JP5052889B2 - Cleaning composition - Google Patents

Description

  The present invention relates to a cleaning composition.

  It has been conventionally proposed to improve the cleaning performance by adding a bleach activator to a cleaning composition containing an inorganic peroxide to generate an organic peracid during cleaning. For example, Patent Document 1 discloses that a bleach activator can be used in a solid bleach containing hydrogen peroxide.

  In general, a nonionic surfactant containing an oxyalkylene group such as an oxyethylene group (also referred to as an oxyalkaneyl group, hereinafter described as an oxyalkylene group) is widely used in a detergent composition because of its high cleaning performance. . However, when the composition contains a nonionic surfactant having an oxyalkylene group, the reaction between the inorganic peroxide and the bleach activator is inhibited, and the cleaning performance improvement effect by the organic peracid may be significantly reduced. It was found.

  An object of the present invention is to provide a cleaning composition that efficiently produces organic peracids and is excellent in bleaching performance. In particular, it is to provide a detergent composition comprising a nonionic surfactant having an oxyalkylene group.

In the present invention, (a) inorganic peroxide (hereinafter referred to as component (a)), (b) -COOM, -SO ₃ M, and -OSO ₃ M [M represents a cation in the molecule. An alkanoyloxybenzene-type bleach activator (hereinafter referred to as component (b)), and (d) a polyglyceryl having an alkyl group having 4 to 20 carbon atoms. The present invention relates to a detergent composition containing an alkyl ether (hereinafter referred to as component (d)) of more than 5% by mass to 35% by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the organic peroxide is produced | generated efficiently and the cleaning composition excellent in the bleaching performance is provided.

<(A) component>
The inorganic peroxide (a) is a substance that generates hydrogen peroxide in water, and examples thereof include percarbonates such as sodium percarbonate and perborates such as sodium perborate. In the cleaning composition of the present invention, the component (a) is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, particularly preferably 1 to 20% by mass, and most preferably 2 to 2%. Contains 15%.

<(B) component>
In the cleaning composition of the present invention, -COOM, -SO ₃ M, and -OSO ₃ M [M represents a cation in the molecule as the component (b) for the purpose of improving the bleaching effect. An alkanoyloxybenzene type bleach activator having a group selected from the above and a hydrocarbon having 5 to 20 carbon atoms.

  As the component (b), a bleach activator represented by the following general formula (b1) is preferable.

[Wherein, R ¹ is a hydrocarbon group having 5 to 20 carbon atoms, n is a number of 1 or 0, and X is —COOM, —SO ₃ M, or —OSO ₃ M]. M represents a cation. ]

  As the component (b), alkanoyloxybenzenesulfonic acid having an alkanoyl group having 8 to 14 carbon atoms and further 8 to 13 carbon atoms or alkanoyloxy having an alkanoyl group having 8 to 14 carbon atoms and further 8 to 13 carbon atoms Benzenecarboxylic acid or a salt thereof is preferred.

  As the component (b), specifically, octanoyloxy-p-benzenesulfonic acid, nonanoyloxy-p-benzenesulfonic acid, 3,5,5-trimethylhexanoyloxy-p-benzenesulfonic acid, decanoyloxy -P-benzenesulfonic acid, dodecanoyloxy-p-benzenesulfonic acid, octanoyloxy-o- or -p-benzenecarboxylic acid, nonanoyloxy-o- or -p-benzenecarboxylic acid, 3,5,5-trimethyl Hexanoyloxy-o- or -p-benzenecarboxylic acid, decanoyloxy-o- or -p-benzenecarboxylic acid, dodecanoyloxy-o- or -p-benzenecarboxylic acid, and salts thereof. As the salt, sodium salt, potassium salt, and magnesium salt are preferable, and sodium salt is particularly preferable from the viewpoint of solubility.

  Among these, nonanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzenecarboxylic acid, dodecanoyloxy-p-benzenesulfonic acid and salts thereof are particularly preferable from the viewpoint of bleaching effect.

  The cleaning composition of the present invention contains the component (b) preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 4% by mass.

<(C) component>
The cleaning composition of the present invention can contain a nonionic surfactant having an alkoxylate group in the molecule as the component (c). (C) As a component, the compound of general formula (c1) is preferable.
^{R 11 -T - [(R 12} O) a -H] b (c1)
[Wherein R ¹¹ is an alkyl group or alkenyl group having 7 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and R ¹² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. a represents a number of 2 to 20, preferably 4 to 10, particularly preferably 5 to 8. T is —O—, —CON— or —N—. When T is —O—, b is 1, and when T is —CON— or —N—, b is 2. ]

Specific examples of the compound of the general formula (c1) include the following compounds.
R ¹¹ —O— (C ₂ H ₄ O) _c —H (c1-1)
[Wherein R ¹¹ represents the above-mentioned meaning. c is a number of 2 to 20, preferably 4 to 12, particularly preferably 6 to 10. ]
_{^{R 11 -O- (C 2 H 4}} O) d - (C 3 H 6 O) e -H (c1-2)
[Wherein R ¹¹ represents the above-mentioned meaning. d and e are each independently a number of 2 to 15, preferably 2 to 10, and ethylene oxide and propylene oxide may be random or block adducts. ]

[Wherein R ¹¹ represents the above-mentioned meaning. The sum of f and g is 3 to 20, preferably 3 to 15, particularly preferably 2 to 10. ]

Of these, nonionic surfactants selected from (c1-1) and (c1-2) are particularly preferred in the present invention.

  The cleaning composition of the present invention contains the component (c), preferably 5 to 35% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 15% by mass.

<(D) component>
The component (d) is a polyglyceryl alkyl ether having an alkyl group having 4 to 20 carbon atoms, preferably a polyglyceryl alkyl ether having an alkyl group having 4 to 9 carbon atoms. In particular, a polyglyceryl alkyl ether represented by the following general formula (d1) is preferable.
RO- (C ₃ H ₆ O ₂ ) _n -H (d1)
[Wherein, R is an alkyl group having 4 to 9 carbon atoms, n is the degree of condensation of glycerol, and is an average of 1 to 10, preferably 2 to 7, more preferably 3 to 5. ]

  The cleaning composition of the present invention contains (d) component in an amount of more than 5% by mass to 35% by mass, preferably more than 5% by mass to 25% by mass, more preferably more than 5% by mass to 20% by mass.

  In the cleaning composition of the present invention, when the component (c) is contained, the mass ratio of the component (c) to the component (d) is (c) / (d) from the viewpoint of increasing the organic peracid production rate. And 1000/1 to 1/50, more preferably 1000/1 to 1/5, more preferably 500/1 to 1/1, and particularly preferably 10/1 to 1/1.

<Other ingredients>
The cleaning composition of the present invention preferably contains an anionic surfactant [hereinafter referred to as component (e)]. Examples of the anionic surfactant include an alkyl group or an alkenyl group having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 15 carbon atoms, a —SO ₃ M group and / or a —OSO ₃ M group in the molecule. An anionic surfactant having [M: counter ion] is preferred. Specifically, alkylbenzene sulfonic acid having the above carbon number, alkyl (or alkenyl) sulfate, polyoxyalkylene alkyl (or alkenyl) ether sulfate having an average addition mole number of alkylene oxide of 1 to 6, olefin sulfonic acid, alkane sulfonic acid , Α-sulfo fatty acid, α-sulfo fatty acid ester and salts thereof are preferred. Among these, an alkyl (or alkenyl) sulfate ester having an alkyl group or alkenyl group having 10 to 16 carbon atoms, an alkyl group or alkenyl group having 10 to 16 carbon atoms, and ethylene oxide (hereinafter referred to as EO) average From polyoxyethylene alkyl (or alkenyl) ether sulfate having an addition mole number of 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, or alkylbenzene sulfonic acid having 10 to 15 carbon atoms, and salts thereof It is preferable to blend one or more selected. As the salt, sodium salt, potassium salt, ammonium salt and alkanolamine salt are preferable from the viewpoint of storage stability. The cleaning composition of the present invention preferably contains 5 to 35% by mass, more preferably 5 to 20% by mass of component (e).

Moreover, it is preferable that the cleaning composition of this invention contains an alkaline agent. Examples of the alkali agent include carbonates, bicarbonates, silicates, orthosilicates, metasilicates, crystalline silicates, phosphates and the like. As the salt, alkali metal salts such as sodium salt and potassium salt are preferable. These alkaline agents can be used alone or as a mixture of two or more. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, and the like. Here, the crystalline silicate has a maximum pH of 11 or more in a dispersion dispersed in 0.1% by mass in ion exchange water at 20 ° C. It is an alkaline substance that requires a 0.1 N HCl aqueous solution, and is distinguished from zeolite (crystalline aluminosilicate). The crystalline silicate is preferably a layered one. JP 7-89712 A, JP 60-227895 A and Phys. Chem. Glasses 7, p127-p138 (1966), Z. Kristallogr., 129, p396. -p404 (1969) etc. can be used. 0.42Na ₂ O · 0.14K crystalline silicate represented by _{2 O · SiO 2 · 0.03CaO ·} 0.0005MgO is preferably used. In addition, powdered and granular products are available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ).

  Moreover, the cleaning composition of this invention can contain the silicate compound (thing other than an alkaline agent) widely utilized as a builder for detergents. Examples of such silicate compounds include crystalline or non-crystalline aluminosilicates and silicates. Of these, zeolite is preferable.

  As the zeolite, a compound represented by the formula (c1) is preferable, and a compound represented by (c2) is more preferable.

a (M ₂ O) · Al ₂ O ₃ · b (SiO ₂ ) · w (H ₂ O) (c1)
(In the formula, M represents an alkali metal atom, a, b, and w represent molar ratios of the respective components. Generally, 0.7 ≦ a ≦ 1.5, 0.8 ≦ b ≦ 6, and w is an arbitrary value. Represents a positive number.)
_{Na 2 O · Al 2 O 3} · n (SiO 2) · m (H 2 O) (c2)
(Here, n represents a number from 1.8 to 3, and m represents a number from 1 to 6.)

  Examples of the zeolite include synthetic zeolite represented by A-type, X-type and P-type zeolite. A suitable average particle size of zeolite is 0.1 to 10 μm. The detergent composition of the present invention preferably contains 1 to 90% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass of zeolite.

  The cleaning composition of the present invention can contain a metal sequestering agent. As the metal sequestering agent, (1) a phosphoric acid compound selected from phosphoric acid, tripolyphosphoric acid and phytic acid, (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1 A phosphonic acid selected from -hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, (3 ) Phosphonocarboxylic acid selected from 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, 畚 och-methylphosphonosuccinic acid, (4) aspartic acid, glutamic acid, glycine (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine Cole ether diamine tetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraamine hexaacetic acid, aminopolyacetic acid selected from diencoric acid, (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, Mention may be made of organic acids selected from oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, (7) aminopoly (methylenephosphonic acid), or polyethylenepolyaminepoly (methylenephosphonic acid). More preferably, the phosphonic acid compound (2), the aminopolyacetic acid compound (5), the organic acid (6), and the compound (7) are suitable. In the present invention, in particular, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, citric acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine2 Most preferred is a compound selected from acetic acid and 2-hydroxyethyliminodiacetic acid. The cleaning composition of the present invention preferably contains 0.01 to 10% by mass, and further 0.1 to 5% by mass of a metal sequestering agent.

  The detergent composition of the present invention comprises a recontamination inhibitor (such as carboxymethyl cellulose), a softening agent (such as dialkyl quaternary ammonium salts and clay minerals), a reducing agent (such as sulfite), and a fluorescent whitening agent (biphenyl). Type, aminostilbene type, etc.), foam control agents (silicone, etc.), perfumes, enzymes (proteases, cellulases, pectinases, amylases, lipases, etc.) and the like can be added.

  Also, as organic builder, carboxylate (aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, maleic acid derivative, oxalate etc.), organic carboxylic acid (salt) polymer (acrylic) Acid polymers and copolymers, polycarboxylic acid polymers and copolymers, glyoxylic acid polymers, polysaccharides and salts thereof, and the like. Of these, organic carboxylic acid (salt) polymers are preferred. In these builder salts, the counter ion is preferably an alkali metal salt or an amine, particularly sodium and / or potassium, monoethanolamine, or diethanolamine. These builders can be used alone or in combination of two or more.

  In addition, surface modification may be performed from the viewpoint of fluidity and caking resistance when the composition is powdery or particulate. As the surface modifier, zeolite can be used. Besides, silicate compounds such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, metal soap, powder surfactants, etc. And water-soluble polymers such as polycarboxylates such as carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, copolymers of acrylic acid and maleic acid or salts thereof. More preferred is zeolite.

  When the cleaning composition of the present invention is in a powder form, the bulk density is preferably 300 to 1000 g / L, more preferably 500 to 900 g / L, and particularly preferably 600 to 800 g / L. The average particle size is preferably 150 to 3000 μm, more preferably 500 to 1500 μm, and particularly preferably 600 to 1200 μm.

  The cleaning composition of the present invention is suitable for textile products such as clothing and bedding.

  The cleaning composition shown in Table 1 was prepared using the components shown in Table 1, and the organic peracid production rate and cleaning power were evaluated by the following methods. The results are shown in Table 1.

<Measurement method of organic peracid production rate>
0.6667 g of the detergent composition was put in 1 L of ion-exchanged water, and stirred for 10 minutes with a magnetic stirrer. Thereafter, 1 mL of a 1% catalase aqueous solution was added and stirred for 3 minutes, and then 10 mL of 20% sulfuric acid and 10 mL of a 10% potassium iodide aqueous solution were added to develop a yellow color. Titration was performed with 1/50 N sodium thiosulfate until the yellow color disappeared, and the organic peracid production rate (%) was determined by the following equation.

<Detergency>
After dissolving 0.6667 g of the detergent composition shown in Table 1 in 1 L of tap water, put 5 pieces of spinach-contaminated cloth prepared as follows, and wash for 10 minutes using a tartometer at 80 rpm. went. After rinsing sufficiently, it was dried and the washing rate was measured by the following formula.
Washing rate (%) = (reflectance after washing−reflectance before washing) / (reflectance of white cloth−reflectivity before washing) × 100
The reflectance was measured using NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

* Preparation of spinach-contaminated cloth After commercially available spinach was pulverized with a mixer, the produced liquid portion was filtered with a cotton cloth. 0.5 g of the obtained liquid was uniformly applied onto a 6 cm × 6 cm cotton gold cloth # 2023 and dried at room temperature for 12 hours for use in the test.

Claims (7)

(A) an inorganic peroxide 0.1 to 60 wt%, showing -COOM, -SO ₃ M, and -OSO ₃ M [M a cation in (b) molecule. An alkanoyloxybenzene-type bleach activator having a group of 5 to 20 carbon atoms and ( d) a polyglyceryl alkyl ether 5 having an alkyl group of 4 to 20 carbon atoms A powder detergent composition comprising more than 35% by mass to 35% by mass and (e) 5 to 35% by mass of an anionic surfactant . The detergent composition according to claim 1 , further comprising (c) a nonionic surfactant having an oxyalkylene group in the molecule, wherein the mass ratio of (c) / (d) is from 10/1 to 1/5. object. The powder cleaning composition according to claim 1 or 2, wherein the component (b) is a bleach activator represented by the following general formula (b1).

[Wherein, R ¹ is a hydrocarbon group having 5 to 20 carbon atoms, n is a number of 1 or 0, and X is —COOM, —SO ₃ M, or —OSO ₃ M]. M represents a cation. ] The powder cleaning composition according to any one of claims 1 to 3, wherein the component (d) is a polyglyceryl alkyl ether having an alkyl group having 4 to 9 carbon atoms. The powder detergent composition according to any one of claims 1 to 4, wherein the component (d) is a polyglyceryl alkyl ether represented by the following general formula (d1).
RO- (C ₃ H ₆ O ₂ ) _n -H (d1)
[In the formula, R is an alkyl group having 4 to 9 carbon atoms, n is the degree of condensation of glycerin, and is an average of 1 to 10. ] (C) Powder cleaning composition of any one of Claims 2-5 which contains 5-35 mass% of components. Furthermore, the powder cleaning composition of any one of Claims 1-6 containing an alkali agent and a silicate compound (thing other than an alkali agent) .