JP7162468B2 - Liquid bleach composition and liquid bleach composition product - Google Patents

Description

The present invention relates to liquid bleach compositions and liquid bleach composition products.

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.
A liquid bleach composition in a plastic pouch (bleach in a pouch) has become popular for the purpose of reducing environmental load. Usually, the contents of the pouch are refilled into a plastic bottle before use.
When refilling a large amount of pouched bleach into a plastic bottle, it is necessary to refill while checking the liquid level of the plastic bottle. A plastic bottle that is refilled and used repeatedly has a window on its side for checking the remaining amount of liquid. 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, a liquid detergent composition containing Blue No. 1 as a pigment has a problem that it tends to lose its color after storage when a bleaching agent is added.
To address these problems, Patent Document 1 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 1, color tone stability can be exhibited.

JP-A-2003-268398

However, although the liquid bleach composition of Patent Document 1 has enhanced color tone stability under sunlight exposure conditions, color tone stability and liquid level visibility after storage at high temperature (e.g., 50°C) are not sufficient. I didn't.

The present invention has been made in view of the above circumstances, and aims to provide a liquid bleach composition and a liquid bleach composition product which are excellent in color tone stability and liquid level visibility.

As a result of intensive studies, the present inventors found that a liquid bleach composition having excellent color tone stability and liquid level visibility after high-temperature storage can be obtained by blending a dye having a specific structure. rice field.
That is, the present invention has the following aspects.

[1] Component (A): hydrogen peroxide; Component (B): one or more dyes selected from compounds represented by the following formula (I) and compounds represented by the following formula (II); C) Component: A liquid bleach composition containing a surfactant.

[2] The liquid bleach composition according to [1], which has a pH of 2 to 8 at 25°C.
[3] Component (C) contains one or more selected from component (c1): nonionic surfactant, component (c2): anionic surfactant, and component (c3): semipolar surfactant. , [1] or [2].
[4] It contains the component (c2) and the component (c3), and the mass ratio represented by the component (c2)/the component (c3) is 0.9 to 2.0, [3 ].
[5] The component (c2) is polyoxyalkylene alkyl ether sulfuric acid or its salt (AES), and the component (c3) is lauramidopropyl dimethylamine oxide (APAX), [3] or [4] The liquid bleach composition according to .
[6] The ratio of mass% of the component (A) to mass ppm of the component (B) ((A) mass%/(B) mass ppm) is 0.005 to 50, [1] to [ 5], the liquid bleach composition according to any one of the above.
[7] The ratio of the mass% of the component (C) to the mass ppm of the component (B) ((C) mass%/(B) mass ppm) is 0.01 to 700, [1] to [ 6], the liquid bleach composition according to any one of the above.
[8] The liquid bleach composition according to any one of [1] to [7] is contained in a container having a container body, and at least a part of the container body has a wavelength range of 400 to 700 nm. A liquid bleach composition product having a light transmittance of 10% or more.

The liquid bleach composition of the present invention is excellent in color tone stability and liquid level visibility.

BRIEF DESCRIPTION OF THE DRAWINGS It is a perspective view which shows an example of the liquid bleach composition product of this invention.

[Liquid bleach composition]
The liquid bleach composition of the present invention (hereinafter also simply referred to as "liquid bleach") is a composition containing components (A), (B) and (C).
The liquid bleaching agent may be an auxiliary agent (so-called bleaching agent) used together with the detergent, or may be a detergent containing bleaching agent (so-called bleaching detergent).
A so-called bleaching agent is a composition intended mainly for bleaching an object to be treated, and focusing on the bleaching effect.
A so-called bleach cleaning agent is a composition intended mainly for cleaning objects to be treated, and is inferior in bleaching effect to a bleaching agent, but emphasizes detergency.

<(A) Component>
(A) Component is hydrogen peroxide.
The content of component (A) is preferably more than 0% by mass and less than 5% by mass, more preferably 0.5% to 4.5% by mass, and 1% to 4% by mass, relative to the total mass of the liquid bleach. 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 one or more dyes selected from compounds represented by the following formula (I) and compounds represented by the following formula (II). The liquid bleaching agent of the present invention tends to be excellent in color tone stability by containing the (B) component. This is presumably because component (B) has excellent stability of the intramolecular charge transfer state even in the presence of hydrogen peroxide, which can cause dye fading.

The compound represented by the above formula (I) includes 1,4-bis[(4-methylphenyl)amino]anthracene-9,10-dione (Qinizarin Green SS, CI Solvent Green 3 , Green No. 202)).
The compound represented by formula (II) above is 1,4-bis(phenylamino)anthracene-9,10-dione.
From the viewpoint of superior color tone stability, the compound represented by the above formula (I) (hereinafter also referred to as "Green No. 202") is preferable as the component (B).

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 0.5 to 10 ppm by mass, relative to the total mass of the liquid bleach. .
(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>
(C) Component is a surfactant. Examples of surfactants include nonionic surfactants (component (c1)), anionic surfactants (component (c2)), semipolar surfactants (component (c3)), and amphoteric surfactants (component (c4)). and cationic surfactants (component (c5)).
(C) component may be used individually by 1 type, and may use 2 or more types together.

((c1) component)
(c1) Component is a nonionic surfactant.
As the component (c1), any one conventionally used in liquid detergents may be used. Oxide adducts, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, hydrogenated castor oil alkylene oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like.
These (c1) components may be used individually by 1 type, and may use 2 or more types together.
Among the above, polyoxyalkylene-type nonionic surfactants are preferred from the viewpoint of the stability of liquid bleaches, detergency, etc., and polyoxyalkylene alkyl ethers represented by the following formula (c1-1) (hereinafter referred to as compounds (c1-1) is particularly preferred.
R ¹ -X-[(EO) _p /(PO) _q ]-R ² (c1-1)
(c1-1) wherein 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. The hydrocarbon group of R ¹ 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 to 20, more preferably 4 to 18, even more preferably 5 to 12, and particularly preferably 6 to 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 (c1-1) 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.
(c1) component may be used individually by 1 type, and may use 2 or more types together.

When the liquid bleaching agent is a so-called bleaching agent, the content of component (c1) is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, relative to the total mass of the liquid bleaching agent. , 0.5 to 7 mass % is more preferable.
(c1) It is easy to improve detergency that content of a component is more than the said lower limit.
(c1) It is easy to improve the appearance stability of a liquid bleaching agent as content of a component is below the said upper limit.

When the liquid bleach is a so-called bleach detergent, the content of component (c1) is preferably 5 to 65% by mass, more preferably 10 to 60% by mass, more preferably 20 to 60% by mass, based on the total mass of the liquid bleach. 55% by mass is more preferred.
(c1) It is easy to improve detergency that content of a component is more than the said lower limit.
(c1) It is easy to improve the appearance stability of a liquid bleaching agent as content of a component is below the said upper limit.

(Component (c2))
Component (c2) is an anionic surfactant.
Component (c2) includes, for example, polyoxyalkylene alkyl ether sulfuric acid or its salt (AES), linear alkylbenzene sulfonic acid or its salt (LAS), α-olefin sulfonate (AOS), linear or branched Alkyl sulfate ester salts (AS), alkyl group-containing alkanesulfonates (SAS), α-sulfo fatty acid ester salts (MES) and the like can be mentioned. Examples of the salt in component (c2) include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
(c2) component may be used individually by 1 type, and may use 2 or more types together.

Specifically, AES is preferably a compound represented by the following formula (c2-1).
R ³ −[(EO) _m /(PO) _n ]—SO ₃ ⁻ M ⁺ (c2-1)
In formula (c2-1), 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.
AES preferably has a linear or branched alkyl group with 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 2.5, even more preferably 1.5 to 2.5.
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 added in blocks or in random.
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 LAS, straight-chain alkyl groups having 8 to 16 carbon atoms are preferable, and those having 10 to 14 carbon atoms are particularly preferable.
AOS having 10 to 20 carbon atoms is preferable.
AS is preferably an alkyl group having 10 to 20 carbon atoms.
SAS preferably has an alkyl group with 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.
As the MES, those having 10 to 20 carbon atoms in the fatty acid residue are preferred.
Among these, AES, LAS, SAS, and AOS are preferred, and AES is more preferred, in terms of excellent detergency and stability.

When the liquid bleaching agent is a so-called bleaching agent, the content of component (c2) is preferably 0 to 10% by weight, more preferably 0.5 to 8% by weight, based on the total weight of the liquid bleaching agent. 0.5 to 7 mass % is more preferred.
When the content of component (c2) is within the above numerical range, it is possible to obtain a liquid bleaching agent having a viscosity suitable for direct application to an object and having better appearance stability.

When the liquid bleach is a so-called bleach detergent, the content of component (c2) is preferably 0 to 40% by mass, more preferably 1 to 20% by mass, more preferably 1 to 20% by mass, based on the total mass of the liquid bleach. 7% by mass is more preferred.
When the content of component (c2) is within the above numerical range, it is possible to obtain a liquid bleaching agent having a viscosity suitable for direct application to an object and having better appearance stability.

(Component (c3))
Component (c3) is a semi-polar surfactant.
Component (c3) includes amine oxide surfactants such as lauryldimethylamine oxide and lauramidopropyldimethylamine oxide (APAX).

((c4) component)
Component (c4) is an amphoteric surfactant.
Component (c4) includes alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidobetaine, imidazolinium betaine, and the like.

((c5) component)
Component (c5) is a cationic surfactant.
Component (c5) includes, for example, 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. Component (c5) is preferably used as methylsulfate or ethylsulfate from the viewpoint of corrosiveness to equipment.

It is preferable to use the liquid bleaching agent in combination with component (c1) and one or more selected from components (c2) to (c5). When the component (c1) and one or more selected from the components (c2) to (c5) are used in combination, the total of the components (c1) and (c2) to (c5) (hereinafter referred to as "other than the component (c1) ” (hereinafter also referred to as “ratio other than c1/c1”) is preferably 0.25 to 20, more preferably 0.25 to 1.5.
When the ratio other than c1/c1 is within the above numerical range, it is easier to improve the appearance stability of the liquid bleach.

The liquid bleach preferably contains component (c2) in order to improve not only bleaching activity but also detergency.
However, if a large amount of AES or LAS is blended as the component (c2), the detergency of the liquid bleach can be improved, but the stability of the liquid bleach is poor, and the composition becomes cloudy and the visibility of the liquid level is reduced. There is In particular, when the inner wall of the container is white, the color of the cloudy liquid bleaching agent becomes the same white as the color of the inner wall of the container, which may further reduce the liquid level visibility.
Therefore, the liquid bleach preferably contains component (c3). When the liquid bleaching agent contains both the (c2) component and the (c3) component, the (c2) component and the (c3) component form a complex, and the cloudiness of the liquid bleaching agent can be suppressed. In addition, the detergency of the liquid bleach is improved.
A combination of AES and APAX is preferable as the combination of the (c2) component and the (c3) component that exhibits such an effect.
Moreover, in order to promote the miscibility of the above component (B) with water, the liquid bleach preferably contains the component (c1). As the component (c1), the above-described compound (c1-1) is preferable, and AE6 (in the above formula (c1-1), R ¹ is a linear alkyl group having 12 and 14 carbon atoms, and R ² is a hydrogen atom, X is O, p is 6, and q is 0.) is more preferred.
As the liquid bleaching agent, it is preferable to use components (c1), (c2) and (c3) in combination, and it is particularly preferable to use AE6, AES and APAX in combination.

When the liquid bleach contains the (c2) component and the (c3) component, the mass ratio represented by (c2) component/(c3) component (hereinafter also referred to as "c2/c3 ratio") is 0.9 to 2.0 is preferred, 1.0 to 1.9 is more preferred, and 1.1 to 1.8 is even more preferred.
When the c2/c3 ratio is within the above numerical range, it is easier to improve the liquid level visibility of the liquid bleach.

The total content of components (c3) to (c5) is preferably 0 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.3 to 3% by mass relative to the total mass of the liquid bleaching agent. % is more preferred, and 0.5 to 1.8% by mass is particularly preferred.
When the total content of components (c3) to (c5) is within the above numerical range, the appearance stability of the liquid bleach can be more easily improved.

The content of component (C) (the total amount of surfactants) is preferably 0.5% by mass or more relative to the total mass of the liquid detergent.
When the liquid bleaching agent is a so-called bleaching agent, the content of component (C) is preferably 0.5 to 30% by mass, more preferably 1.5 to 25% by mass, relative to the total mass of the liquid bleaching agent. , 3 to 15 mass % is more preferable.
(C) It is easy to improve the detergency of a liquid bleach as content of a component is more than the said lower limit.
(C) It is easy to improve the external appearance stability of a liquid bleaching agent as content of a component is below the said upper limit.

When the liquid bleach is a so-called bleach detergent, the content of component (C) is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, more preferably 20 to 70% by mass, based on the total mass of the liquid bleach. 60% by mass is more preferred.
(C) It is easy to improve the detergency of a liquid bleach as content of a component is more than the said lower limit.
(C) It is easy to improve the external appearance stability of a liquid bleaching agent as content of a component is below the said upper limit.

The ratio of mass% of component (A) to mass ppm of component (B) ((A) mass%/(B) mass ppm, hereinafter also referred to as “A/B ratio”) is 0.005 to 50 It is preferably 0.1 to 10, more preferably 0.5 to 5.
When the A/B ratio is at least the above lower limit, it is easy to suppress the coloring of the laundry (the ability to dye the fabric).
When the A/B ratio is equal to or less than the above upper limit, the color tone stability of the liquid bleach is likely to be maintained.

The ratio of mass% of component (C) to mass ppm of component (B) ((C) mass%/(B) mass ppm, hereinafter also referred to as “C/B ratio”) is 0.01 to 700 Preferably, 0.1 to 70 is more preferable, and 1 to 65 is even more preferable.
When the C/B ratio is at least the above lower limit, it is easy to suppress the coloring of the washed material (the ability to dye the fabric).
When the C/B ratio is equal to or less than the above upper limit, the color tone stability of the liquid bleach is likely to be maintained.

<Optional component>
The liquid bleaching agent of the present invention may contain, in addition to the above components (A) to (C), optional components commonly used in liquid bleaching agents.
Optional components include, for example, pH adjusters, chelating agents, radical trapping agents, organic solvents, buffering agents, perfumes, solvents, hydrotropic agents, antibacterial agents, and bleaching activators.

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

(chelating agent)
Chelating agents include 1-hydroxyethane-1,1-diphosphonic acid (HEDP).
When the liquid bleach contains a chelating agent, the content of the chelating agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on the total mass of the liquid bleaching agent. .1 to 1 mass % is more preferred.
When the content of the chelating agent is within the above numerical range, it is easy to suppress swelling of the container after storage.

(radical trap agent)
Radical trapping agents include, for example, p-methoxyphenol and dibutylhydroxytoluene.
The radical trapping agents may be used singly or in combination of two or more.
The content of the radical trapping agent is preferably 0 to less than 0.2% by mass, more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.05% by mass, relative to the total mass of the liquid bleaching agent. .
When the content of the radical trapping agent is equal to or less than the above upper limit, it is easy to suppress the odor of the liquid bleach.

(Organic solvent)
As the organic solvent, a water-miscible organic solvent is preferred. As used herein, the term "water-miscible organic solvent" refers to an organic solvent that dissolves 20 g or more in 1 L of deionized water at 25°C.
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; diethylene glycol. Alkyl ethers such as monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether and 3-methoxy-3-methyl-1-butanol; aromatic ethers such as phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether; be done. 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.
When the liquid bleaching agent contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably 0.1 to 15% by weight based on the total weight of the liquid bleaching agent.

(buffer)
Buffers include citric acid, borate compounds such as sodium tetraborate, and the like.
When the liquid bleaching agent contains a buffering agent, the content of the buffering agent is preferably 0.01 to 2% by weight relative to the total weight of the liquid bleaching agent.

(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 perfumes commonly used in liquid bleaches can be blended.
When the liquid bleaching agent contains perfume, the content of the perfume is preferably 0.01 to 1.0% by weight based on the total weight of the liquid bleaching agent.

(solvent)
It preferably contains water as a solvent.
The liquid bleach 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 particularly preferably 80 to 90% by mass, relative to the total mass of the liquid bleach.

(Hydrotropic agent)
Hydrotropic agents include, for example, toluenesulfonic acid, xylenesulfonic acid, benzoates, and urea.
When the liquid bleaching agent contains a hydrotropic agent, the content of the hydrotropic agent is preferably 0.01 to 15% by weight relative to the total weight of the liquid bleaching agent.

(Antibacterial agent)
Antibacterial agents include, for example, 4,4′-dichloro-2-hydroxydiphenyl ether (common name: diclosan), 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), bis- (2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanide hydrochloride, 8-oxyquinoline, polylysine and the like.
When the liquid bleach contains an antibacterial agent, 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, based on the total mass of the liquid bleach, 0.005 to 0.5 mass % is more preferred, and 0.01 to 0.3 mass % is particularly preferred.

(Bleach activator)
A bleach activator is a substance that has no bleaching effect per se, but reacts with hydrogen peroxide in a liquid bleaching agent to turn it into a highly oxidizing organic peracid.
A known compound can be used as the bleaching 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 them, 4-decanoyloxybenzoic acid (DOBA), sodium 4-dodecanoyloxybenzenesulfonate (DOBS, sodium 4-lauroyloxybenzenesulfonate (OBS)), sodium 4-nonanoyloxybenzenesulfonate (NOBS) ) is preferred.
The bleaching activator may be used singly or in combination of two or more.
When the liquid bleach contains a bleaching activator, the content of the bleaching activator is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, relative to the total mass of the liquid bleaching agent. % is more preferred, and 0.4 to 1% by mass is even 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 increases.
When the content of the bleaching activator is equal to or less than the above upper limit, it is easy to improve the appearance stability of the liquid bleaching agent.

The total amount of components constituting the liquid bleach of the present invention does not exceed 100% by weight.

・pH
The pH of the liquid bleach at 25° C. is preferably 2 to 8, more preferably 2.5 to 7, even more preferably 4 to 6.5, and particularly preferably 5 to 6.5.
When the pH of the liquid bleach at 25°C is at least the above lower limit, the detergency of the liquid detergent is likely to be improved.
When the pH of the liquid bleach at 25°C is equal to or less than the above upper limit, the color tone stability of the liquid detergent can be easily improved.
The pH of the liquid bleach at 25°C can be adjusted by adding a pH adjuster, if necessary.
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.

[Method for producing liquid bleach]
The liquid bleaching agent of the present invention can be produced, for example, by mixing components (A) to (C) and, if necessary, optional components, and adjusting the pH to a predetermined value, if necessary.

[How to use liquid bleach]
The liquid bleaching agent of the present invention can be used, for example, by adding the liquid bleaching agent alone or in water together with a known detergent or softener to make a washing liquid, adding the article to be washed into the washing liquid, and washing the article in a washing machine. method, a method of dissolving a liquid bleach in advance in water, immersing the article to be washed in this solution, and then washing it with a washing machine. Alternatively, after applying the liquid bleach 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 in the washing liquid is not particularly limited. The amount of liquid bleach added to water is, for example, 2 to 15 mL of liquid bleach per 10 L of water.

[Liquid bleach composition product]
The liquid bleach composition product of the present invention (hereinafter also simply referred to as "bleach product") is obtained by storing the liquid bleach of the present invention in a container having a container body.
FIG. 1 is a perspective view showing an example of the bleach product of the present invention. The bleaching agent product 1 of FIG. 1 includes a container body 100 having an octagonal flat appearance in a front view and containing a liquid bleaching agent 10 and a detachably attached cap 110 .
At least part of the container body 100 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 viewed. 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.

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 obtained by bonding metal foil to paper, a laminate obtained by bonding paper to plastic, a laminate obtained by bonding metal foil to plastic, and the like can also 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.

[Examples 1 to 16, Comparative Example 1]
Each component was mixed according to the composition shown in Tables 1 and 2 to obtain each liquid bleach. Examples 4 to 7 and 13 to 16 are reference examples.
The unit of composition in the table is "ppm by mass" for component (B), and "% by mass" for components other than component (B).
"-" in the table indicates that the component was not blended.
"Amount" in the table is the amount of pH adjuster required to bring the pH of each example liquid bleach to the value in the table.
"Balance" in the table means that water is blended so that the total amount (% by mass) of all compounding components contained in the liquid bleach of each example is 100% by mass.
Raw materials used in this example are as shown in [Raw materials used] below.

[raw materials used]
<(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 Green 3 (Green No. 202, structure is the following formula (I), manufactured by Kisumi Kasei Co., Ltd., Green No. 202).

<Comparative product of component (B)>
· b'-1: C.I. I. Solvent Blue 63 (Blue No. 403, structure is the following formula (III), manufactured by Kisumi Kasei Co., Ltd., Blue No. 403).

<(C) Component>
((c1) component)
・c1-1a ( ^AE6 ): polyoxyethylene alkyl ether, manufactured by Lion Corporation, trade name “Rheox CL-60”; a compound in which R ² is a hydrogen atom, X is O, p is 6, and q is 0;
・c1-1b ( ^AE9 ): polyoxyethylene alkyl ether, manufactured by Lion Corporation, trade name “Rheox CL-90”; a compound in which R ² is a hydrogen atom, X is O, p is 9, and q is 0;
・c1-1c (EOPO): polyoxyethylene polyoxypropylene alkyl ether (EOPO type nonion), polyoxyethylene polyoxypropylene alkyl ether (EOPO type nonion, natural alcohol CO1270 (C12/C14 = 7/3 (mass ratio) , Procter & Gamble Co.), a nonionic surfactant obtained by block addition of 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide in this order); In (c1-1), R ¹ is a linear alkyl group having 12 or 14 carbon atoms, R ² is a hydrogen atom, X is O, p is 16, and q is 2 A compound that is
· c1-2: Softanol, secondary alcohol ethoxylate, manufactured by Nippon Shokubai Co., Ltd., trade name "Softanol 70".
(Component (c2))
· c2-1 (AES): polyoxyalkylene alkyl ether sulfate sodium salt (AES, 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” A compound in which R ³ is an alkyl group having 12 carbon atoms, M ⁺ is a sodium ion, m is 2, and n is 0 in the above formula (c2-1).
· c2-2 (LAS): Linear alkyl (C10-14) sodium benzenesulfonate (LAS), manufactured by Lion Corporation, trade name “Lipon LS250”.
· c2-3: Soap, manufactured by NOF Corporation, trade name "coconut fatty acid".
((c3) component)
・c3-1 (APAX): lauramidopropyl dimethylamine oxide (APAX), trade name “GENAMINOX AP” manufactured by Clariant; in the following formula (c3-1), R ⁴ is a linear alkyl having 11 carbon atoms group, R ⁵ and R ⁶ are methyl groups, and t is 3.

((c5) component)
· c5-1: lauryl dimethylethyl ammonium ethyl sulfate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Cathiogen ES-L"; in the following formula (c5-1), R ⁷ is a dodecyl group, R ⁸ is a methyl group, A compound in which R ⁹ is a methyl group, R ¹⁰ is an ethyl group, and Z ₁ ^- is an ethyl sulfate ion.

<Optional component>
· Chelating agent: 1-hydroxyethane-1,1-diphosphonic acid (HEDP), manufactured by Italmatch, trade name "Dequest 2010".
・Solvent ¹ : 3-methoxy- ³ -methyl- ¹ -butanol, trade name “ ^Solfit ” manufactured by Kuraray Co., Ltd.; A compound that is a hydrogen atom.
^{CH3OCR11 (} _CH3 ) _{CHR12CHR13OR14} ^{( IV} )
- Solvent 2: diethylene glycol monobutyl ether (butyl carbitol), manufactured by Nippon Nyukazai Co., Ltd., trade name "butyl diglycol".
- Hydrotropic agent: p-toluenesulfonic acid (PTS), manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name "PTS acid".
Radical trapping agent: p-methoxyphenol, trade name “MQ-F” manufactured by Kawaguchi Chemical Industry Co., Ltd.
- Buffering agent: citric acid, manufactured by Kanto Kagaku Co., Ltd., trade name "citric acid".
· Antibacterial agent 1: Polyhexamethylene biguanide (Proxel IB), manufactured by Lonza Japan Co., Ltd., trade name "Proxel IB"; a compound of the following formula (V).

Antibacterial agent 2: 4,4'-dichloro-2'-hydroxydiphenyl ether (Tinosan), manufactured by BASF, trade name "Tinosan HP100".
Bleaching activator: sodium 4-lauroyloxybenzenesulfonate (OBS), synthesized according to the procedure described in paragraph [0114] of JP-A-2011-57745.
Perfume: Perfume composition A described in Tables 1 to 6 of JP-A-2011-225743.
- pH adjuster: sulfuric acid (manufactured by Nissan Chemical Industries, Ltd.), sodium hydroxide (manufactured by Asahi Glass Co., Ltd.).
- Water: Purified water.

The following evaluations were performed on the obtained liquid bleaching agent of each example. The results are also shown in Tables 1 and 2.

<Evaluation of Color Stability>
Clear glass bottles were each filled with 100 g of the liquid bleach of each example and sealed with a cap. This bottle was left standing at 50° C. for 30 days and stored under light shielding.
After such storage, the appearance of the liquid was visually observed, and the stability of the color tone of the liquid bleaching agent was visually evaluated according to the following evaluation criteria in comparison with the color tone of the liquid bleaching agent before storage.
"Evaluation criteria"
◯: The color tone was maintained.
x: Color tone deteriorated.

<Evaluation of liquid level visibility>
The liquid bleach of each example after standing and stored at 50 ° C. for 30 days is packed in a pouch with a spout and poured into a container with a window through which the liquid level can be visually confirmed (a container with a white inner wall), The visibility of the liquid level was visually evaluated according to the following evaluation criteria.
"Evaluation criteria"
⊚: The liquid level is easy to distinguish (distinguishable at a glance).
◯: The liquid level is somewhat easy to distinguish.
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 was applied to each of the 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 color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name SE2000), using a raw cloth (polyester tropical cloth before dropping chili oil) before staining, and The Z value (reflectance) of the oil-stained cloth before and after the washing test was measured, and the washing rate was calculated from the following formula for evaluation. 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"
⊚: The average cleaning rate is 30% or more.
◯: The average value of cleaning rate is 20% or more and less than 30%.
Δ: The average cleaning rate is 10% or more and less than 20%.
x: The average value of cleaning rate is less than 10%.

<Evaluation of Appearance Stability>
The appearance of each liquid bleaching agent was visually observed after being stored at 50° C. for 30 days, and the appearance stability (solution stability) of the liquid bleaching agent was evaluated according to the following evaluation criteria.
"Evaluation criteria"
⊚: No separation for 30 days.
◯: Uniform and no separation for 20 days, but turbidity, separation or floating observed after 30 days.
x: Turbidity, separation or floating observed in less than 20 days.

As shown in Tables 1 and 2, Examples 1 to 16 to which the present invention was applied were excellent in color tone stability and liquid level visibility.
On the other hand, Comparative Example 1, in which the comparative component was used instead of the component (B), was evaluated as "Poor" in color tone stability and liquid level visibility.

It was found that the liquid bleach composition of the present invention is superior in color tone stability and liquid level visibility.

1 liquid bleach composition product 10 liquid bleach composition 20 window 100 container body 110 cap

Claims (4)

(A) component: hydrogen peroxide;
(B) component: a dye that is a compound represented by the following formula (I);
(C) component: a surfactant;
contains
A liquid bleach composition in which the component (C) uses the following component (c1), the following component (c2), and the following component (c3) in combination.
(c1) component: nonionic surfactant
(c2) component: anionic surfactant
(c3) component: semi-polar surfactant

A liquid bleach composition according to claim 1, having a pH of 2-8 at 25°C. The mass ratio of the component (c1) to components other than the component (c1) is 0.25 to 1.5,
3. The liquid bleach composition according to claim 1, wherein the mass ratio represented by component (c2)/component (c3) is from 1.1 to 1.8. 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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