JP4459611B2 - Liquid bleach products - Google Patents

Description

  The present invention relates to a liquid bleach composition and a liquid bleach product using the same.

  Dirt in places where water is frequently used such as bathroom tiles, bathtubs, kitchen tiles, joints, plastics, pottery, drain pipes, etc. in the area around the house is mostly due to organic substances caused by mold, and the main component is surfactant. In order to remove these stains, conventionally, a bleaching agent mainly containing an alkali metal hypochlorite is frequently used.

As a method for easily using such a bleaching agent, a method of spraying a liquid bleaching agent using a dispenser is often employed, and in order to prevent mist from splashing or splashing of the liquid during spraying, Liquid bleaching agents whose foaming power is improved by blending an activator have been proposed (for example, Patent Documents 1 to 3 below).
However, the conventional liquid bleaching agent has insufficient adhesion retention, so it cannot remove dirt and mold to a satisfactory level, and the bleaching agent must be sprayed in the same place over and over again. Therefore, there was an economic problem due to fatigue of wrists and arms and waste of bleach.

On the other hand, in order to improve adhesion and retention of vertical surfaces and inclined surfaces, a thickening method by salting out using a complex of two or more kinds of surfactants has been proposed (for example, Patent Documents 4 and 4 below). 5).
JP-A-63-72798 JP-A 63-165495 JP-A-8-41495 JP-A-6-184594 Japanese Patent Laid-Open No. 10-60491

  However, when the bleaching agent is thickened by the above conventional method, it is difficult to spray the bleaching agent in a spray pattern having a spread from the dispenser, and after spraying, the liquid from the discharge port of the dispenser container is difficult to spray. There was a problem in terms of usability and the like because sagging was likely to occur.

  The present invention has been made in view of the above circumstances, and is excellent in adhesion retention when sprayed on a vertical surface or an inclined surface as well as on a horizontal surface, and can prevent dripping from a discharge port. It is an object to provide a liquid bleach composition and a liquid bleach product using the same.

  As a result of intensive studies to achieve the above object, the present inventor, in addition to the alkali metal hypochlorite salt and the bleach base of the alkali agent, a surfactant, and a polyalkylene glycol derivative, The inventors have found that by adding a polyethylene glycol derivative having a hydrocarbon group having an aromatic ring, a favorable adhesion retention property to the surface to be cleaned can be obtained and liquid dripping can be prevented, and the present invention has been achieved.

That is, the liquid bleach product of the present invention comprises a container main body and a discharge means for discharging the liquid in the container main body, and the discharge means has a foam-forming mechanism. (A) Hypochlorous acid Acid alkali metal salt 1-5% by mass , (b) alkali agent 0.1-5% by mass , (c) surfactant 0.01-3% by mass , (d) compound represented by the following chemical formula (I) And (e) a compound represented by the following chemical formula (II) , wherein the total content of the compound (d) and the compound (e) is 0.1% by mass or more and 0.4% by mass or less. And a liquid bleaching agent composition in which the mass ratio [(d) / (e)] of the content of the compound (d) and the content of the compound (e) is 0.3 or more and 6 or less. It is characterized by.
R ¹ —O — [(EO) p, (AO) q] —R ² (I)
(Wherein R ¹ and R ² are a hydrogen atom or a branched or straight chain alkyl group having 1 to 7 carbon atoms, EO is an oxyethylene group, and AO is one kind selected from an oxyalkylene group having 3 to 8 carbon atoms, or Represents two or more, p represents the average number of moles added of ethylene oxide (EO), and is a numerical value of 1 ≦ p ≦ 500, q represents the average number of moles added of alkylene oxide (AO), and 0 ≦ q ≦ (The value is 10.)
R ³ —O— (EO) r—R ⁴ (II)
(In the formula, R ³ represents a hydrocarbon group having an aromatic ring, R ⁴ represents a hydrogen atom or a branched or straight chain alkyl group having 1 to 7 carbon atoms, EO represents an oxyethylene group, and r represents ethylene oxide (EO ) Represents the average number of moles added, and is a numerical value of 1 ≦ r ≦ 30.)

The liquid bleaching agent composition preferably has a viscosity of 10 mPa · s or more after 1 minute from the start of stirring, measured with a B-type viscometer under the conditions of a temperature of 25 ° C. and a rotation speed of 60 rpm.
Further, as the surfactant (c), (c-1) one or more selected from fatty acid alkali metal salts having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and (c-2) Alkylamine oxide having a branched or straight chain alkyl group having 8 to 20 carbon atoms, alkyl sulfate ester salt having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and a branched or straight chain having 8 to 20 carbon atoms 1 type or 2 types or more selected from the group consisting of polyoxyethylene alkyl ether sulfates having an alkyl group are used, and the total content of component (c) is 0.01 to 2% by mass , the value of (c-1) / (c -2) represented by the mass ratio is preferably in the range on the 7/3 than the lower 3/7 than.

The liquid bleach composition of the present invention has good bleaching performance, is excellent in adhesion retention when sprayed using a discharge container such as a dispenser, and prevents dripping from the discharge port.
The liquid bleach product of the present invention provides good adhesion retention even when sprayed on a soiled object on a vertical surface or inclined surface as well as a horizontal surface, and the bleaching action by the liquid bleach composition is effective. Is obtained. In addition, dripping from the discharge port of the discharge container is prevented, and it is excellent in usability.

Hereinafter, embodiments of the present invention will be described in more detail.
Examples of the alkali metal hypochlorite of the component (a) used in the present invention include sodium hypochlorite and potassium hypochlorite, and sodium hypochlorite is particularly preferable. The content of the alkali metal hypochlorite of the component (a) in the bleaching composition of the present invention is usually 0.1 to 10% by weight, preferably 1 to 5% by weight of the whole bleaching composition. It is a range. When the content of the component (a) is less than 0.1% by mass, the bleaching power is insufficient, and when it exceeds 10% by mass, the detergency is not particularly improved.

  Although it does not restrict | limit especially as an alkali agent of (b) component used for this invention, A caustic alkali, a silicate, etc. are mentioned. As the caustic alkali, sodium hydroxide, potassium hydroxide and the like are used, and as the silicate, sodium metasilicate and the like are used. Of these, sodium hydroxide is preferably used. The content of the alkaline agent as the component (b) in the bleaching composition of the present invention is usually in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight of the entire bleaching composition. . When the content of the component (b) is less than 0.1% by mass, the stability of the alkali metal hypochlorite decreases with time. The effect by cannot be demonstrated.

  The surfactant of the component (c) used in the present invention is not particularly limited, and for example, known anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric interfaces that are generally blended in detergents and the like. One or more of the active agents can be appropriately selected and used. A surfactant having a thickening action is preferred. In particular, (c-1) one or two or more fatty acid alkali metal salts having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and (c-2) a branched or branched structure having 8 to 20 carbon atoms, or Alkylamine oxide having a linear alkyl group, alkyl sulfate ester salt having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and polyoxyethylene having a branched or straight chain alkyl group having 8 to 20 carbon atoms It is preferable to use a combination of one or more selected from the group consisting of alkyl ether sulfates.

The fatty acid alkali metal salt of (c-1) is not particularly limited, but is a fatty acid alkali metal salt having a linear or branched alkyl group having 8 to 20 carbon atoms, and a fatty acid alkali metal having an unsaturated alkyl group. Those containing a salt are preferred. Preferable examples of the alkali metal salt of the unsaturated fatty acid include, for example, coconut fatty acid (derived from coconut oil) containing an average of about 12 carbons, and tallow fatty acid (containing tallow fats) containing an average of about 18 carbon atoms. Origin), sodium salts such as oleic acid and linoleic acid, and potassium salts. As the component (c-1), an alkali metal salt of an unsaturated fatty acid may be used alone. For example, an unsaturated fatty acid such as oleic acid or linoleic acid, lauric acid, myristic acid, palmitic acid, stearic acid A sodium salt, a potassium salt, etc. of a mixture with a saturated fatty acid such as may be used.
When the alkali metal salt of a mixture of an unsaturated fatty acid and a saturated fatty acid is used as the component (c-1), the proportion of the alkali metal salt of the unsaturated fatty acid in the component (c-1) is 2% by mass or more. It is preferable that it is 7 mass% or more especially. When the proportion of the unsaturated metal salt of the unsaturated fatty acid is too small, the viscosity of the liquid bleaching composition is lowered, and as a result, the adhesion retention is deteriorated.

Although it does not restrict | limit especially as an alkylamine oxide of (c-2) component, It is preferable that it is a tertiary alkylamine oxide, and it is a tertiary alkylamine oxide represented by the following general formula (III). Further preferred.

（式中、Ｒ^５は炭素数８〜２０の直鎖又は分岐鎖のアルキル基、Ｒ^６は炭素数１〜３のアルキル基、Ｒ^７は炭素数１〜３のアルキル基をそれぞれ表す。）

(In the formula, R ⁵ represents a linear or branched alkyl group having 8 to 20 carbon atoms, R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents an alkyl group having 1 to 3 carbon atoms.)

In the general formula (III), examples of R ⁵ include octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, myristyl group, and mixtures of alkyl groups having different carbon numbers derived from natural products. It is done. Among these, a dodecyl group, a myristyl group, and an alkyl group derived from coconut oil are preferable. Examples of R ⁶ and R ⁷ include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
Specific examples of the tertiary alkylamine oxide represented by the general formula (III) include lauryldimethylamine oxide, myristyldimethylamine oxide, coconut dimethylamine oxide, and the like.

As the alkyl sulfate ester salt of component (c-2), an alkyl sulfate ester salt represented by the following general formula (IV) is desirable.
R ⁸ O—SO ₃ —M (IV)
(In the formula, R ⁸ represents a linear or branched alkyl group having ⁸ to 20 carbon atoms, and M represents a cationic group.)
Specific examples of the cation group (M) include sodium, potassium, triethanolamine group, ammonium group and the like.
Preferable examples of the alkyl sulfate ester salt represented by the general formula (IV) include sodium lauryl sulfate and sodium myristyl sulfate.

The polyoxyethylene alkyl ether sulfate salt of component (c-2) is preferably a polyoxyethylene alkyl ether sulfate salt represented by the following general formula (V).
_{^{R 9 - (EO) n-}} SO 3 -M ... (V)
(In the formula, R ⁹ represents a linear or branched alkyl group having 8 to 20 carbon atoms, EO represents an oxyethylene group, and M represents a cationic group. N represents the average number of added moles of ethylene oxide (EO)). 1 to 10)
Specific examples of the cation group (M) include sodium, potassium, triethanolamine group, ammonium group and the like.
Preferable examples of the polyoxyethylene alkyl ether sulfate salt represented by the general formula (V) include sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate.

The total content [(c-1) + (c-2)] of the component (c) in the liquid bleach composition of the present invention is preferably 0.01 to 3% by mass of the total composition, more preferably. Is in the range of 0.1 to 2% by weight. When the content of the component (c) is less than 0.01% by mass, the adhesion retention is inferior, and when it exceeds 3% by mass, the decomposition of the alkali metal hypochlorite is promoted and the stability is lowered.
The ratio of the content of the component (c-1) and the component (c-2) is not particularly limited, but the mass ratio value represented by (c-1) / (c-2) is 8/2 or more. preferably in the range of the lower 2/8 or more, more preferably in the range of the 7/3 than the lower 3/7 than. When the ratio (c-1) increases, the viscosity of the system decreases, and when the ratio (c-2) increases, decomposition of the alkali metal hypochlorite tends to be accelerated.

The component (d) is a polyoxyalkylene glycol derivative, and a compound represented by the above general formula (I) is used. Specific examples of the alkyl group for R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a pentyl group, and a hexyl group.
When the average addition mole number (p) of ethylene oxide (EO) is less than 1, sufficient adhesion retention is not obtained, and when the p exceeds 500, or the average addition mole number (q) of alkylene oxide (AO) is If it exceeds 10, the stability of the system is lowered, and precipitation occurs particularly under low temperature storage, which is not preferable.

The component (e) is a polyoxyethylene glycol derivative, and the compound represented by the general formula (II) is used. Specific examples of R ³ include a phenyl group, a benzyl group, and a naphthyl group. Specific examples of R ⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and the like. If the average added mole number (r) of ethylene oxide (EO) is less than 1, the stability of the alkali metal hypochlorite decreases, and if it exceeds 30, the viscosity of the system decreases, which is not preferable.

The total content [(d) + (e)] of the component (d) and the component (e) in the liquid bleach composition of the present invention is 0.01% by mass or more and 0.5% by mass with respect to the entire composition. % Or less is preferable, and more preferably 0.1% by mass or more and 0.4% by mass or less. When the total content of component (d) and component (e) is less than 0.01% by mass, dripping from the container outlet tends to occur, and when it exceeds 0.5% by mass, alkali metal hypochlorite is used. Decomposition is promoted.
The ratio (mass basis) of the component (d) and the component (e) represented by [(d) / (e)] is preferably in the range of 0.1 to 10, more preferably 0.3 to 6. It is as follows. When the [(d) / (e)] is less than 0.1, coarse bubbles are not formed in the viscous liquid bleach composition, and as a result, desired adhesion retention is not obtained. Further, when [(d) / (e)] exceeds 10, liquid dripping from the discharge port cannot be suppressed.

  Other optional components can be added to the liquid bleach composition of the present invention as necessary. Specifically, aromatic sulfonates such as toluene sulfonate, xylene sulfonate, cumene sulfonate, and the like as builders that improve the cleaning performance; solvents; dyes; It is possible to mix | blend in the range which does not disturb. Moreover, it can prepare by a conventional method by adding balance amount of water to said essential component and other arbitrary components.

  In the present invention, the viscosity of the liquid bleach composition is preferably 10 mPa · s or more. As the viscosity of the liquid bleach composition in the present specification, the viscosity one minute after starting stirring, measured with a B-type viscometer (using a second rotor) under the conditions of a temperature of 25 ° C. and a rotational speed of 60 rpm. Adopted. If the viscosity of the liquid bleach composition is lower than the above range, adhesion retention may be inferior, and as a result, the desired bleaching effect cannot be obtained. The viscosity of the liquid bleach composition is more preferably 50 mPa · s or more. The upper limit of the viscosity is not particularly limited as long as it can be discharged from the discharge container to be used, but is preferably 300 mPa · s or less, more preferably 200 mPa · s or less in order to obtain good discharge properties and usability. is there.

The liquid bleach composition of the present invention is preferably used by being housed in a discharge container equipped with a foam-forming mechanism for ejecting the content liquid in the form of foam.
When the liquid bleaching agent composition of the present invention is sprayed onto a soiled object on a vertical surface or an inclined surface using a discharge container equipped with a discharge means having a foaming mechanism, excellent foaming properties are obtained, and the object to be cleaned Since it adheres with a moderate spread on the surface, it is possible to uniformly cover the dirty part. In addition, excellent adhesion retention can be obtained, and there is no dripping from the discharge port, and good bleaching performance can be obtained. Therefore, it can be suitably used especially for hard surfaces such as bathrooms, kitchens and toilets.

  In addition, the bleaching composition of the present invention does not form a foam when the object to be cleaned is dirt in a deep place such as a water pipe in a bathroom or a kitchen, but the solution is poured directly from the opening of the container body. It can also be used. In this case, the discharge means may not be provided. In such a method of use, the bleaching composition of the present invention can be smoothly discharged with good fluidity when poured out from a container, there is no dripping from the discharge port after pouring, Further, since it easily adheres uniformly to the dirty surface to be cleaned, it has the advantage that the effect of removing the stain by the bleaching component can be obtained safely and efficiently.

As an embodiment of a discharge container suitably used for the liquid bleach product of the present invention, for example, a discharge container described in JP-A-2003-41300 can be used. FIG. 1 is a cross-sectional view of the main part of the discharge container. The discharge container 1 of this embodiment is provided with a trigger sprayer (discharge means) 6 at the opening of the container body 2. The trigger sprayer 6 is configured to discharge the liquid bleaching composition in the container body 2 by pulling the trigger 3 and operating the piston 4 and the spring 5.
The trigger sprayer 6 is provided with a foaming mechanism. Examples of the foam-forming mechanism include known foam-forming mechanisms such as a structure in which a foam-forming cylinder is provided on the flight path of the liquid bleach composition and a structure in which a mesh screen is provided on the flight path of the liquid bleach composition. It can be used as appropriate.

  For example, when a foam-forming cylinder is provided as the foam-forming mechanism, the foam-forming cylinder is provided outside the nozzle hole 10. Then, the liquid bleaching composition injected from the nozzle hole 10 entrains air inside the foaming cylinder while colliding with the inner wall of the foaming cylinder, and as a result, is discharged in the form of foam. As for a foaming cylinder, it is desirable that the uneven surface part is formed in the inner wall surface. Further, it is desirable that the foam-forming cylinder is arranged so as to have a central axis substantially the same as the central axis in the flight direction of the liquid bleach composition. The minimum diameter of the inner wall of the foam tube is preferably about 2 to 8 mm.

  On the other hand, when a mesh screen is provided as a foaming mechanism, a mesh screen in which a plurality of mesh holes are formed is provided so as to close the discharge port outside the nozzle hole 10. Then, the liquid bleaching composition injected from the nozzle hole 10 entrains air while colliding with the mesh screen, and is discharged as foam from the mesh hole. It is desirable that the mesh screen is disposed substantially orthogonal to the center axis in the flight direction of the liquid bleach composition.

  Moreover, the structure which combined the mesh-like screen and the foaming cylinder is also preferable. For example, when a mesh screen is provided near the outlet of the foam cylinder, the liquid bleach composition entrains air inside the foam cylinder while colliding with the inner wall of the foam cylinder, and also when the screen passes through the mesh screen. Since air is entrained on the surface, bubbles can be included more effectively.

  The discharge means is not limited to the above example. For example, a structure in which a foaming mechanism is provided in a pump sprayer that discharges the composition stored in the container main body through the dip tube by moving the pump head up and down is used. You can also.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not restrict | limited by the following Example.
(Examples 1-8, Comparative Examples 1-3)
A liquid bleach composition was prepared with the formulation shown in Table 1 below (unit: mass%). The viscosity, anti-drip property, and adhesion retention of the obtained liquid bleach composition were evaluated by the following methods. The evaluation results are shown in Table 1.

<Measurement of viscosity>
Using a B-type viscometer (manufactured by TOKIMEC; DVL-B2), a value one minute after the start of stirring was measured at 25 ° C. under the conditions of a rotation speed of 60 rpm and a second rotor.

<No dripping when sprayed 10 times (prevents dripping)>
Using a trigger type dispenser (manufactured by Yoshino Kogyo; YT87l-FM) with a foam-forming mechanism that was adjusted so that the sample was sprayed in a steady state, there was no liquid dripping from the discharge port after spraying 10 times. evaluated. The case where no dripping was observed is indicated by ○, and the case where dripping occurred is indicated by x.

<Measurement of adhesion retention rate (adhesion retention)>
Using a trigger-type dispenser (Yoshino Kogyo; YT87l-FM) with a foam-forming mechanism, adjusted so that the sample is sprayed in a steady state, a vertically standing spray panel (30 × 30 cm; manufactured by ABS) The liquid bleach composition was sprayed for 2 strokes from the position at a separation distance of 20 cm in the center portion, and the mass of the panel was measured after 1 minute. The adhesion retention rate was calculated by the following formula. The measurement was performed three times under the same conditions, and the average value of the adhesion retention rate of three times is indicated as ◯, the case of 60% or more and less than 80% as Δ, and the case of less than 60% as ×.

The following materials were used as components marked with an annotation (*) in Table 1.
* 1 Neutral fatty acid manufactured by Nippon Oil & Fats Co., Ltd. neutralized with potassium hydroxide * 2 "Lauric acid" manufactured by Nippon Oil & Fats Co., Ltd. neutralized with sodium hydroxide * 3 "Aromox DMC-" manufactured by Lion Chemical Co., Ltd. W
* 4 “ALOMOX DM14D-N” manufactured by Lion Chemical Co., Ltd.
* 5 “Sannor DM1470” manufactured by Lion Chemical Co., Ltd.
* 6 “Sannor LM-1130” manufactured by Lion Chemical Co., Ltd.
* 7 “PEG # 6000M” manufactured by Lion Chemical Co., Ltd.
* 8 “PEG # 4000” manufactured by Lion Chemical Co., Ltd.
* 9 “2-Ethylhexyl glycol” manufactured by Nippon Emulsifier Co., Ltd.
* 10 “Dimethylpropylene diglycol” manufactured by Nippon Emulsifier Co., Ltd.
* 11 “Diethyl diglycol” manufactured by Nippon Emulsifier Co., Ltd.
* 12 “Phenyl glycol” manufactured by Nippon Emulsifier Co., Ltd.
* 13 “Phenyl Diglycol” manufactured by Nippon Emulsifier Co., Ltd.
* 14 “Benzyl glycol” manufactured by Nippon Emulsifier Co., Ltd.
* 15 “Benzyl Diglycol” manufactured by Nippon Emulsifier Co., Ltd.
* 16 “Kayafect Yellow S” manufactured by Nippon Kayaku Co., Ltd.

It is the schematic sectional drawing which showed the principal part of the discharge container concerning embodiment of this invention.

Explanation of symbols

1. 1. Discharge container 2. Container body Trigger 4. Piston 5. Spring 6. Trigger type sprayer (discharge means)

Claims (3)

A container body and a discharge means for discharging the liquid in the container body, the discharge means having a foam-forming mechanism;
(A) 1-5% by mass of alkali metal hypochlorite, (b) 0.1-5% by mass of alkaline agent, (c) 0.01-3% by mass of surfactant, (d) the following chemical formula (I ) And (e) a compound represented by the following chemical formula (II), and the total content of the compound (d) and the compound (e) is 0.1% by mass or more and 0.0. A liquid bleaching agent having a mass ratio [(d) / (e)] of not less than 4 and not more than 4% by mass and a content of the compound (d) and the content of the compound (e) is not less than 0.3 and not more than 6 A liquid bleach product containing the composition.
R ¹ —O — [(EO) p, (AO) q] —R ² (I)
(Wherein R ¹ and R ² are a hydrogen atom or a branched or straight chain alkyl group having 1 to 7 carbon atoms, EO is an oxyethylene group, and AO is one kind selected from an oxyalkylene group having 3 to 8 carbon atoms, or Represents two or more, p represents the average number of moles of ethylene oxide added and is a numerical value of 1 ≦ p ≦ 500, q represents the average number of moles of added alkylene oxide, and 0 ≦ q ≦ 10. )
R ³ —O— (EO) r—R ⁴ (II)
(Wherein R ³ represents a hydrocarbon group having an aromatic ring, R ⁴ represents a hydrogen atom or a branched or straight chain alkyl group having 1 to 7 carbon atoms, EO represents an oxyethylene group, and r represents an average of ethylene oxide. Indicates the number of added moles and is a numerical value of 1 ≦ r ≦ 30.) Of the liquid bleach composition, temperature 25 ° C., was measured under the conditions at a B type viscometer rotational speed 60 rpm, the viscosity after 1 minute from the start of stirring is 10 mPa · s or more claim 1, wherein the liquid bleaching agent Product . As the surfactant (c), (c-1) one or more selected from fatty acid alkali metal salts having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and (c-2) carbon Alkylamine oxide having a branched or straight chain alkyl group having 8 to 20 carbon atoms, alkyl sulfate ester salt having a branched or straight chain alkyl group having 8 to 20 carbon atoms, and a branched or straight chain chain having 8 to 20 carbon atoms 1 type or 2 types or more selected from the group consisting of polyoxyethylene alkyl ether sulfates having an alkyl group are used in combination, and the total content of the component (c) is 0.01 to 2% by mass, (c-1) / value of the mass ratio represented by (c-2) is in a range on the 7/3 than the lower 3/7 than the liquid bleach product according to claim 1 or 2.

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