloth−reflectance of uncontaminated cloth) × 100 (1)

[Evaluation method for drying odor control]
In the normal course of a washing machine (JW-Z23A type, manufactured by Haier) using 10 cleaning towels used for half a year at home for about 2 days in normal life, with each detergent composition Laundry treatment was performed (pour tap water having a water temperature of about 20 ° C. and a hardness of about 3 ° DH, a bath ratio of 20 times). At that time, the washing treatment was performed at a washing solution concentration of 833 ppm for each cleaning composition.
In addition, a new 100% cotton skin shirt (manufactured by BVD) is washed in a fully automatic washing machine (NA-F70SD1 manufactured by Matsushita Electric Industrial Co., Ltd.) for clothing with a bath ratio (water temperature approx. The tap water was poured 5 times at a temperature of 20 ° C. and a hardness of about 3 ° DH. At that time, a commercial synthetic detergent top (manufactured by Lion Co., Ltd.) was used as the detergent, and the laundry treatment was performed with the amount of detergent used per wash being 25 g / 30 L of tap water.

After the washing of the hand towel, the hand towel was dried in a room having a room temperature of about 24 ° C. and a relative humidity of 90% RH and dried for 5 hours. After that, 6 expert panelists performed sensory evaluation to smell the smell of 10 towels after washing and drying.
The sensory evaluation was performed by scoring according to the following evaluation criteria (a). Specifically, according to the 6-level odor intensity display in the evaluation standard (a), the expert panelist evaluates the odor of each of the 10 hand towels after indoor drying by sensory evaluation, and comprehensively judges them to give a score. Was determined.
Evaluation criteria (a)
5 points: intense odor 4 points: strong odor 3 points: odor intensity that can be easily detected 2 points: odor intensity enough to detect what odor 1 point: odor intensity that can finally be detected 0 Point: Odorless

Subsequently, out of the scores of 6 people, the average score for 4 people excluding the highest and lowest points was determined, and the deodorizing effect was evaluated according to the following evaluation criteria (b). In the evaluation criteria (b), 3 points or more were considered acceptable.
Evaluation criteria (b)
5 points: less than 0.25 points 4 points: 0.25 points or more and less than 0.5 points 3 points: 0.5 points or more and less than 1.5 points 2 points: 1.5 points or more and less than 2.5 points 1 point: 2.5 points or more, less than 3.5 points 0 point: 3.5 points or more

Table 3: Composition and evaluation result of cleaning composition (Example) (Numerical values in composition table are% by mass)

Table 4: Composition of cleaning composition (Example) and evaluation results (numerical values in composition table are% by mass)

Table 5: Composition of cleaning composition (comparative example) and evaluation results (numerical values in composition table are% by mass)

Claims (2)

(A) From the group which has 2 or more groups chosen from the group which consists of a quaternary ammonium group and an amino group in a molecule | numerator, and consists of a C8-C36 alkyl group and a C8-C36 alkenyl group A compound having one or more selected groups, and (B) an α-sulfo fatty acid alkyl ester and / or a soap,
A cleaning composition for clothing having a molar ratio of (A) / (B) of 0.04 to 0.5.   The cleaning composition for clothing according to claim 1, wherein the component (A) and the component (B) form a complex.