JP2007177047A - Liquid bleaching agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid bleaching agent composition capable of suppressing sun-dried smell and excellent in preservation stability as well. <P>SOLUTION: This liquid bleaching agent comprises (A) hydrogen peroxide, (B) a smectite type clay mineral with <20 ppm manganese content and (C) a nonionic surfactant. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid bleach composition.

Currently, bleach is widely accepted by consumers and its usage is increasing year by year.
There are two types of bleaching agents: chlorine bleaching agents and oxygen bleaching agents. Among them, oxygen bleaching agents containing hydrogen peroxide as a bleaching component are widely used in clothing including not only white products but also colored products. Since it can be used, it is widely used for clothing.
Also, there are two types of oxygen bleaches, powder type and liquid type. The liquid type is widely recognized because of its convenience and ease of water solubility. These liquid bleaches are generally filled in containers such as plastic bottles and supplied to ordinary households.

On the other hand, bleaching agents are used not only for removal of stains such as tea, coffee, fruits and blood, but also for applications such as sterilization, deodorization and deodorization.
In recent years, deodorization and deodorization have seen increasing demand from consumers, and there are many laundry products that appeal to these other than bleaching agents. In particular, deodorizing and deodorizing products for suppressing odor generation during indoor drying have attracted attention. For example, Patent Document 1 describes a method for improving stain removal and deodorization by using a surfactant, clay, and a bleaching agent in combination.
Special Table 2000-515204

However, since the stability of hydrogen peroxide in water is usually low, storage stability is an important issue for oxygen-based liquid bleach compositions. When storage stability is low, when stored in a container, hydrogen peroxide is decomposed and gas is generated due to various components, temperature, pH, etc. contained in the composition, and the container is swollen or cracked. May cause problems.
In particular, as described in Patent Document 1, when a bleaching agent and clay are used in combination, the storage stability is very poor, and hydrogen peroxide is decomposed, so that the performance is rapidly reduced. .

On the other hand, when clothes, bedding, etc. are washed and sun-dried outdoors, alteration of proteins, lipids and the like occurs due to the influence of ultraviolet rays and the like, and odor (sun-dried odor) is generated.
Such a sun-dried odor has a strong odor intensity compared to the odor after drying in the room, but it is popular with many consumers as a “sun fragrance” when taken in.
However, the sun-dried odor is changed to an unpleasant odor such as a burnt odor or a raw odor over time. Therefore, there is a need for technology that can control sun-dried odors. However, as mentioned above, sun-dried odors are familiar to consumers, and so far no studies have been conducted on how to control sun-dried odors. .

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the liquid bleach composition which can suppress the sun-dried odor and was excellent also in storage stability.

As a result of intensive studies, the present inventors have found that the above problem can be solved by combining hydrogen peroxide, a specific smectite clay mineral, and a nonionic surfactant, and have completed the present invention. .
That is, this invention is a liquid bleach composition characterized by containing the following (A)-(C).
(A) Hydrogen peroxide (B) Smectite type clay mineral having a manganese content of less than 20 ppm (C) Nonionic surfactant

  ADVANTAGE OF THE INVENTION According to this invention, the liquid bleach composition which can suppress the sun-dried odor and was excellent also in storage stability can be provided.

Below, the liquid bleach composition of this invention is demonstrated in detail.
[(A) component (hydrogen peroxide)]
The component (A) is essential for the liquid bleach composition to function as an oxygen bleach. Moreover, it works as a cleaning auxiliary component of the component (C) and improves the effect of suppressing sun-dried odor.
In the liquid bleach composition, the blending amount of the component (A) is not particularly limited, but is usually preferably 0.1 to 10% by mass, and preferably 0.5 to 8% by mass with respect to the total amount of the composition. Is more preferable and 0.8-5 mass% is still more preferable. When the blending amount of the component (A) is 0.1% by mass or more, the ability to suppress sun-dried odor is improved, and when it is 10% by mass or less, the storage stability is good, and it is easy to use for home use, for example. .

[Component (B) (Smectite-type clay mineral having a manganese content of less than 20 ppm)]
In the present invention, the component (B) is particularly effective for suppressing sun-dried odor. This is mainly due to the adsorption of sun-dried odors that are adsorbed on objects to be cleaned such as clothing when the object (clothing etc.) is processed using the liquid bleach composition. Conceivable.

In the present invention, the “smectite clay mineral” is a natural clay mineral and a substance obtained by synthesis, and belongs to the smectite group and has a specific layered structure. Specifically, it is a 2: 1 layered silicate of 2 octahedron type (dioctahedral type) or 3 octahedron type (trioctahedral type), and is a generic name of layer charge of 0.6 to 0.2.
As the smectite type clay mineral, those having a dioctahedral trilayer structure or a trioctahedral trilayer structure are preferable.
Examples of the smectite type clay mineral having a dioctahedral type three-layer structure include montmorillonite, nontronite, beidellite, and pyrophyllite.
Examples of the smectite clay mineral having a trioctahedral three-layer structure include saponite, hectorite, stevensite, and talc.
Among these, those having a trioctahedral three-layer structure are preferable, and saponite and / or hectorite is particularly preferable.

The component (B) has a manganese content of less than 20 ppm. When the manganese content is 20 ppm or more, the storage stability of the liquid bleach composition is poor, and the quality tends to deteriorate.
For the effect of the present invention, the manganese content in the component (B) is preferably 2 ppm or less, more preferably 0.2 ppm or less. The lower the manganese content, the better the effect of the present invention and the better the liquid appearance of the liquid bleach composition.

The measurement of the manganese content in the component (B) can be performed, for example, by inductively coupled plasma spectroscopy (ICP spectroscopy (inductively coupled plasma spectroscopy)). ICP spectroscopic analysis can be performed, for example, by the following procedure.
First, a 60 mass% nitric acid aqueous solution (for atomic absorption, manufactured by Kanto Chemical Co., Inc.) is diluted with ion-exchanged water to prepare a 5 mass% nitric acid aqueous solution.
Next, 1.0 g of component (B) was added to a 5% by mass aqueous nitric acid solution, and the volume was increased to 100 mL. Using the obtained component-containing solution, an ICP spectroscopic analyzer (OPTIMA5300DV, PerkinElmer Co., Ltd.) (Manufactured), the manganese content contained in the component (B) is measured.

Examples of the smectite-type clay mineral having a manganese content of less than 20 ppm include synthetic products produced by synthesis (synthetic smectite), purified products obtained by purifying natural clay minerals, and having a manganese content of less than 20 ppm. It is done.
In the present invention, the component (B) is preferably synthetic smectite. Synthetic smectite does not contain manganese, or even if it contains manganese, its content is very low and is excellent in the effects of the present invention.
As the synthetic smectite, commercially available products can be used. For example, Laponite RD (synthetic hectorite) manufactured by Wilber Ellis Co., Ltd. Optigel SH (synthetic hectorite) manufactured by Zude Chemie Catalysts Co., Ltd., and Kunimine Kogyo Co., Ltd. Examples include Smecton SA (synthetic saponite).

  The component (B) is, for example, a method by hydrothermal synthesis described in the Clay Handbook 2nd edition (edited by the Japan Clay Society, Gihodo Publishing Co., Ltd. (1987), P193-256), and Japanese Patent Publication No. 63-6486. It can be prepared by synthesizing by the methods of JP-B-46-813, JP-B-51-33080, JP-B-61-1848, and JP-B-3479676. It can also be prepared by using a natural smectite-type clay mineral as a starting material, synthesizing by the alteration method described in the above document, hydrothermal synthesis method or the like and then purifying by the purification method described in the above patent document.

As the component (B), any one type may be used alone, or two or more types may be used in combination.
Although the compounding quantity of (B) component in a liquid bleach composition is not restrict | limited in particular, 0.1-10 mass% is preferable with respect to the liquid bleach composition whole quantity, and 0.2-5. 0 mass% is more preferable and 0.5-3.0 mass% is especially preferable. When the blending amount is 1% by mass or more, a good effect is obtained in terms of performance such as the ability to suppress sun-dried odor. When it is 10% by mass or less, the viscosity and the like are easy to use as a liquid bleaching composition, and it is also preferable in terms of cost.

[(C) component (nonionic surfactant)]
In the present invention, the component (C) is effective for suppressing sun-dried odor. This is considered to be due to the removal of oils such as sebum, which is thought to cause sun-dried odor when dried, when the object (clothing, etc.) is treated with the liquid bleach composition. It is done.
(C) As a component, what is generally used for the liquid bleach composition etc. can be used, More specifically, for example, polyoxyalkylene alkyl ether, alkyl (poly) glycoside, sorbitan fatty acid ester, poly Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester oxyethylene propylene block polymer, fatty acid monoglyceride, and amine oxide.

Among these, polyoxyalkylene alkyl ethers are preferable because they are excellent in the effect of suppressing sun-dried odor, and compounds represented by the following general formula (a) are particularly preferable.
R ¹ O— (EO) _n —H (a)
[Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms; EO represents an oxyethylene group; n represents an average number of moles of EO added; It is a range. ]

In the general formula (a), the alkyl group or alkenyl group represented by R ¹ has 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms.
Specific examples of the alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group.
Moreover, as an alkenyl group, the alkenyl group corresponding to the said alkyl group is mentioned, For example, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group etc. are mentioned.

In the said general formula (a), the average added mole number n of EO is 4-30, 5-20 are preferable and 7-16 are more preferable.
Here, the number of added moles means the number of moles of ethylene oxide reacted with 1 mole of alcohol used.

In the case of a nonionic surfactant obtained by reacting an ethylene oxide with an alcohol, a nonionic surfactant having a distribution with a different number of added moles, usually centering on the average number of added moles n, is obtained by addition reaction of ethylene oxide. It is done.
In the nonionic surfactant represented by the general formula (a), when the average added mole number n is 3 to 15, particularly 3 to 6, the use of a product having a sharp distribution of the added mole number results in a product aroma. Is preferable. As the nonionic surfactant having a sharp distribution of the number of added moles, the number of added moles relative to the total mass of the nonionic surfactant represented by the general formula (a) is from (nav-2) to (nav + 2). The total mass ratio (Yi) of those included in the range is 55% by mass or more, and Yi is more preferably 70% by mass, and particularly preferably 80% by mass or more.
The method for producing such a nonionic surfactant having a sharp distribution of the number of added moles of ethylene oxide is not particularly limited. For example, it is distilled from a reaction product synthesized from a higher alcohol and ethylene oxide by a conventional method. It can be obtained by fractionating the one having the necessary molecular weight range.
Further, for example, it can be easily obtained by addition reaction of ethylene oxide to an aliphatic alcohol or the like using a specific alkoxylation catalyst.
In this case, as the alkoxylation catalyst, for example, an alkoxylation catalyst described in JP-B-6-15038 can be used. Specifically, magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ are added can be used.
The distribution of the number of moles of ethylene oxide added in the nonionic surfactant represented by the general formula (a) is, for example, high-speed using a product name ZORBAXC8 (manufactured by DuPont) for the column and a mixed solvent of acetonitrile and water for the mobile phase. It can be easily measured by liquid chromatography (HPLC).

Formula (a) compounds represented by may be used singly or may be used as a mixture of R ¹ are different compounds in Formula (a). Such a mixture can also be obtained, for example, by adding ethylene oxide to two or more kinds of alcohols.

As the component (C), any one type may be used alone, or two or more types may be used in combination.
In the liquid bleach composition, the blending amount of the component (C) is not particularly limited, but is usually preferably 1 to 20% by mass, and 3 to 15% by mass with respect to the total amount of the liquid bleach composition. More preferably, 5-12 mass% is especially preferable. When the blending amount is 1% by mass or more, a good effect is obtained in terms of performance such as the ability to suppress sun-dried odor. It is preferable in terms of stability and cost of the composition that the content is 20% by mass or less.

[Optional ingredients]
The liquid bleach composition of the present invention may contain optional components other than those described above. Preferable optional components include (D) a phosphonic acid-based metal trapping component and (E) a phenol-based radical trapping agent.

[(D) component (phosphonic acid-based metal-trapping component)]
In the liquid bleach composition of the present invention, the component (D) is not essential, but by blending the component (D), decomposition of the component (A) is suppressed, and the storage stability of the liquid bleach composition is improved. Further improve.
That is, when a trace amount of iron ion or copper ion is present in the composition, the stability of the bleaching composition is lowered and the component (A) is decomposed. As a result, the gas generated by the decomposition of the component (A) may cause the container to bulge or crack. In order to suppress the influence of these metal ions, it can be said that the larger the value of the logarithmic value (log K) of a chelate stability constant K that is generally used is better as an index of chelate efficiency.
Accordingly, the component (D) preferably has a phosphonic structure and has a logarithmic value (log K) of the chelate stability constant for Fe ³⁺ and Cu ²⁺ of 10 or more, and more preferably 12 or more.

As component (D), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid salt, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid Examples thereof include organic phosphonic acid derivatives such as acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid.
Among these, 1-hydroxyethane-1,1-diphosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, and the like are more preferable.
Examples of main commercial products of 1-hydroxyethane-1,1-diphosphonic acid include Albright Wilson's product name BRIQUEST ADPA, Cylest's product name Kirest PH-210, Monsanto's product name DEQUEST 2010, and the like. . The same effect can be obtained by using any of these.

(D) component can be used 1 type or in mixture of 2 or more types.
Although the compounding quantity of (D) component in a liquid bleach composition is not restrict | limited in particular, 0.1-3 mass% is preferable with respect to the liquid bleach composition whole quantity, and 0.2-2. 5 mass% is more preferable and 0.6-1.5 mass% is especially preferable. When it is at least the lower limit value, the effect of preventing the decomposition of the component (A) is excellent, and when it is at most the upper limit value, the liquid appearance is good and its stability is also good.

[(E) component (phenolic radical trapping agent)]
The “phenolic radical trapping agent” is one or more compounds selected from phenol and phenol derivatives, and has a function of trapping radicals. Whether or not the compound has a function of scavenging radicals is determined by comparing ESR measurement (electron spin resonance method) with a radical trapping agent compared to when hydrogen peroxide acts on a solid metal (for example, copper). Further, it can be determined that when added, it has a function of trapping radicals when the radical concentration in the system is low.
In the liquid bleach composition of the present invention, the component (E) is not essential, but by mixing the component (E), the decomposition of the component (A) and other optional components (fragrances, pigments, polymers, etc.) is suppressed. In order to improve the storage stability of the liquid bleach composition, it is preferable to contain the component (E). Especially when the pH at 25 ° C. is 4 to 8 because the effect of trapping radicals is higher than that of other radical trapping agents when the pH at 25 ° C. is in the range of 4 to 8. Preferably contains the component (E).

  Examples of “phenol and phenol derivatives” include compounds having a phenolic hydroxyl group (OH group) and compounds having a substituent derived from a phenolic OH group. Of these, compounds having a phenolic OH group are preferred.

  As the “compound having a phenolic OH group”, a compound in which a benzene ring has one or more phenolic OH groups as a substituent, one or more phenolic OH groups, and one or more other substituents are included. And the like.

The “substituent derived from a phenolic OH group” is a group in which a hydrogen atom of a phenolic OH group is substituted with an atom or group other than a hydrogen atom.
As the compound having a substituent derived from a phenolic OH group, an ester derivative of a phenolic OH group or an ether derivative of a phenolic OH group is preferable.
The “ester derivative of a phenolic OH group” refers to a compound having an ester group formed by an ester reaction of a hydrogen atom of a phenolic OH group with a fatty acid having about 1 to 3 carbon atoms.
“An ether derivative of a phenolic OH group” has a group in which a hydrogen atom of a phenolic OH group is substituted with an aryl group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group to form an ether bond. Compounds are shown.
The ester derivative and ether derivative of the phenolic OH group may have two or more substituents derived from the phenolic OH group (an ester group, a group having an ether bond, etc.), or other substituents. You may have.

In the case where the benzene ring in “phenol and phenol derivative” has two substituents (phenolic OH group, substituent derived from phenolic OH group, and other substituents), these substitution positions are ortho positions. , Any of meta position and para position may be used. Similarly, also when it has three or more substituents, the substitution position of those substituents is not limited.
Examples of the substituent other than the substituent derived from the phenolic OH group or the phenolic OH group include aryl groups such as an alkyl group having 1 to 5 carbon atoms (preferably a methyl group and an ethyl group) and a phenyl group. .

  As the component (E), G.I. E. Penketh, J. et al. Appl. Chem., 7, 512 (1957), a compound having an oxidation-reduction potential (OP) of 1.25 V or less is preferable, and a compound of 0.75 V or less is particularly preferable.

  The structural formulas of typical compounds are shown below as specific examples of the component (E). In the formulae, Me represents a methyl group, and Et represents an ethyl group.

  Preferred examples of the component (E) include methoxyphenol, dimethoxyphenol, catechol, hydroquinone, dibutylhydroxytoluene (BHT) and the like. Among these, methoxyphenol is preferable, and 4-methoxyphenol is particularly preferable.

(E) A component can be used 1 type or in mixture of 2 or more types.
Although the compounding quantity of (E) component in a liquid bleach composition is not specifically limited, 0.01-1 mass% is preferable with respect to the liquid bleach composition whole quantity, and 0.03-0. 6 mass% is more preferable, and 0.05 to 0.3 mass% is particularly preferable. When the content is 0.01% by mass or more, the effect of suppressing the decomposition of the component (A), particularly the effect of suppressing the decomposition of the component (A) when the pH at 25 ° C. is in the range of 4 to 8 is good. When the content is 6% by mass or less, the stability of the preparation is good and coloring of the preparation hardly occurs.

  In addition, since both (D) component and (E) component have the effect which suppresses decomposition | disassembly of (A) component, what is necessary is just to mix | blend either one in the point of the effect, It is preferable to mix.

In the liquid bleach composition, other optional components other than the component (D) and the component (E) can be appropriately blended as long as the effects of the present invention are not impaired.
However, in view of the liquid appearance and the like, it is preferable not to add an ionic compound, particularly a cationic compound.

-Surfactants other than nonionic surfactants Examples of surfactants other than nonionic surfactants include anionic surfactants, cationic surfactants, and amphoteric surfactants.

More specifically, examples of the anionic surfactant include alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; linear or branched alkyl group or alkenyl group. And alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt added with an average of 0.5 to 8 mol of ethylene oxide; α-sulfo fatty acid ester salt; higher fatty acid salt and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, and alkaline earth metal salts such as magnesium.
As alkylbenzenesulfonic acid or its salt, a C8-C16 thing is preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and is added with an average of 0.5 to 8 moles of ethylene oxide. Is preferred.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
As higher fatty acid salts, those having 10 to 20 carbon atoms are preferred.

A quaternary ammonium salt is mentioned as a cationic surfactant.
Any conventionally proposed quaternary ammonium salt can be used. For example, in the case of a dialkyl type quaternary ammonium salt, the long chain alkyl group has 6 to 24 carbon atoms, particularly 10 to 20 carbon atoms. The alkyl group having 1 to 3 carbon atoms or the hydroxyalkyl group is preferable.

  Examples of the amphoteric surfactant include carbobetaine, sulfobetaine, hydroxysulfobetaine and the like, and the number of carbon atoms is preferably 10-20.

-High molecular compound A polymeric compound may be mix | blended with a liquid bleaching agent composition in order to improve a stain removal performance further. Specifically, it is called a soil release polymer, and is a polymer compound having an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene unit as a skeleton. In addition, although superposition | polymerization polymerizes by random or a block, what superposed | polymerized by the block is preferable.

  Examples of the alkylene terephthalate include ethylene terephthalate, propylene terephthalate, butylene terephthalate, and mixtures thereof. Among these, ethylene terephthalate is preferable. Examples of the alkylene isophthalate include ethylene isophthalate, propylene isophthalate, butylene isophthalate, and mixtures thereof. Among them, ethylene isophthalate is preferable. Examples of polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene, and the like, but polyoxyethylene is preferable.

The mass average molecular weight of the polymer compound is desirably 500 or more, preferably 800 or more, particularly preferably 1500 or more, in order to improve the solubility and dispersibility in water. The upper limit of the mass average molecular weight is 8000 or less, preferably 7000 or less, and particularly preferably 6000 or less. When used in this mass average molecular weight range, the coating and bleaching performance of polyester oily soil is sufficiently exhibited, and the liquid bleaching agent composition has a good liquid appearance, which is preferable in practical use.
In the present specification, the mass average molecular weight is a value obtained by conversion using PEG (polyethylene glycol) as a calibration curve when the solvent is measured with THF (tetrahydrofuran) by GPC (gel permeation chromatography).

Such a method for producing a polymer compound is disclosed in various documents, textbooks, patents and the like.
For example, the method described in Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948), Journal of Polymer Science, Vol. 8, pages 1 to 22 (1951), Japanese Patent Application Laid-Open No. 61-218699. May be used, and other methods may be used.
Specific examples of these polymer compounds include those commercially available under the trade names TexCareSRN-100 (manufactured by Clariant GmbH, Germany) and trade names TexCareSRN-300 (manufactured by Clariant GmbH, Germany).
Particularly preferred is TexCare SRN-100 (manufactured by Clariant GmbH, Germany).
When such a preferable polymer compound is used, a liquid oxygen bleach composition having high solubility in water and thus high transparency can be obtained.

  When the polymer compound is blended, the polymer compound is used in the liquid bleach composition in an amount of 0.1 to 3% by mass, preferably 0.2 to 2% by mass. By using in this range, the performance expected by blending can be fully expressed. Moreover, it is preferable also in terms of cost.

-Organic peracid precursor When an organic peracid precursor is blended, the bleaching effect can be further improved.
Typical examples of organic peracid precursors include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, and undecanoyloxybenzenesulfonate. Sodium, sodium dodecanoyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, deca Examples include noyloxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene and the like. Among these, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, and the like are more preferable.

・ Hydrotrope In addition, monohydric alcohols such as ethanol, isopropanol, and phenylpolyoxyethylene alcohol, ethylene glycol, propylene glycol, polyethylene, etc., in order to stably blend various components such as fragrances into the liquid bleach composition Hydrotropes such as polyhydric alcohols such as glycol and glycerin can be blended.

-Fragrance | flavor As a fragrance | flavor, the fragrance | flavor composition which normally mix | blended multiple combinations of the following fragrance | flavor raw materials is used suitably.
A list of perfume ingredients used as perfumes can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and “Synthetic fragrance chemistry and commercial knowledge”, Motoichi Into, Chemical Industry Daily (1996) and “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., each of which is incorporated herein by reference.
0.001-20 mass% is suitable for the compounding quantity of a fragrance | flavor with respect to the composition whole quantity, More preferably, 0.01-10 mass% is mix | blended.

  Liquid bleach compositions generally include other liquid salts such as sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate, sodium borate, silicone salts, bactericides, fluorescent dyes, enzymes, etc. The component mix | blended with an agent composition and a liquid bleach composition can be mix | blended as needed.

In the liquid bleach composition of the present invention, the pH at 25 ° C. is preferably 4 to 8, more preferably 5 to 7. When the pH is within the above range, the effect of the present invention is excellent, and in particular, the storage stability is further improved.
The pH can be adjusted by appropriately selecting a pH adjuster (acidic substance, alkaline substance) and adding an appropriate amount.
Examples of the alkaline substance include sodium tetraborate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia (usually used as an aqueous solution) and the like.
Examples of the acidic substance include inorganic acids such as boric acid, sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids (usually used as an aqueous solution) such as p-toluenesulfonic acid, citric acid, and phosphonic acid derivatives.
Among these, sodium tetraborate and boric acid are preferable as the pH adjuster in consideration of the stability of the component (B).
When the pH at 25 ° C. of the liquid bleach composition is 4 to 8, the liquid bleach composition preferably contains the above-described component (D) and / or (E). Thereby, the liquid external appearance, storage stability, etc. of a liquid bleaching agent composition improve.

[Production method]
The liquid bleach composition of the present invention can be produced by a conventional method. For example, the above-mentioned essential materials and preferable materials and optional components appropriately selected are dissolved and mixed in water so as to have an appropriate concentration, and the pH is adjusted using an acidic substance or an alkaline substance as described above. It can be manufactured by adjusting.

[how to use]
The method of using the liquid bleach composition of the present invention is not particularly limited, and may be the same as the method of using a general liquid bleach. For example, the liquid bleach composition of the present invention may be applied to a soiled object, and the object may be washed with a solution in which a commercially available detergent is dissolved. Alternatively, a certain amount of the liquid bleach composition of the present invention may be added to a commercially available detergent solution to wash the object.

The liquid bleach composition of the present invention can be stored, for example, in a suitable container to make a bleach product.
The container for storing the liquid bleach composition is not particularly limited, and can be stored in a generally used container. Such containers include, for example, nozzle-type containers and inner-plug-type containers equipped with measuring caps, squeeze containers and pump containers equipped with automatic measuring mechanisms or simple measuring mechanisms, and trigger containers and squeeze spraying liquids or applying them in foam. Examples include containers, application containers having an application surface for applying liquid, and refill containers (pouches, thin bottles, replacement bottles, etc.).
As a container for storing the liquid bleach composition of the present invention, a container for storing a hydrogen peroxide preparation as proposed in, for example, Japanese Patent Application Laid-Open No. 2003-338997, Japanese Patent Application Laid-Open No. 11-100594 and the like is proposed. The container is preferred.

  As described above, the liquid bleach composition of the present invention can suppress sun-dried odor and has good storage stability.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited at all by the following example.
[Examples 1 to 16, Comparative Example 14]
A liquid bleaching composition was prepared by the following procedure with the compositions and blending amounts shown in Tables 1 to 3.
First, component (B) was added to ion-exchanged water and sufficiently dispersed, and then component (C), component (D) and an optional component were added. Then, (A) component was added and it adjusted to pH shown in Tables 1-3 with the pH adjuster, and obtained the liquid bleaching composition.
As a pH adjuster, sodium tetraborate decahydrate and / or boric acid was used.

The measurement of the manganese content in the component (B) shown in Tables 1 to 3 was performed according to the following procedure.
A 60 mass% nitric acid aqueous solution (for atomic absorption, manufactured by Kanto Chemical Co., Inc.) was diluted with ion-exchanged water to prepare a 5 mass% nitric acid aqueous solution.
Next, 1.0 g of each component (B) was added to a 5% by mass nitric acid aqueous solution and made up to 100 mL. Using the obtained component-containing solution (B), the content of manganese contained in the component (B) was measured with an ICP spectrometer (OPTIMA5300DV, manufactured by PerkinElmer Co., Ltd.), and the results were evaluated as follows. Evaluated by criteria. The evaluation results are also shown in Tables 1-3.
X: 20 ppm or more.
Δ: 2 ppm or more and less than 20 ppm.
○: 0.2pp or more and less than 2ppm.
A: Less than 0.2 ppm.

The following evaluation was performed about the obtained liquid bleach composition.
(1) Evaluation of sun-dried odor suppression degree Human body dirt was evenly attached to a commercially available cotton towel (33 cm × 41 cm), and a quartered cloth was used as a contaminated cloth.
For the above-mentioned contaminated cloth, Terg-O-Tometer (manufactured by US Testing) (120 rpm, 25 ° C., 4 ° DH tap water 900 mL, bath ratio 30) was used, and a commercial detergent (product name “Top” (Lot) .050315C7C), Lion Corporation) 0.067% by weight and liquid bleaching composition 0.133% by weight, washed for 10 minutes, dehydrated for 1 minute, rinsed for 3 minutes and dehydrated for 1 minute. Repeated twice. A T-shirt (manufactured by DVD) was used for adjusting the bath ratio.
After drying the dehydrated contaminated fabric outdoors in the sun until the sun exposure reaches 0.1 MJ / m ² , the evaluator evaluates the intensity of the odor (sun-dried odor) according to the following criteria. Judged.
<Criteria>
5: Odorless,
4: Smell that can be detected somehow,
3: Smell to understand what smell
2: Smell that can be easily detected,
1: Strong smell,
0: Strong smell For these determination results, the average score of 10 subjects was determined. The results are also shown in Tables 1-3.

(2) Evaluation of liquid appearance Each liquid bleaching composition 50mL was stored with the screw vial, respectively, and the liquid external appearance one day after the storage start was evaluated with the following criteria. The results are also shown in Tables 1-3.
<Criteria>
○: No change.
Δ: Slightly turbid.
X: Separation or cloudiness.

(3) Storage stability After filling each liquid bleaching composition 500mL to the main body bottle of the container comprised from the main body bottle shown in Table 4, a nozzle cap, and a measuring cap, and closing a nozzle cap and a measuring cap firmly, It was left in a constant temperature room at 50 ° C for one month. The swelling of the container after being left was visually determined according to the following criteria, and the storage stability was evaluated. The results are also shown in Tables 1-3.
<Criteria>
A: No swelling is observed.
○: The body part slightly swells.
(Triangle | delta): The trunk | drum clearly swells and shakes when touched.
X: The bottom part pops out or bursts.

* 1 to 6 in Tables 1 to 3 indicate the following.
* 1: 35% by mass aqueous solution manufactured by Mitsubishi Gas Chemical Company.
* 2: Each of the following smectite clay minerals.
Smectite A: Hectorite; manufactured by Wilber Ellis Co., Ltd., product name “Laponite RD”.
Smectite B: Hectorite; product name “Optigel SH” manufactured by Zude Chemie Catalysts Co., Ltd.
Smectite C: Saponite; product name “Smecton SA” manufactured by Kunimine Kogyo Co., Ltd.
Smectite D: Montmorillonite; manufactured by Kunimine Industry Co., Ltd., product name “Kunipia F”.

* 3: General formula _{^{R 11 O- (EO) n '}} -H [R 11 is an alkyl group, n' is an average addition mole number of ethylene oxide (EO). ] The nonionic surfactant represented by this. Nonions A to D are as follows.
Nonion A: polyoxyethylene alkyl ether in which R ¹¹ is a linear alkyl group of C12 and n ′ is 20; manufactured by Nippon Emulsion Co., Ltd.
Nonion B: Polyoxyethylene alkyl ether (90% by mass aqueous solution) in which R ¹¹ is a mixture of a linear alkyl group of C12 and a linear alkyl group of C14, and n ′ is 15, manufactured by Lion Chemical Co., Ltd.
Nonion C: polyoxyethylene alkyl ether in which R ¹¹ is a linear alkyl group of C12 and n ′ is 9; manufactured by Nippon Emulsion Co., Ltd.
Nonion D: a compound in which R ¹¹ is a mixture of a linear alkyl group of C12 and a linear alkyl group of C14, and n ′ is 15 (90% by mass aqueous solution); manufactured by Lion Chemical Co., Ltd.

* 4: Hydroxyethane-1,1-diphosphonic acid (60 mass% aqueous solution); product name “BRIQUEST ADPA” manufactured by Albright Wilson Co., Ltd.
* 5: Made by Kawaguchi Chemical Co., Ltd.
* 6: The fragrances A to D are the fragrance compositions A to D described in Tables 7 to 14 of JP-A-2003-268398, respectively.

* 11-15 in Table 4 shows the following, respectively.
* 11: High density polyethylene; manufactured by Mitsui Chemicals.
* 12: manufactured by Dainichi Seika Co., Ltd .; product name “PE-M AZ MA1058 Blue”.
* 13: Value measured with calipers.
* 14: Polypropylene, manufactured by Mitsui Chemicals.
* 15: manufactured by Dainichi Seika Co., Ltd .; product name “PE-M AZ MA1732 Yellow”.

As is clear from the above results, in Examples 1 to 16, the sun-dried odor suppression degree and the storage stability were both good.
Moreover, Examples 1, 3, 5 to 7, 9 to 10, 12 to 13, and 15 to 16 satisfying the following requirements (1) to (6) also had good liquid appearance.
(1) Content of (A) component is 1.0-3.0 mass%.
(2) The component (B) is smectite A or B.
(3) The component (C) is contained at a ratio of 3.0 to 15% by mass.
(4) As a component (C), any one or more of nonions A to C are contained.
(5) The component (D) is contained at a ratio of 0.5 to 1.5% by mass.
(6) The component (E) is contained at a ratio of 0.05 to 2.0% by mass.
On the other hand, the comparative example 1 which does not contain (A) component, the comparative example 2 which does not contain (B) component, and the comparative example 3 which does not contain (C) component had low sun-dried odor suppression degree. Further, Comparative Example 4 using a smectite clay mineral having a manganese content of 20 ppm or more was poor in both storage stability and liquid appearance.

Claims (6)

A liquid bleach composition comprising the following (A) to (C):
(A) Hydrogen peroxide (B) Smectite type clay mineral having a manganese content of less than 20 ppm (C) Nonionic surfactant The liquid bleach composition according to claim 1, wherein the (C) nonionic surfactant is a compound represented by the following general formula (a).
R ¹ O— (EO) _n —H (a)
[Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms; EO represents an oxyethylene group; n represents an average number of moles of EO added; It is a range. ]   The liquid bleach composition according to claim 1 or 2, further comprising (D) a phosphonic acid-based metal scavenger.   Furthermore, (E) Liquid bleach composition as described in any one of Claims 1-3 containing a phenolic radical trap agent.   The liquid bleach composition according to any one of claims 1 to 4, wherein the pH at 25 ° C is in the range of 4 to 8. It is for clothes, The liquid bleach composition as described in any one of Claims 1-5.