JP2012111868A - Liquid bleaching agent article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid bleaching agent article breathing good smell when a covering cap is opened, without limitation on fragrance materials.SOLUTION: This liquid bleaching agent article is configured such that a liquid bleaching composition, containing (A) a fragrance composition, (B) a nonionic surfactant in an amount of 2.5-50 mass% and (C) hydrogen peroxide, is filled in a liquid-pouring container in which a spout implement, comprising an inside plug mounted on the mouth of a housing container housing the liquid bleaching composition and equipped with a pouring nozzle, and the covering cap mounted on the inside plug, is attached on the mouth of the housing container. Here, the amount of dissolved gas in 500 g of the liquid bleaching agent composition is 1.0-2.0 mL; the volume ratio of (the spout implement volume (mL) after filling the liquid bleaching agent composition)/(the space volume (mL) of the housing container) is 1/1 to 4/1; and the area ratio of (the upper cross section (cm) of the housing container)/(the cross section (cm) of the inside plug) is 2.5/1 to 3.5/1.

Description

  The present invention relates to liquid bleach articles. More specifically, the present invention relates to a liquid oxygen bleach product for textiles used for washing textiles such as clothing.

  In recent years, liquid bleaches have been widely used due to their convenience, and perfumes are blended from the viewpoint of palatability (for example, Patent Documents 1 and 2). According to the invention of Patent Document 1, a liquid oxygen bleaching agent that does not deteriorate the stability due to a fragrance has been proposed. According to the invention of Patent Document 2, a liquid oxygen bleaching agent using a perfume that masks oxygen odor and does not change aroma after storage has been proposed. Furthermore, according to Patent Document 3, a bleaching composition excellent in smell is also proposed.

Japanese Patent Laid-Open No. 3-115399 Japanese Unexamined Patent Publication No. 60-23498 JP 2000-160193 A

  However, although the liquid bleach composition of Patent Documents 1 and 2 is excellent in the stability of the composition and masking of the oxygen odor, no consideration is given to the smell of the fragrance. Further, according to Patent Document 3, although the fragrance of the fragrance is improved, the limitation of the fragrance is indispensable, and it is not possible to satisfy the palatability of various users.

  Therefore, an object of the present invention is to provide a liquid bleaching article having a good odor without limiting the flavor.

  As a result of intensive studies, the inventors have filled a liquid bleaching composition containing a perfume composition, a nonionic surfactant, and hydrogen peroxide into a liquid pouring container having a specific pouring tool. The present invention has been completed by finding that the odor is good when the overcap (measuring cap) is opened without limiting the above.

That is, the liquid bleach article of the present invention comprises (A) a fragrance composition, (B) a nonionic surfactant: 2.5 to 50% by mass, and (C) a liquid bleach composition containing hydrogen peroxide. ,
A storage container for storing the liquid bleach composition is provided with a pouring tool comprising an inner plug mounted on a mouth portion of the container and provided with a pouring nozzle, and an overcap mounted on the inner plug. Fill the liquid dispensing container attached to the mouth,
The volume of dissolved gas in 500 g of the liquid bleach composition is 1.0 mL or more and 2.0 mL or less, and the volume of the void volume (mL) of the storage container after filling the liquid bleach composition / volume of the extraction tool (mL). The area ratio is 1/1 to 4/1, and the area ratio of the upper sectional area (cm ² ) of the storage container / the sectional area (cm ² ) of the inner plug is 2.5 / 1 to 3.5 / 1. It is characterized by being.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid bleach article | item which is excellent in smell generation without limiting a fragrance | flavor can be provided. Excellent smell especially when stored at low temperatures.

It is a schematic diagram which shows an example of the liquid extraction container (enlarged view of an extraction tool) used for the liquid bleaching article of this invention. It is a schematic diagram which shows an example of the storage container used for the liquid bleach article | item of this invention. It is a schematic diagram which shows an example of the storage container used for the liquid bleach article | item of this invention. It is a schematic diagram which shows an example of the storage container used for the liquid bleach article | item of this invention. It is a schematic diagram which shows an example of the extraction tool used for the liquid bleach article | item of this invention.

  Hereinafter, the present invention will be described in detail.

The liquid bleach article of the present invention comprises:
(A) Perfume composition (hereinafter referred to as “component (A)”), (B) Nonionic surfactant (hereinafter referred to as “component (B)”): 2.5 to 50% by mass, (C ) A liquid bleach composition containing hydrogen peroxide (hereinafter referred to as “component (C)”),
A storage container for storing the liquid bleach composition is provided with a pouring tool comprising an inner plug mounted on a mouth portion of the container and provided with a pouring nozzle, and an overcap mounted on the inner plug. Fill the liquid dispensing container attached to the mouth,
The volume of dissolved gas in 500 g of the liquid bleach composition is 1.0 mL or more and 2.0 mL or less, and the volume of the void volume (mL) of the storage container after filling the liquid bleach composition / volume of the extraction tool (mL). The area ratio is 1/1 to 4/1, and the area ratio of the upper sectional area (cm ² ) of the storage container / the sectional area (cm ² ) of the inner plug is 2.5 / 1 to 3.5 / 1. It is characterized by being.
[(A) component]
(A) A component is a fragrance | flavor composition and becomes a scent component when an overcap is opened.

  Here, the fragrance composition includes a fragrance composition that is a fragrance raw material alone or a mixture of a fragrance raw material, a fragrance solvent, a fragrance stabilizer, and the like. A list of perfume ingredients used as perfumes can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. I and II, Stephen 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 "Performerly Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil Dol. Lajaujis Anonis, Allured Pub. Co. (1993).

The content of the fragrance composition is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.2% by mass in the composition. If the perfume composition is less than 0.01% by mass, the base odor of hydrogen peroxide may be felt when the overcap is opened. On the other hand, if it exceeds 1% by mass, the scent is good when the overcap is opened, but a large amount of the fragrance component remains in the clothes when washing, which inhibits the scent of the softener and the like. May end up.
[Component (B)]
The component (B) is a nonionic surfactant and contributes to bleaching performance and smell.
Nonionic surfactants include polyoxyalkylene alkyl ether, alkyl (poly) glycoside, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester oxyethylene propylene block polymer, fatty acid A monoglyceride etc. are mentioned.
Among the above, polyoxyalkylene alkyl ether is preferable from the viewpoint of stability in a liquid bleach composition containing a bleaching component such as hydrogen peroxide and ease of controlling the amount of dissolved gas in the composition. A polyoxyalkylene alkyl ether represented by the following formula is particularly preferred.
R—O— (AO) _n —H
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms; AO represents an oxyalkylene group; n represents the average number of moles of AO added; The number is preferably 3-15. ]
In the above formula, in R, the alkyl group has 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms. The carbon number of the alkenyl group is the same as the carbon number of the alkyl group. When the carbon number is 8 or more, the detergency is improved, and when the carbon number is 16 or less, the solubility is improved.
Of these, alkyl groups are preferred, and specific examples include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl, and dodecyl, tetradecyl. The group is particularly preferred.

  Examples of AO include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxypentylene group. Of these, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is preferable. AO may be added individually by 1 type and 2 or more types may be added.

  Although n depends on the type of AO, for example, when AO is an oxyethylene group and / or oxypropylene group, it is preferably 3-15, and more preferably 3-8.

  In addition, n is preferably an AO adduct having a narrow ratio of 55% by mass or more, which represents a distribution ratio of AO adducts having different numbers of added moles of AO represented by the following general formula (S). The narrow ratio is preferably 55% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. By being at least the lower limit of the range, the liquid stability of the liquid bleach composition and the ease of controlling the amount of dissolved gas are improved. The narrow ratio is preferably as high as possible from the viewpoint of liquid stability and controllability of dissolved gas amount, but the upper limit is substantially 95% by mass or less.

[ _Wherein n _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most abundant in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an i added mole number of ethylene oxide present in the entire ethylene oxide adduct. ]
The narrow rate can be controlled by, for example, a method for producing a polyoxyalkylene alkyl ether represented by the above formula. Such a production method is not particularly limited, but as a suitable method, for example, a surface-modified composite metal oxide catalyst described in JP-A No. 2000-144179 is used to convert the fatty acid alkyl ester. Examples thereof include a method of addition polymerization of ethylene oxide.

(B) Content of a component is 2.5-50 mass%, 3-50 mass% is preferable, More preferably, it is 5-30 mass%, Most preferably, it is 5-15 mass%. When the content of the component (B) is less than 2.5% by mass, the dissolved gas amount deviates from the desired range, so that no smell can be felt, and it is difficult to completely dissolve the fragrance in the composition. Storage stability will also be worse. If it exceeds 50% by mass, the lipophilicity of the composition becomes high, and the fragrance becomes difficult to be released into the voids of the container.
[Component (C)]
Component (C) is hydrogen peroxide and has an oxidizing power.
By using the component (C), a bleaching function can be imparted to the liquid bleach composition of the present invention.
As for content of (C) component, 0.1-5 mass% is preferable, Most preferably, it is 1-3 mass%. If the content of the component (C) is 0.1% by mass or more, the bleaching function is exhibited in proportion to the content, and if it is 5% by mass or less, the scent smells when the overcap is opened ( C) The base odor of the component is not felt.
[Amount of dissolved gas]
The dissolved gas amount in the present invention is a gas amount measured by the following method.
First, the composition stored in the liquid dispensing container described in each example is shaken 30 times, and then allowed to stand overnight (12 hours) at room temperature (25 ° C.). Place the composition in an Erlenmeyer flask with a 500 mL sleeve so that the headspace is 55 mL, apply silicone grease on the top of the sleeve of the glass tube with the sleeve (inner diameter 5 mm), and place the lower end of the glass tube at a height of 1 cm above the bottom of the flask. Install it so that it is sealed. At this time, the liquid level of the glass tube is marked with a magic to be the initial (A). This is placed in an ultrasonic device filled with water at 30 ° C. (± 1 ° C.), and the rise (B) of the liquid when ultrasonic waves are applied for 15 minutes is measured. And the amount of dissolved gas can be calculated by the following formula.

Dissolved gas amount (mL) = (BA) × 0.02
The amount of dissolved gas is preferably 1.0 to 2.0 mL. The amount of dissolved gas is greatly related to the release of the fragrance, and if it is less than 1.0 mL, the fragrance component is not gradually released, and the odor is not sustained for a long time. If it exceeds 2.0 mL, the fragrance component will be excessively dissolved in the composition, and no odor will be felt when the overcap is opened.
[Liquid dispensing container]
Hereinafter, an embodiment of a liquid dispensing container of the present invention will be described with reference to the accompanying drawings.
FIG. 1: is the sectional view of (a) extraction tool 1 of the liquid extraction container which is one Embodiment of the storage container of this invention, and (b) The front view of a plug body.

  In order to align the pouring direction when the inner plug 14A is screwed into the storage container 10 that stores the liquid bleach composition (hereinafter also referred to as the content liquid), the inner plug and the storage container are aligned. The fitting portion is provided with a ratchet structure.

  The liquid pouring container is mounted on a storage container 10 (partially shown) for storing the content liquid and the mouth portion 10a of the storage container 10 and tilts the storage container 10 so that the content liquid is removed from the hollow portion 12a. An inner plug body 14A having an approximately cylindrical dispensing nozzle 12 to be dispensed, and a storage cylinder portion (measuring unit) that receives, temporarily stores and measures the content liquid dispensed from the nozzle 12 (provided with a weighing scale) And an overcap 18 that covers the nozzle 12 and can be detachably attached to the inner plug body 14A. The ratchet structure 26 causes the inner plug body 14A to generate a ratchet effect on the container. It is to be fixed.

  In addition, a male thread part is formed on the outer surface part at the upper end part of the cylindrical wall part 20 of the inner plug body 14A, and a female thread part is formed on the lower inner surface part of the overcap 18. The upper end portion is covered with the lower portion of the overcap 18, and the overcap 18 is rotated and screwed together.

  The inner plug body 14 </ b> A is formed with a hook-shaped portion 24 for covering and mounting the mouth portion 10 a of the storage container 10 from the outer periphery thereof. The outer periphery of the mouth portion 10a of the storage container 10 at each of the opposing portions of the outer periphery of the mouth portion 10a of the storage container 10 and the inner periphery of the flange-like portion 24 of the inner plug body 14A has an axial center (reference numeral An engagement portion 26b that protrudes radially outward from (O) is provided, and a valve-like shape for engaging the engagement portion 26b on the inward wall surface of the flange-like portion 24 of the inner plug 14A. An engaging claw portion 26a is provided, and the engaging claw portion 26a extends radially inward from the inward wall surface without being fixed at the axial end.

In addition, as the storage container 10, a resin-molded one having polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), or a multilayer structure of ethylene vinyl alcohol (EVOH) and polyethylene can be suitably used.
It is.

  As the inner plug body 14A and the overcap 18, those formed of PE, PP, ABS or the like can be preferably used.

  FIG. 1: is the sectional view of (a) extraction tool 1 of the liquid extraction container which is one Embodiment of the storage container of this invention, and (b) The front view of a plug body.

  2A is a plan view, FIG. 2B is a front view, and FIG. 2C is a right side view of a storage container 1 according to an embodiment of the storage container of the present invention.

  FIG. 3 is a (a) plan view, (b) a left side view, (c) a front view, and (d) a right side view of a storage container 2 which is an embodiment of the storage container of the present invention.

  FIG. 4 is a (a) plan view, (b) front view, and (c) right side view of a storage container 3 which is an embodiment of the storage container of the present invention.

  FIGS. 5A and 5B are (a) a plan view and (b) a front view of a pouring tool 2 (comprising an inner plug body having a pouring nozzle and an overcap) which is an embodiment of the storage container of the present invention.

In FIGS. 2 to 5, the engaging portion / screwing portion of the storage container and the inner plug body and the screwing portion of the inner plug body and the overcap are omitted, but the same structure as in FIG. 1 should be used. I can do it.
[Void volume of storage container / volume of dispensing tool]
The void volume of the storage container is the volume of internal air present in the storage container when the storage container is filled with the liquid bleach composition and the pouring tool is attached.

  Specifically, after standing for 24 hours in an environment of 25 ° C. and 50% RH, distilled water is put into a storage container to the full, and the volume of the storage container is measured from the amount of distilled water (mL) at that time. The void volume of the storage container can be calculated by subtracting the amount (mL) of the liquid bleach composition contained in the container from the volume of the storage container.

  As shown in FIG. 1, the pouring tool is composed of an overcap and an inner plug, and the volume of the pouring tool is the internal volume of the pouring tool.

  Specifically, after standing for 24 hours in an environment of 25 ° C. and 50% RH, the pouring tool is inverted so that the overcap is at the bottom, and distilled water is poured into the bottom end of the fitting portion with the storage container of the inner plug body. The volume of the extraction tool can be determined from the amount of distilled water required (mL).

In the present invention, the volume ratio of the void volume of the storage container to the volume of the extraction tool is preferably 1/1 to 4/1, and particularly preferably 1/1 to 2/1. When the volume ratio is smaller than 1/1, the fragrance component present in the pouring tool increases, and the smell perceived from the opening of the inner plug body becomes worse when the overcap is opened. If it is 4/1 or more, the void volume of the storage container will be too large, and if a large amount of fragrance is not used, no smell will be felt, so it is not suitable for the present invention.
[Upper cross-sectional area of storage container / Cross-sectional area of inner plug]
In the present invention, the upper cross-sectional area of the storage container is defined as the cross-sectional area of the storage container at a position 1 cm below the lower end of the fitting portion with the pouring tool when the bottle is erected.

  The cross-sectional area of the inner plug is defined as the cross-sectional area of the upper end portion of the cylindrical wall portion. In FIG. 1, it becomes a cross-sectional area of the upper end of the cylindrical wall portion 20 of the inner plug body 14A. It can also be measured from the cross-sectional area of the overcap opening.

In the present invention, the area ratio of the upper cross-sectional area of the storage container / the cross-sectional area of the inner plug is preferably 2.5 / 1 to 3.5 / 1, particularly preferably 3.0 / 1. When the area ratio is lower than the lower limit, there is little convection on the upper part of the storage container, so that no scent is felt from the opening of the inner plug when the overcap is opened. If the area ratio exceeds the upper limit, the cross-sectional area of the inner plug body will be small, and when the overcap is opened, no odor will come out from the opening of the inner plug body, or the cross-sectional area of the upper part of the storage container Is too large for the cross-sectional area of the inner plug, so no convection occurs in the storage container and no smell is felt.
[Optional ingredients]
In addition to the components (A) to (C), an anionic surfactant, an amphoteric surfactant, a chelating agent, and a radical trapping agent are included in the liquid bleach composition in the liquid bleach article of the present invention. , PH adjusters, hydrotropes, inorganic salts, boric acid compounds, bleach activators, cyclodextrins, smectite clay minerals, cationic compounds, anti-contamination agents, water, etc. It can mix | blend suitably in the range.
(Anionic surfactant)
Examples of the anionic surfactant include linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), polyoxyethylene alkyl ether sulfate (AES), α-olefin sulfonate (AOS), and alkane sulfonate. , Α-sulfo fatty acid ester salt (α-SF), polyoxyethylene alkyl ether carboxylate and the like.
(Amphoteric surfactant)
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Can be mentioned.

As the amidoamine salt type surfactant, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide And salts of long-chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide; palmitic acid diethanolaminopropylamide salt, stearic acid diethanolaminopropylamide salt, and the like.
(Chelating agent)
The chelating agent is a chelate having a logarithmic value (log K) of the chelate stabilization constant for Fe ³⁺ and Cu ²⁺ of 10 or more and a logarithmic value (log K) of the chelate stabilization constant for Ca ²⁺ of 5.5 or more, respectively. It is an agent. The logarithmic values (log K) of chelate stabilization constants for Fe ³⁺ and Cu ²⁺ are each preferably 12 or more.
When a trace amount of iron ions or copper ions are present in the liquid bleach composition of the present invention, the stability of the component (C) may be lowered. In order to block these metal ions, a chelating agent is effective, and a logarithmic value (log K) of a chelate stability constant is generally used as an index of chelating agent efficiency. I can say that.
The chelate stability constant is determined by the following formula (I).

Equilibrium reaction between metal ion and chelating agent ... M + AZ⇔MZ _A
M: metal ion, Z: chelating agent, MZ: complex salt, A: number of Z bound to one M,
[MZ _A ]: MZ _A concentration (mol / L), [M]: M concentration (mol / L),
[Z]: represents the concentration (mol / L) of Z.

Chelating agents include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, Examples include organic phosphonic acid derivatives such as ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid. Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetrakismethylenephosphonic acid are preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable.
As 1-hydroxyethane-1,1-diphosphonic acid, a commercially available product can be used. For example, “Feliox 115” manufactured by Rhodia Japan Co., Ltd .; “BRIQUEST ADPA” manufactured by Albright Wilson Co .; “Chillest PH-210”; “DEQUEST 2010” manufactured by Monsanto, etc. The same effect can be obtained by using any of these.

The content of the chelating agent is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.3 to 3% by mass in 100% by mass of the liquid bleach composition. % Is particularly preferred. If the content of the chelating agent is within the above range, the liquid appearance becomes better, and the storage stability of the liquid bleach composition and the stability of the component (C) and the bleach activator described later are further improved. It becomes easy to do.
(Radical trapping agent)
As the radical trapping agent, a phenol radical trapping agent is preferably used. In particular, when the pH of the liquid bleach composition is 5 or more, the addition of the above-mentioned chelating agent may result in insufficient suppression of the decomposition of component (C), but the radical trapping agent is used in combination with the chelating agent. If it carries out, decomposition | disassembly of (C) component can be suppressed effectively.

  In addition, when the liquid bleach composition is applied to clothing due to misuse, etc. and left for a long time, the (C) component due to the metal component or the component (C) highly reactive with the component (C) Abnormal decomposition can occur, which can damage the clothing. In such a case, if a phenol radical trapping agent is blended in the liquid bleach composition, damage to clothing can be suppressed.

Phenol-based radical trapping agents are phenol and phenol derivatives. Preferred examples of the phenol derivative include a compound having a phenolic OH group, an ester derivative of a phenolic OH group, an ether derivative, and the like. The substitution position may be any of ortho, meta, and para positions. Among these, a compound having a phenolic OH group is more preferable, and in particular, an oxidation-reduction potential (O.P.) described in “GE Penketh, J. Appl. Chem”, pages 7,512 to 521 (1957). P.) A compound having ₀ of 1.25 V or less (more preferably 0.75 V or less) is preferable.

  Examples of such phenol derivatives include dimethoxyphenol, catechol, hydroquinone, 4-methoxyphenol, dibutylhydroxytoluene (BHT), and 4-methoxyphenol is particularly preferable.

The content of the radical trapping agent is preferably 0.01 to 6% by mass and more preferably 0.05 to 1% by mass in 100% by mass of the liquid bleach composition. If the content of the radical trapping agent is within the above range, the effect of suppressing the decomposition of the component (C) can be sufficiently obtained, and the economic efficiency can be improved.
(PH adjuster)
Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, citric acid and phosphonic acid derivatives; sodium borate, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid Sodium hydrogen, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like can be used.

A pH adjuster can be used 1 type or in mixture of 2 or more types.
(Hydrotrope agent)
Examples of the hydrotrope agent include water-miscible organic solvents. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol; glycols such as propylene glycol, butylene glycol, hexylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, mass average molecular weight Polyethylene glycol having a weight average molecular weight of about 400, polyglycols such as dipropylene glycol, and the like; alkyl ethers of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, and the like.

The content of the hydrotrope is preferably 0.1 to 15% by mass in 100% by mass of the liquid bleach composition.
(Inorganic salts)
As inorganic salts, sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate, sodium silicate, magnesium sulfate, magnesium silicate, magnesium chloride and the like can be used.
(Boric acid compound)
Examples of the boric acid compound include orthoboric acid (H ₃ BO ₃ ); a salt formed by borate ion (BO ₃ ³⁻ ) or (BO ₄ ⁵⁻ ), or an anion salt condensed with them (condensed borate salt) ) And the like.

  Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; ammonium salt and the like. Of these, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.

  Among the boric acid compounds described above, particularly preferred are orthoboric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, ammonium tetraborate and the like. Acid and sodium tetraborate are more preferable.

  As the sodium tetraborate, hydrated salts such as sodium tetraborate · pentahydrate and sodium tetraborate · 10 hydrate (borax) are particularly preferable.

Boric acid compounds can be used alone or in combination.
The content of the boric acid compound is not particularly limited, and is preferably 0.2 to 10% by mass and more preferably 1 to 5% by mass in 100% by mass of the liquid bleach composition. The content in the case of using the water-containing salt of tetrasodium borate as boric acid compound, sodium tetraborate _{(Na 2} B 4 _{O 7)} concentration calculated in terms of _(i.e., Na ₂ B 4 _{O 7} amount) Indicates.

When the content of the boric acid compound is 0.2% by mass or more, the removal efficiency especially for aqueous stains is improved. On the other hand, when the content of the boric acid compound is 10% by mass or less, the storage stability of the liquid bleach composition at a low temperature is improved.
(Bleaching activator)
Bleach activators include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, dodecanoyl Sodium oxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, Examples include organic peracid precursors such as undecanoyloxybenzene and dodecanoyloxybenzene.

  Among these, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, and decanoyloxybenzoic acid can be preferably used.

  Bleach activators can be used alone or in combination.

The content of the bleach activator is preferably 0.1 to 5.0% by mass and more preferably 0.1 to 2.0% by mass in 100% by mass of the liquid bleach composition. When the content of the bleach activator is within the above range, the bleaching power and storage stability of the liquid bleach composition are improved, and the economic efficiency is also improved.
(Cyclodextrin)
Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

  These cyclodextrins have a large internal volume (Å3) per molecular weight in the order of γ, β, α. Since the inclusion capacity is higher as the internal volume per molecular weight is larger, it is considered that the component (B) is easier to include, and it is considered that the coating detergency of the liquid bleach composition is improved, and β-cyclodextrin and γ-cyclodextrin are preferred. .

  These may be used alone or in combination of two or more.

The content of cyclodextrin is preferably 0.01 to 1.4% by mass, more preferably 0.1 to 1.4% by mass, and 0.3 to 1.4% by mass in 100% by mass of the liquid bleach composition. % Is more preferable, and 0.6 to 1% by mass is particularly preferable.
(Smectite clay mineral)
The smectite-type 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.

In the present invention, synthetic smectite is preferred as the smectite clay mineral.
As the synthetic smectite, commercially available ones can be used. For example, Laponite RD (synthetic hectorite) manufactured by Wilber Ellis Co., Ltd. Optigel SH (synthetic hectorite) manufactured by Sud Chemie Catalysts Co., Ltd., smecton manufactured by Kunimine Industries Co., Ltd. SA (synthetic saponite) etc. are mentioned.

  These may be used alone or in combination of two or more.

The blending amount of the smectite clay mineral is preferably 0.1 to 10% by mass, more preferably 0.2 to 5.0% by mass, and 0.5 to 3.0% by mass in 100% by mass of the liquid bleach composition. % Is particularly preferred. 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.
(Cationic compound)
Examples of the cationic compound include a cationic surfactant and a cationic polymer.

  As cationic surfactants, various quaternary ammonium salts such as mono long chain hydrocarbon type quaternary ammonium salts, di long chain hydrocarbon type quaternary ammonium salts, amidoamine type surfactants, amide ester type surfactants Agents and the like.

  The cationic polymer is not particularly limited as long as it is a polymer having a cationic group, and examples thereof include dimethyldiallylammonium-based polymers and biguanide-based polymers.

  Among the above cationic compounds, dimethyldiallylammonium polymers and biguanide polymers can be suitably used.

  Commercially available dimethyldiallylammonium-based polymers include MERQUAT100 (Calgon), Adekathioace PD-50 (ADEKA), Daidol EC-004, Daidol HEC, Daido Kasei Co., Ltd., etc. Is mentioned.

  Examples of commercially available biguanide polymers include poly (hexamethylene biguanide) hydrochloride and trade name Proxel IB (registered trademark, manufactured by Arch Chemicals Japan Co., Ltd.).

As content of a cationic compound, 0.001-2 mass% is preferable, and 0.01-2 mass% is more preferable. If it is 0.001 mass% or more, the disinfection effect and the antibacterial effect are good, and if it exceeds 2 mass%, the storage stability tends to be lowered.
(Recontamination inhibitor)
As a recontamination preventive agent, water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit, carboxymethyl cellulose, polyethylene glycol having a mass average molecular weight of 600 to 20000, polyvinyl Pyrrolidone can be used.

Among these, a water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit is preferable. Specific examples of commercially available products include “TexCare” manufactured by Clariant Japan. SRN-100 (weight average molecular weight 3000) "," TexCare SRN-300 (weight average molecular weight 7000) ".
(water)
In the liquid bleach composition according to the present invention, the water content is preferably 10 to 95% by mass and more preferably 20 to 90% by mass in 100% by mass of the liquid bleach composition.
[Production of liquid bleach composition]
A liquid bleaching agent composition can be manufactured according to a conventional method. For example, a solvent such as water (for example, ion-exchanged water) such that the components (A) to (C) described above and an optional component as required are in a desired content in terms of the pure content of each component. It is obtained by dissolving and mixing in the solution and further adjusting to a predetermined pH using a pH adjuster as necessary.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
[Raw materials]
As the component (A), the fragrance compositions A to D described in Tables 1 to 6 were used.

In the component (B), the following compounds were used as nonionic surfactants.
B-1: Polyoxyethylene alkyl ether (ethylene oxide adduct) represented by the following general formula (I), which has a narrow ratio represented by the general formula (S) (the number of added moles of ethylene oxide is different) An ethylene oxide adduct whose ratio of the distribution of the ethylene oxide adduct is specified, manufactured by Lion Corporation.
^{_{R 1 O- (CH 2 CH 2}} O) n '-H ··· (I).
[Wherein, R ¹ represents an alkyl group; n represents an average number of moles of ethylene oxide added. ]
Narrow ratio 84 mass%, alkyl group R ¹ = C ₁₂ H ₂₅ —, ethylene oxide (EO) average added mole number n ′ = 5.
B-2: Polyoxyethylene alkyl ether (12 carbon atoms of alkyl group, average addition mole number of EO 15; trade name “EMALEX 715”, manufactured by Nippon Emulsion Co., Ltd.)
In addition, the narrow rate of B-1 and B-2 was calculated | required as follows.
Using high performance liquid chromatography (HPLC), the distribution of ethylene oxide adducts with different numbers of added moles of ethylene oxide in the resulting synthesized product was measured under the following measurement conditions. And the narrow rate (mass%) of B-1-B-2 was computed based on the said Numerical formula (S).
(Conditions for measuring the distribution of ethylene oxide adducts by HPLC)
Apparatus: LC-6A (manufactured by Shimadzu Corporation).
Detector: SPD-10A.
Measurement wavelength: 220 nm.
Column: Zorbax C8 (manufactured by Du Pont).
Mobile phase: acetonitrile / water = 60/40 (volume ratio).
Flow rate: 1 mL / min.
Temperature: 20 ° C.
As the component (C), the following compounds were used.
C-1: Hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd.).
As optional components, the following compounds and the like were used.
LAS: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Corporation, “Lypon LH-200 (LAS-H)”, pure content 96 mass%)], the blending amount in the table is pure content As a value (mass%).
SAS: secondary alkanesulfonic acid Na (manufactured by Clariant Japan KK, trade name “SAS30” (pure content: 30% by mass)), and the blending amount in the table indicates a value (% by mass) as a pure component.
MQ: 4-methoxyphenol (product name “MQ-F”, manufactured by Kawaguchi Chemical Co., Ltd.).
HEDP: 1-hydroxyethane-1,1-diphosphonic acid (manufactured by Rhodia Japan Co., Ltd., trade name “Feriox 115”), and the blending amount in the table indicates a value (mass%) as a pure component.
Na borate: sodium tetraborate pentahydrate (Borax, trade name “Neobor”)
Bleach activator: sodium 4-dodecanoyloxybenzenesulfonate (manufactured by Mitsui Chemicals)
Cyclodextrin: β-cyclodextrin (manufactured by Nippon Shokuhin Kako Co., Ltd., trade name “Seldex B-100”)
Smectite: Smectite-type synthetic silicate laponite RD (product of Laporte, UK, Laponite RD, Laporte Industries Ltd., UK)
Cationic compound: polyhexamethylene biguanide hydrochloride (manufactured by Arch Chemicals Japan Co., Ltd., “Proxel IB”), the compounding amount in the table indicates the value (mass%) as a pure component.
SR agent: manufactured by Clariant Japan Co., Ltd., trade name “Texcare SRN-100”, and the blending amount in the table indicates a value (mass%) as a pure component.
[Examples 1-18, Comparative Examples 1-13]
<Preparation of liquid bleach composition>
The liquid bleaching compositions shown in Tables 7 to 9 were produced as follows according to a conventional method.
First, the component (B) was placed in a 1 L beaker containing a stirring bar having a size of 8 mmφ × 40 mm. Next, component (A) and optional components were added while stirring at 700 rpm, purified water was added, and then component (C) was added to produce a liquid bleach composition.
In addition, the unit of the compounding quantity in Tables 7-9 is the mass%, and shows the pure amount conversion amount.
<Evaluation>
[Measurement of dissolved gas content]
The liquid bleaching agent composition of each example was filled in the liquid dispensing container described in each example with the filling amount shown in Tables 7 to 9, and the cap (medium plug body, overcap) was tightly closed, and then shaken 30 times. Let stand overnight (12 hours) at room temperature (25 ° C.). Then slowly put the composition into a 500 mL Erlenmeyer flask with 55 mL of head space so that the headspace is 55 mL, apply silicone grease on the upper part of the glass tube (5 mm inner diameter), and place the lower end of the glass tube 1 cm above the bottom of the flask. Install so that it is hermetically sealed. At this time, the liquid level of the glass tube is marked with a magic to be the initial (A). This is placed in an ultrasonic device filled with water at 30 ° C. (± 1 ° C.), and the rise (B) of the liquid when ultrasonic waves are applied for 15 minutes is measured. After the measurement, the dissolved gas amount was calculated by the following formula.

Dissolved gas amount (mL) = (BA) × 0.02
In addition, when it was not the said head space with the filling amount of each example, two liquid pouring containers filled with the liquid bleach composition were used.
[Odor evaluation]
The liquid bleaching agent composition of each example was filled in the liquid dispensing container described in each example in the filling amounts shown in Tables 7 to 9, and the overcap was tightly closed, and then one day in an environment of 10 ° C. and 50% RH. Leave still. Thereafter, the overcap was opened, and three expert panelists evaluated the smell from the bottle mouth (inner plug opening) and the absence of the base odor of component (C).
The smell was classified into the following evaluation criteria and evaluated.
(Evaluation criteria)
5 points: very scented 4 points: very scented 3 points: scented 2 points: slightly scented or slightly base odor 1 point: odorless, or Two or more points that felt the base odor were considered acceptable.

  The following containers were used as liquid dispensing containers.

The liquid extraction container (storage container, extraction tool) used for dissolved gas amount measurement and smell evaluation will be described with reference to FIGS.
FIG. 1 is (a) a cross-sectional view of the liquid pouring container used for the dissolved gas amount measurement and odor generation evaluation, and (b) a front view of the inner plug, and the volume of the pouring tool is 45 mL in actual measurement. The cross-sectional area of the extraction tool was 12.6 cm ² .
2A is a plan view, FIG. 2B is a front view, and FIG. 2C is a right side view of the storage container 1 used for measurement of dissolved gas amount and evaluation of smell generation. The upper cross-sectional area of the container was 38.2 cm ² .
3A is a plan view, FIG. 3B is a left side view, FIG. 3C is a front view, and FIG. 3D is a right side view of the storage container 2 used for dissolved gas amount measurement and odor evaluation. The measured volume was 605 mL, and the upper cross-sectional area of the storage container was 63.0 cm ² .
4A is a plan view, FIG. 4B is a front view, and FIG. 4C is a right side view of the storage container 3 used for measurement of dissolved gas amount and evaluation of smell generation. The volume of the storage container is measured to be 575 mL. The upper cross-sectional area of the container was 28.3 cm ² .
5A is a plan view and FIG. 5B is a front view of the pouring tool 2 used for measurement of dissolved gas amount and evaluation of smell generation. The volume of the pouring tool is 28 mL in actual measurement, and the cross-sectional area of the pouring tool is 11. It was 3 cm ² .

  In addition, the material of the extraction tools 1-2 was a polypropylene, and the material of the storage containers 1-3 was a high density polyethylene.

  As is clear from Examples 1 to 18 described in Tables 7 to 8, it was confirmed that the liquid bleaching composition shown in each Example had good odor.

On the other hand, about the comparative example of Table 9,
(B) Comparative Examples 1 and 2 in which the content of the component is out of range, Comparative Examples 3 to 4 and Comparative Examples 7 to 8 in which the volume ratio of void volume / pourer volume of the storage container is out of range, upper part of the storage container It was confirmed that in Comparative Examples 5 to 6 and Comparative Examples 9 to 10 where the area ratio of the cross-sectional area / the cross-sectional area of the inner plug body was out of the range, no smell was felt.

DESCRIPTION OF SYMBOLS 10 Storage container 10a Mouth part 12 of a storage container Outlet nozzle 14A Middle plug body 24 Gutter-shaped part 26 Ratchet structure (fitting part)
26a engaging claw part 26b engaging part 30 slit 50 formed in bowl-shaped part pouring tool 51 overcap 52 inner plug body O axis center

Claims (2)

(A) a fragrance composition, (B) a nonionic surfactant: 2.5 to 50% by mass, (C) a liquid bleach composition containing hydrogen peroxide,
A storage container for storing the liquid bleach composition is provided with a pouring tool comprising an inner plug mounted on a mouth portion of the container and provided with a pouring nozzle, and an overcap mounted on the inner plug. Fill the liquid dispensing container attached to the mouth,
The volume of dissolved gas in 500 g of the liquid bleach composition is 1.0 mL or more and 2.0 mL or less, and the volume of the void volume (mL) of the storage container after filling the liquid bleach composition / volume of the extraction tool (mL). The area ratio is 1/1 to 4/1, and the area ratio of the upper sectional area (cm ² ) of the storage container / the sectional area (cm ² ) of the inner plug is 2.5 / 1 to 3.5 / 1. A liquid bleach article characterized in that The fragrance composition of component (A) is contained in an amount of 0.01 to 1% by mass, the nonionic surfactant of component (B) is an alkylene oxide addition type nonionic surfactant, The liquid bleach article according to claim 1, containing 50% by mass.