JP7228969B2 - liquid bleach composition - Google Patents

Description

The present invention relates to liquid bleach compositions.

The liquid bleach composition is excellent in the effect (detergency) of removing dirt adhering to the items to be washed. Among them, compositions containing hydrogen peroxide as a bleaching agent are currently widely used because they are easy to use even for colored articles.
For the purpose of reducing the environmental load, liquid bleach compositions in plastic pouches have become popular. Usually, the contents are refilled from the pouch into a plastic bottle before use.
In particular, large-capacity pouches with spouts cannot be refilled with all the liquid at once, so it is necessary to refill while checking the liquid level in the bottle. Plastic bottles that are refilled and used repeatedly often have a window formed on the side surface for checking the remaining amount of liquid. This window is transparent or translucent. Therefore, by coloring the liquid bleach composition, it becomes easier to visually recognize the liquid through the window (the visibility of the liquid level is increased). By increasing the liquid level visibility, the liquid level can be easily checked at the time of refilling or use. In addition, since the spread of the liquid can be visually recognized even during application and washing, usability can be improved.

Liquid bleach compositions containing hydrogen peroxide tend to fade during storage. For example, Blue No. 1, which is incorporated in the liquid detergent composition of Patent Document 1, loses its color after storage when it is mixed with a bleaching agent. Therefore, it has been desired to prevent fading of liquid bleach compositions.
To address these problems, Patent Document 2 proposes a liquid bleach composition containing hydrogen peroxide, a phenolic radical trapping agent, a dye, and a surfactant. According to the liquid bleaching composition of Patent Document 2, color tone stability can be exhibited.

Japanese Patent No. 5331332 JP 2003-268398 A

However, the composition of Patent Document 2 has a problem that it has a unique odor caused by the phenol-based radical trapping agent.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid bleach composition which is excellent in color tone stability, liquid level visibility and detergency, and which suppresses odor.

The present inventors have found that the following liquid bleach composition can solve the above problems.
That is, the present invention has the following aspects.
[1] Component (A): more than 0% by mass to less than 5% by mass of hydrogen peroxide relative to the total mass of the liquid bleach composition,
(B) component: a dye having a quinone skeleton;
(C) component: 1-hydroxyethane-1,1-diphosphonic acid;
(D) component: a surfactant of 5% by mass or more with respect to the total mass of the liquid bleach composition,
Component (E): Contains 0 to less than 0.2% by mass of a phenolic radical trapping agent relative to the total mass of the liquid bleach composition, has a pH of 2 to 4 at 25°C, and a viscosity at 25°C of A liquid bleach composition that is 10 mPa·s or more.
[2] The liquid bleach composition of [1], further comprising component (F): a bleach activator.
[3] The liquid bleach composition of [1] or [2] is contained in a container having a container body, and at least part of the container body has a light transmittance of 10 in the wavelength range of 400 to 700 nm. % or more of a liquid bleach composition product.

The liquid bleach composition of the present invention is excellent in color tone stability, liquid level visibility and detergency, and can suppress odor.

BRIEF DESCRIPTION OF THE DRAWINGS It is a perspective view which shows an example of the liquid bleach composition product of this invention. Fig. 2 is a perspective view showing another example of the liquid bleach composition product of the present invention; Fig. 2 is a perspective view showing another example of the liquid bleach composition product of the present invention; Fig. 2 is a perspective view showing another example of the liquid bleach composition product of the present invention;

≪Liquid bleach composition≫
The liquid bleach composition of the present invention contains components (A) to (D) and does not contain or contains a small amount of component (E). Furthermore, it is preferable that the component (F) is included.
<(A) Component>
(A) Component is hydrogen peroxide.
The content of component (A) is more than 0% by mass and less than 5% by mass relative to the total mass of the liquid bleach composition. 0.5 to 4.5% by mass is preferred, and 1 to 4% by mass is more preferred.
(A) It is easy to improve detergency as content of a component is more than the said lower limit.
(A) It is easy to improve color tone stability as content of a component is below the said upper limit.

<(B) Component>
Component (B) is a dye having a quinone skeleton. (B) component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
Component (B) includes dyes having a p-benzoquinone skeleton, dyes having a 1,4-naphthoquinone skeleton, and dyes having an anthraquinone skeleton. Dyes having an anthraquinone skeleton (hereinafter referred to as anthraquinone-based dyes) are preferred.

Examples of anthraquinone dyes include C.I. I. Solvent Blue 63 (C.I. Solvent Blue 63, Blue No. 403), C.I. I. Solvent Violet 13 (C.I. Solvent Violet 13, Murasaki No. 201), C.I. I. Acid Green 25 (C.I. Acid Green 25, Green No. 201), C.I. I. Acid Blue 112, C.I. I. Solvent Green 3 (Green No. 202), C.I. I. Vat Blue 6 (C.I. Bat Blue 6, Blue No. 204), C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Acid Violet 43 (Purple No. 401), C.I. I. Acid Blue 41, C.I. I. Acid Blue 62, C.I. I. Acid Blue 78, C.I. I. Direct Green 28 (C.I. Direct Green 28), C.I. I. Acid Violet 34, C.I. I. Acid Vioret 41, C.I. I. Acid Vioret 51, C.I. I. Acid Blue 23, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 40, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 80, C.I. I. Acid Blue 126, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 138, C.I. I. Acid Blue 143, C.I. I. Acid Blue 182, C.I. I. Acid Blue 183, C.I. I. Acid Blue 203, C.I. I. Acid Blue 204, C.I. I. Acid Blue 205, C.I. I. Acid Green 36, C.I. I. Acid Green 40, C.I. I. Acid Green 41, C.I. I. Acid Green 44, C.I. I. Acid Brown 27 (C.I. Acid Brown 27), C.I. I. Acid Black 48 (C.I. Acid Black 48), C.I. I. Acid Black 50, C.I. I. Disperse Red 9 (C.I. Disperse Red 9), C.I. I. Solvent Violet 14, C.I. I. Disperse Violet 1, C.I. I. Acid Green 27 and the like.
As used herein, "C.I." is an abbreviation for Color Index.
The structure of each dye is described in "Legal Dyes Handbook" (edited by Japan Cosmetic Industry Association) and Dye Handbook (edited by Synthetic Organic Chemistry Society).

A compound represented by the following formula (B1) is preferable as the anthraquinone dye.

In formula (B1), X ¹ , X ² , X ³ and X ⁴ are each independently —NR ¹¹ R ¹² , hydrogen atom, —OH or —NO 2 , R ¹¹ and ^{R 12} _are each independently hydrogen an atom, a linear or branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group which may be substituted, and Y ¹ , Y ² and Y ³ , Y ⁴ are each independently a hydrogen atom, a halogen atom, —CN, —R ¹⁵ , —OR ¹⁶ , —SO ₃ H, —SO ₃ Na, or —CONH ₂ . R ¹⁵ and R ¹⁶ are each independently a linear or branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group which may be substituted with a substituent.
Preferably at least one of X ¹ , X ² , X ³ and X ⁴ is —NR ¹¹ R ¹² , more preferably at least one of X ¹ and X ² is —NR ¹¹ R ¹² and X ³ and X ⁴ , Y ³ and Y ⁴ are hydrogen atoms.
Substituents for the phenyl group include alkyl groups having 1 to 15 carbon atoms, —CO ₂ H, —CO ₂ Na, —SO ₃ H, —SO ₃ Na, or —NR ¹³ C(O)R ¹⁴ (R ¹³ , R ¹⁴ are each independently a hydrogen atom, a straight or branched chain alkyl group having 1 to 15 carbon atoms), and a phenyl group.
It is preferable that one of R ¹¹ and R ¹² is a hydrogen atom and the other is a linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group that may be substituted with a substituent.

Among the anthraquinone dyes represented by the above formula (B1), C.I. I. Solvent Blue 63 (Blue No. 403), C.I. I. Solvent Violet 13 (Purple No. 201), C.I. I. Acid Green 25 (Green No. 201), C.I. I. Solvent Green 3 (Green No. 202), C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Acid Violet 43 (Purple No. 401), C.I. I. Acid Violet 34, C.I. I. Acid Blue 45, C.I. I. Acid Green 41, and C.I. I. More preferably, one or more selected from the group consisting of Solvent Violet 14, C.I. I. Solvent Blue 63 (Blue No. 403), C.I. I. Solvent Violet 13 (Purple No. 201), C.I. I. Acid Green 25 (Green No. 201), C.I. I. Solvent Green 3 (Green No. 202), C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, and C.I. I. More preferably, one or more selected from the group consisting of Acid Violet 43 (Murasaki No. 401).

The content of component (B) is preferably 0.1 to 100 ppm by mass, more preferably 0.5 to 30 ppm by mass, and even more preferably 1 to 10 ppm by mass relative to the total mass of the liquid bleach composition.
(B) It is easy to improve liquid level visibility as content of a component is more than the said lower limit.
(B) When the content of the component is equal to or less than the above upper limit, it is difficult to color the laundry.

<(C) Component>
Component (C) is 1-hydroxyethane-1,1-diphosphonic acid. (C) Component acts as a chelating agent.
The content of component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, more preferably 0.1 to 1% by mass, relative to the total mass of the liquid bleach composition. preferable.
When the content of component (C) is within the above range, swelling of the container after storage can be easily suppressed.

<(D) Component>
(D) Component is a surfactant. Surfactants include nonionic surfactants, anionic surfactants, amphoteric surfactants, semipolar surfactants, and cationic surfactants. Component (D) may be used singly or in combination of two or more.

[Nonionic surfactant]
Examples of nonionic surfactants include those conventionally used in liquid detergents, such as polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts such as higher amines, polyoxyethylene polyoxy Propylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester , N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like. These nonionic surfactants may be used singly or in combination of two or more.
Among the above, polyoxyalkylene-type nonionic surfactants are preferred from the viewpoint of the stability of the liquid bleach, detergency, etc., and the polyoxyalkylene alkyl ether represented by the following formula (I) (hereinafter referred to as compound (I ) is particularly preferred.
R ¹ -X-[(EO) _p /(PO) _q ]-R ² (I)
[In formula (I), R ¹ is a hydrocarbon group, -X- is a divalent linking group, and R ² is a hydrogen atom, an alkyl group or an alkenyl group. EO is an oxyethylene group, and p is a number representing the average repeating number of EO. PO is an oxypropylene group, and q is a number representing the average repeating number of PO. ]
R ¹ preferably has 6 to 22 carbon atoms, more preferably 8 to 22 carbon atoms, still more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 16 carbon atoms.
The hydrocarbon group of R ¹ may be linear or branched, and may or may not have an unsaturated bond.
-X- includes -O-, -COO-, -CONH- and the like, and -O- is preferred. When -X- is -O-, R ² is preferably a hydrogen atom.
p is preferably 3-20, more preferably 4-18, particularly preferably 5-12, most preferably 6-9. q is preferably 0-6, more preferably 0-3. Also, the sum of p and q is preferably 5-20.
When q is not 0, that is, when compound (I) has both EO and PO, EO and PO may be added blockwise or randomly. Examples of the method of adding EO and PO in blocks include a method of introducing ethylene oxide and then propylene oxide, and a method of introducing propylene oxide and then ethylene oxide. The addition mole number distribution of ethylene oxide and propylene oxide is not particularly limited.
Nonionic surfactants may be used singly or in combination of two or more.

In one aspect, the liquid bleach composition may be used as an adjunct with detergents. At this time, the content of the nonionic surfactant is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the liquid bleach composition. .
When the content of the nonionic surfactant is at least the above lower limit, the detergency is likely to be improved.
When the content of the nonionic surfactant is equal to or less than the above upper limit, it is easy to improve the appearance stability of the liquid.

In other aspects, the liquid bleach composition may be used alone as a bleach-laden detergent. At this time, the content of the nonionic surfactant is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, even more preferably 20 to 60% by mass, based on the total mass of the liquid bleach composition.
When the content of the nonionic surfactant is at least the above lower limit, the detergency is likely to be improved.
When the content of the nonionic surfactant is equal to or less than the above upper limit, it is easy to improve the appearance stability of the liquid.

[Anionic surfactant]
Examples of anionic surfactants include polyoxyalkylene alkyl ether sulfuric acid or salts thereof, linear alkylbenzene sulfonic acids or salts thereof, α-olefin sulfonates, linear or branched alkyl sulfate ester salts, and alkanes having alkyl groups. sulfonates, α-sulfo fatty acid ester salts, and the like. Salts of these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more types.

Specifically, the polyoxyalkylene alkyl ether sulfuric acid or its salt is preferably a compound represented by the following general formula (II).
R ³ −[(EO) _m /(PO) _n ]—SO ₃ ⁻ M ⁺ (II)
[In formula (II), R ³ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group and PO represents an oxypropylene group. m represents the average repetition number of EO and is a number of 0 or more. n represents the average number of repetitions of PO and is a number from 0 to 6. 0<m+n. M ⁺ is the counter cation. ]
The polyoxyalkylene alkyl ether sulfate preferably has a linear or branched alkyl group of 10 to 20 carbon atoms and is added with an average of 1 to 5 mol of alkylene oxide.
The carbon number of R ³ is preferably 10-20, more preferably 12-14.
The average repeating number of EO is preferably 0 to 5, more preferably 0.5 to 3.
The average repeating number of PO is preferably 0 to 3, more preferably 0.
Examples of M ⁺ include alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion, and cations derived from alkanolamine such as monoethanolamine and diethanolamine.
In (EO) _m /(PO) _n , EO and PO may be random addition or block addition.
A commercially available product may be used, or it may be produced by a known synthesis method. Known production methods include a method of reacting a polyoxyalkylene alkyl ether with sulfuric anhydride or with chlorosulfonic acid.

As the straight-chain alkylbenzenesulfonic acid or salt thereof, those having a straight-chain alkyl group with 8 to 16 carbon atoms are preferred, and those with 10 to 14 carbon atoms are particularly preferred.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferred.
As the alkyl sulfate ester salts, those having 10 to 20 carbon atoms in the alkyl group are preferable.
The alkanesulfonate preferably has an alkyl group of 10 to 20 carbon atoms, more preferably 14 to 17 carbon atoms. Among them, those in which the alkyl group is a secondary alkyl group (that is, secondary alkanesulfonate) are particularly preferred.
The α-sulfo fatty acid ester salt preferably has a fatty acid residue with 10 to 20 carbon atoms.
Among these, polyoxyalkylene alkyl ether sulfuric acid or its salt, linear alkylbenzene sulfonic acid or its salt, alkanesulfonate, and α-olefin sulfonate are preferable in terms of excellent detergency and stability. Alkylene alkyl ether sulfuric acid or a salt thereof is more preferred.

The content of the anionic surfactant is preferably 0 to 40% by mass, more preferably 0.2 to 20% by mass, and even more preferably 0.5 to 10% by mass, relative to the total mass of the liquid bleach composition. 1 to 5% by weight is particularly preferred.
If the content is within the above range, it is possible to obtain a bleach composition having a viscosity suitable for direct application to an object and having better storage stability.

[Amphoteric Surfactant]
Amphoteric surfactants include alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidobetaine, imidazolinium betaine and the like.

[Semi-polar surfactant]
Examples of semipolar surfactants include amine oxide type surfactants such as lauryldimethylamine oxide and lauramidopropyldimethylamine oxide.

[Cationic surfactant]
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts and the like, with alkyltrimethylammonium salts being preferred. Counter ions of these salts include halogen ions such as fluoride ion, chloride ion, bromide ion, and iodide ion. For example, methylsulfate ion, ethylsulfate ion and the like can be mentioned. Cationic surfactants are preferably used in the form of methylsulfate and ethylsulfate from the viewpoint of corrosiveness to equipment.
The total content of the amphoteric surfactant, semipolar surfactant, and cationic surfactant is preferably 0 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total mass of the liquid bleach composition. Preferably, 0.3 to 3% by mass is more preferable, and 0.5 to 1.5% by mass is particularly preferable.

In the present invention, the content of component (D) (total amount of surfactant) is 5% by mass or more relative to the total mass of the liquid bleach composition.
In one aspect, the liquid bleach composition may be used as an adjunct with detergents. In this case, the content of component (D) is preferably 5 to 20% by mass, more preferably 7 to 15% by mass, based on the total mass of the liquid bleach composition.
(D) It is easy to improve detergency as content of a component is more than the said lower limit.
(D) It is easy to improve appearance stability as content of a component is below the said upper limit.

In other aspects, the liquid bleach composition may be used alone as a bleach-laden detergent. In this case, the content of component (D) is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, and even more preferably 30 to 60% by mass, relative to the total mass of the liquid bleach composition.
(D) It is easy to improve detergency as content of a component is more than the said lower limit.
(D) It is easy to improve appearance stability as content of a component is below the said upper limit.

<(E) Component>
(E) Component is a phenolic radical trapping agent.
Examples of component (E) include p-methoxyphenol and dibutylhydroxytoluene.
(E) component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

The content of component (E) is 0 to less than 0.2% by mass, preferably 0 to 0.1%, more preferably 0 to 0.05% by mass, relative to the total mass of the liquid bleach composition. .
(E) It is easy to suppress the odor of a liquid bleach composition as content of a component is below the said upper limit.

<(F) Component>
Component (F) is a bleach activator. Component (F) is a substance that does not have a bleaching effect per se, but reacts with hydrogen peroxide in a liquid bleaching composition to turn into a highly oxidizing organic peracid.
A known compound can be used as a bleach activator. For example, tetraacetylethylenediamine; alkanoyloxybenzenesulfonic acid or a salt thereof having an alkanoyl group having 1 to 18 carbon atoms, preferably 8 to 12 carbon atoms; alkanoyl group having 1 to 18 carbon atoms, preferably 8 to 12 carbon atoms alkanoyloxybenzoic acid or a salt thereof. Among these, 4-decanoyloxybenzoic acid (DOBA), sodium 4-dodecanoyloxybenzenesulfonate (DOBS), and sodium 4-nonanoyloxybenzenesulfonate (NOBS) are preferred.
Component (F) may be used singly or in combination of two or more.

The content of component (F) is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.4 to 1% by mass relative to the total mass of the liquid bleach composition. is more preferred.
When the content of the bleaching activator is at least the above lower limit, the bleaching power against yellowing in the liquid bleach composition increases.
Appearance stability can be improved when the content of the bleaching activator is equal to or less than the above upper limit.

<Optional component>
The liquid bleaching composition of the present invention may contain optional components commonly used in liquid bleaching compositions, in addition to the above components (A) to (F).
Optional components include pH adjusters, organic solvents, perfumes, hydrotropic agents, antibacterial agents, buffers, and solvents.

[pH adjuster]
Examples of pH adjusters include sodium hydroxide, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and ammonia.

[Perfume]
The perfume includes a perfume raw material alone, or a perfume composition comprising a perfume raw material, a perfume solvent, a perfume stabilizer, and the like, and can be blended with perfumes commonly used in liquid bleach compositions.
The content of perfume is preferably 0.01 to 1.0% by weight relative to the total weight of the liquid bleach composition.

[Hydrotropic agent]
Examples of hydrotropic agents include water-miscible organic solvents such as alcohols having 2 to 4 carbon atoms, glycols, polyglycols, and alkyl ethers; toluenesulfonic acid, xylenesulfonic acid, benzoates, and urea. be done.
The content of the hydrotrope agent is preferably 0.01-15% by weight relative to the total weight of the liquid bleach composition.
Water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol; glycols such as propylene glycol, butylene glycol and hexylene glycol; polyglycols such as dipropylene glycol; Alkyl ethers such as monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether and 3-methoxy-3-methyl-1-butanol, and aromatic ethers such as phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether. Among these, ethanol, propylene glycol, diethylene glycol monobutyl ether (butyl carbitol), 3-methoxy-3-methyl-1-butanol, phenoxyethanol and diethylene glycol monophenyl ether are preferred.
The water-miscible organic solvents may be used singly or in combination of two or more. The content of the water-miscible organic solvent is preferably 0.1-15% by weight relative to the total weight of the liquid bleach composition. In the present invention, the water-miscible organic solvent refers to an organic solvent that dissolves 20 g or more in 1 L of deionized water at 25°C.

[Antibacterial agent]
Antibacterial agents include diclosan, triclosan, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanide hydrochloride, 8-oxyquinoline, polylysine and the like.
The content of the antibacterial agent is preferably more than 0% by mass and 3% by mass or less, more preferably 0.001 to 1% by mass, and 0.005 to 0.5% by mass, relative to the total mass of the liquid bleach composition. is more preferable, and 0.01 to 0.3% by mass is particularly preferable.

[Buffer]
Buffers include citric acid, borate compounds such as sodium tetraborate, and the like.
The content of the buffering agent is preferably 0.01-2% by mass relative to the total mass of the liquid bleach composition.

[solvent]
It preferably contains water as a solvent.
The liquid bleach composition of the present invention is preferably an aqueous solution and preferably does not form an emulsion.
The water content is preferably 30% by mass or more, more preferably 35 to 95% by mass, even more preferably 50 to 95% by mass, and most preferably 80 to 90% by mass, relative to the total mass of the liquid bleach composition. .
The total content of each component of the liquid bleach composition of the present invention does not exceed 100% by mass.

The pH of the liquid bleach composition of the present invention at 25° C. is 2-4, preferably 2-3, more preferably 2.5-3. When the pH of the liquid bleach composition is within the above range, the color tone stability is excellent.
The pH of the liquid bleach composition can be adjusted by adding a pH adjuster, if desired.
In the present specification, pH means a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) at 25°C.

The viscosity of the liquid bleach composition of the present invention at 25° C. is 10 mPa·s or more, preferably 20 to 300 mPa·s, more preferably 30 to 200 mPa·s. When the viscosity of the liquid bleach composition is at least the lower limit of the above range, the effect of suppressing foaming is excellent, and the liquid level visibility is excellent. Usability is easy to improve as it is below an upper limit.
The viscosity of the liquid bleach composition can be adjusted by adjusting the solvent, amount of hydrotropic agent added, pH and the like.
In this specification, viscosity means a value measured using a B-type (Brookfield type) viscometer at a temperature of 25°C.

<<Method for producing liquid bleach composition>>
The liquid bleach composition of the present invention can be prepared, for example, by mixing components (A) to (D), and optionally components (E), (F), and optional components, and adjusted to a predetermined pH as required. It can be manufactured by adjusting

≪How to use the liquid bleach composition≫
The method of using the liquid bleach composition of the present invention includes, for example, adding the liquid bleach composition alone or together with a known detergent or softener to water to prepare a washing liquid, putting the article to be washed in this washing liquid, and washing the washing machine. and a method of preliminarily dissolving the liquid bleach composition in water, immersing the article to be washed in this solution, and then washing it with a washing machine. Moreover, after applying the liquid bleach composition to the article to be washed, the article may be left to stand as appropriate, and then normal washing may be performed.
Examples of items to be washed include textile products such as clothes, fabrics, sheets, curtains, and carpets.
The content of the liquid bleach composition in the washing liquid is not particularly limited. The amount of liquid bleach composition added to water is, for example, 2 to 15 mL of liquid bleach composition per 10 L of water.

≪Liquid bleach composition products≫
The liquid bleach composition product of the present invention contains the liquid bleach composition of the present invention in a container having a container body.
FIG. 1 is a perspective view showing an example of the liquid bleach composition product of the present invention. The liquid bleach composition product 1 of FIG. 1 comprises a container body 100 having a substantially rectangular parallelepiped appearance for containing the liquid bleach composition 10 and a detachably attached cap 110 .
At least part of the container body has a light transmittance of 10% or more. In this specification, light transmittance is a value in a wavelength range of 400 to 700 nm, and SolidSpec-3700 manufactured by Shimadzu Corporation was used for measuring light transmittance.
For example, in FIG. 1, the container body 100 has a window portion 20 on the side surface through which the inside can be visually recognized. The window portion 20 is formed along the longitudinal direction (height direction) of the container body 100 . The window portion 20 has a light transmittance of 10% or more.
The area of the window part 20 is preferably 0.5 area % or more with respect to the total surface area of the container.

The liquid bleach composition product 2 of FIG. 2 includes a container body 100a having a flat, octagonal appearance in a front view containing the liquid bleach composition 10a, and a detachably attached cap 110a.
The container main body 100a has a window portion 20a on its side surface through which the inside can be visually recognized. The window portion 20a is formed along the longitudinal direction (height direction) of the container body 100a. The window portion 20a has a light transmittance of 10% or more.
The area of the window portion 20a is preferably 0.5 area % or more with respect to the total surface area of the container.

The liquid bleach composition product 3 of FIG. 3 includes a container body 100b having a substantially cylindrical appearance that houses the liquid bleach composition 10b, and a detachably attached cap 110b.
The container body 100b has an overall light transmittance of 10% or more.
The liquid bleach composition product 4 of FIG. 4 comprises a generally cylindrical-appearing container body 100b containing the liquid bleach composition 10b and a detachably attached cap 110b. A product 3 is provided with a label 120 having a transparent portion 130. - 特許庁
When the label 120 having the transparent portion 130 is provided on the container body 100b, the transparent portion 130 serves as a window portion, and the inside can be visually recognized through the transparent portion 130. - 特許庁The transparent portion 130 is formed along the longitudinal direction (height direction) of the container body 100b.

Preferably the container is a flexible container. “Flexible” means that the container flexibly deforms without breaking when the pressure inside the container changes.
Examples of flexible containers include plastic containers, paper containers, and metal containers.
Constituent materials for plastic containers include polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyacetal (POM), and polyethylene naphthalate. (PEN), polystyrene (PS), acrylonitrile-butadiene-styrene resin (ABS), cellulose propionate (CP), polyarylate, polycarbonate, acrylonitrile-styrene copolymer resin (AS), and the like.
Aluminum etc. are mentioned as a constituent material of a metal container.
In addition, a laminate in which metal foil is attached to paper, a laminate in which paper is attached to plastic, a laminate in which metal foil is attached to plastic, and the like can be used.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.
Each component was mixed according to the composition shown in Tables 1, 2 and 3 to obtain each liquid bleach composition.
The unit of the compounding amount in the table is "mass ppm" for component (B) and "mass %" for components other than component (B), and all the components show the amount in terms of pure content.
Blanks in the table indicate that the component was not included.
"Balanced" means that water is blended so that the total amount (% by mass) of all compounding components contained in the composition of each example is 100% by mass.
The components shown in the table are described below.

<(A) Component>
· a-1: Hydrogen peroxide (35 mass% industrial hydrogen peroxide, manufactured by Mitsubishi Gas Chemical Company, Inc.).
<(B) Component>
・b-1: C.I. I. Solvent Violet 13 (Murasaki No. 201, structure is the following formula (B1-1)), manufactured by Kisumi Kasei Co., Ltd., Murasaki No. 201.
· b-2: C.I. I. Solvent Blue 63 (Blue No. 403, structure is the following formula ((B1-2)), manufactured by Kisumi Kasei Co., Ltd., Blue No. 403.
· b-3: C.I. I. Solvent Green 3 (Green No. 202, the structure is the following formula ((B1-3)), manufactured by Kisumi Kasei Co., Ltd., Green No. 202.
<Comparative product of component (B)>
· b'-1: C.I. I. Acid Blue 74 (blue No. 2, structure is the following formula (B'-1)), manufactured by Daiwa Kasei Co., Ltd., Blue No. 2.
· b'-2: C.I. I. Food Blue 2 (Blue No. 1, manufactured by Koyo Chemical Co., Ltd., Food Blue No. 1 (Brilliant Blue FCF), structure represented by the following formula (B'-2)).

<(C) Component>
· c-1: 1-Hydroxyethane-1,1-diphosphonic acid (HEDP), manufactured by Italmatch, trade name "Dequest 2010".
<(D) Component>
・d-1 (AE6 ⁾ : polyoxyethylene alkyl ether, manufactured by Lion Corporation, trade name “Rheox CL-60”; a compound which is an alkyl group, wherein R ² is a hydrogen atom, X is O, p is 6, and q is 0;
・d-2 (AE9): ^{polyoxyethylene} alkyl ether, manufactured by Lion Corporation, trade name “Rheox CL-90”; a compound which is an alkyl group, wherein R ² is a hydrogen atom, X is O, p is 9 and q is 0;
d-3 (AES): Sodium polyoxyalkylene alkyl ether sulfate (sodium polyoxyethylene lauryl ether sulfate, average number of added moles of EO: 2) (manufactured by Shin Nippon Rika Co., Ltd., trade name "Sinoline SPE-1250"). )
d-4 (LAS): linear alkyl (carbon number 10-14) sodium benzenesulfonate, manufactured by Lion Corporation, trade name “Lipon LS250”.
d-5 (APAX): lauramidopropyl dimethylamine oxide, manufactured by Clariant, trade name “GENAMINOX AP”; in the following formula (III), R ⁴ is a linear alkyl group having 11 carbon atoms; a compound in which ⁵ and ^R6 are methyl groups and q is 3;

d-6: Lauryldimethylethylammonium ethylsulfate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name “Cathiogen ES-L”) In the following formula (IV), R ⁷ is a dodecyl group, R ⁸ is a methyl group, and R ⁹ is a methyl group, R ¹⁰ is an ethyl group, and Z ₁ ^- is an ethyl sulfate ion.

d-7: polyoxyethylene polyoxypropylene alkyl ether (EOPO type nonion, natural alcohol CO1270 (C12/C14 = 7/3 (mass ratio), manufactured by Procter & Gamble), 8 mol of ethylene oxide and , a nonionic surfactant obtained by block addition of 2 mol of propylene oxide and 8 mol of ethylene oxide in this order).
· d-8: Soap, manufactured by NOF Corporation, trade name "coconut fatty acid".

<(E) component>
· e-1: p-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “MQ-F”).
<(F) Component>
· f-1: Sodium 4-lauroyloxybenzenesulfonate (OBS), synthesized according to the procedure described in paragraph 0114 of JP-A-2011-57745.
<Optional component>
· ProxelIB: Polyhexamethylene biguanide, manufactured by Lonza Japan Co., Ltd., trade name "Proxel IB"; a compound of the following formula (V).

Perfume: Perfume composition A described in Tables 1 to 6 of JP-A-2011-225743.
- Solvent: butyl carbitol, trade name "butyl diglycol" manufactured by Nippon Nyukazai Co., Ltd.
· p-toluenesulfonic acid (PTS): manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name "PTS acid".
- pH adjuster: sulfuric acid (manufactured by Nissan Chemical Industries, Ltd.), sodium hydroxide (manufactured by Asahi Glass Co., Ltd.).
- Water: Purified water.

<Evaluation of Color Stability>
Clear glass bottles were each filled with 100 g of the liquid bleach composition of each example and sealed with a cap. The bottle was stored at 50° C. for 20 days.
After such storage, the appearance of the liquid was visually observed, and the color tone stability of the liquid bleach composition was visually evaluated according to the following evaluation criteria.
[Evaluation Criteria for Color Stability]
○: The color tone was maintained.
x: The color tone is obviously deteriorated.

<Evaluation of liquid level visibility>
The liquid bleach composition of each example after standing and stored at 50 ° C. for 20 days is packed in a pouch with a spout, poured into a container with a window through which the liquid level can be seen, and the visibility of the liquid level is confirmed. was visually evaluated according to the following evaluation criteria.
[Evaluation criteria for liquid level visibility]
◯: The liquid level is easy to distinguish (distinguishable at a glance).
Δ: The liquid level is somewhat easily discernible.
x: It is not easy to distinguish the liquid level (cannot be distinguished at first glance).

<Evaluation of detergency>
(1) Preparation of oil stain cloth 0.02 mL of chili oil (manufactured by SB Co., Ltd.) was dropped on a polyester tropical cloth cut to 3 cm x 3 cm, and air-dried overnight at room temperature. Dirty cloth."
(2) Washing Test 0.12 mL of the same liquid bleach composition was applied to each of five oil-stained cloths and allowed to stand for 5 minutes.
After that, put 900 mL of tap water adjusted to a water temperature of 15 ° C. into a cleaning tester (Terg-O-Tometer), 0.75 g of detergent (manufactured by Lion Corporation, trade name "Top Clear Liquid") and oil stain cloth Five pieces were placed and washed at 120 rpm for 10 minutes (bath ratio 20 times).
After washing, it was dehydrated and rinsed with 900 mL of tap water (15° C.) for 3 minutes. After rinsing, the fabric was dehydrated and dried with an iron, and the fabric was defined as "oil-stained cloth after washing".
3) Evaluation of detergency The detergency was evaluated using a colorimetric colorimeter (manufactured by Nippon Denshoku Co., Ltd., trade name SE2000), using a raw cloth before staining (polyester tropical cloth before dripping chili oil), and before and after the washing test. The Z value of the oil-stained cloth was measured and evaluated by calculating the cleaning rate from the following formula. For the evaluation, the average value of the detergency calculated for five oil-stained cloths was obtained, and the detergency was evaluated according to the following evaluation criteria.
Cleaning rate (%) = (Z value of oil stained cloth after washing - Z value of oil stained cloth before washing) / (Z value of raw cloth - Z value of oil stained cloth before washing ) x 100
[Evaluation criteria for detergency]
◯: The average value of cleaning rate is 15% or more.
x: The average value of cleaning rate is less than 15%.

<Evaluation of Odor>
As evaluation criteria, a model liquid bleach composition having the composition shown below was used.
Composition: 3% hydrogen peroxide, 10% AE(6), 2% AES, 0.2% HEDP, 0.02% Proxel IB, 0.01% fragrance, sodium hydroxide required to adjust pH to 4, purified water balance .
100 g of the model liquid bleaching composition (standard product) and 100 g of the bleaching composition of each example were placed in glass bottles, and the odor at the mouth of the bottle was sensory compared. The results were evaluated according to the following evaluation criteria.
[Evaluation Criteria for Odor]
◯: The unpleasant odor of the product is felt to be equal to or lower than that of the standard product.
x: The unpleasant odor of the product is perceived stronger than that of the standard product.

<Measurement of viscosity>
The liquid temperature of the liquid cleaning agent of each example was adjusted to 25° C. in a constant temperature bath and used as a measurement sample. The viscosity of the measurement sample was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., "model BM") (rotor No.
2, rotation speed 60 rpm, measurement of viscosity 60 seconds after the start of rotation).

Examples 1 to 15 to which the present invention was applied were excellent in color tone stability, liquid level visibility, detergency and odor. In particular, in Examples 2, 4, 5, 6 to 9, 11, and 13 to 15, in which the viscosity of the liquid was high, the liquid surface hardly foamed when poured into a container, and the visibility of the liquid level was excellent.
Comparative Examples 1, 4, and 11, in which the content of the component (E) was large, were inferior in the odor of the composition.
In Comparative Examples 3 and 5, which had a high pH, the composition faded to a nearly transparent color tone, so the liquid level could not be determined at a glance.
Comparative Examples 2, 6, and 12, in which the total amount of component (D) was small, were inferior in detergency.
Comparative Examples 7, 8, 9, and 10 using dyes having no quinone skeleton did not contain the component (E), and although the pH and viscosity were comparable to those of Examples, the composition did not fade. The color became almost transparent, and the liquid surface could not be determined at a glance.

1, 2, 3, 4 Liquid bleach composition product 10, 10a, 10b Liquid bleach composition 20, 20a Window 100, 100a, 100b Container body 110, 110a, 110b Cap 120 Label 130 Transparent part

Claims (4)

(A) component: more than 0% by mass to less than 5% by mass of hydrogen peroxide relative to the total mass of the liquid bleach composition,
(B) Component: C.I. I. Solvent Violet 13 (Purple No. 201), and C.I. I. a dye having one or more quinone skeletons selected from the group consisting of Solvent Green 3 (Green No. 202);
(C) component: 1-hydroxyethane-1,1-diphosphonic acid;
(D) component: a surfactant of 5% by mass or more with respect to the total mass of the liquid bleach composition,
(E) component: 0 to less than 0.2% by mass of a phenolic radical trapping agent relative to the total mass of the liquid bleach composition;
A liquid bleach composition having a pH of 2 to 4 at 25°C and a viscosity of 10 mPa·s or more at 25°C (excluding those containing a boron compound and the following polyol compound) .
Polyol compounds: glucose, mannose, galactose, fructose, ribose, erythrose, xylulose, gluconic acid, galactonic acid, mannonic acid, glucuronic acid, maltose, cellobiose, lactose, sucrose, sorbitol, alkylglucosides of these sugars, sorbitan fatty acid esters, A compound selected from polyoxyethylene sorbitan fatty acid esters, glycerin, glycerin monoalkyl ethers, glycerin derivatives, alkyldiols, and alkylenediols. 2. The liquid bleach composition of claim 1, further comprising (F) component: bleach activator. The liquid according to claim 1 or 2, wherein the component (D) comprises one or more selected from the group consisting of anionic surfactants, semipolar surfactants and cationic surfactants, and a nonionic surfactant. bleach composition. The liquid bleach composition according to any one of claims 1 to 3 is stored in a container having a container body,
A liquid bleach composition product, wherein at least part of the container body has a light transmittance of 10% or more in a wavelength region of 400 to 700 nm.

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