JP2831955B2 - Liquid bleach composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to liquid bleach compositions. More specifically, the present invention relates to a bleaching composition which does not cause decomposition of hydrogen peroxide even when mixed with detergent or tap water and has excellent storage stability.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaching agents are limited in the types of fibers that can be used, and cannot be used for colors and patterns. Oxygen bleaching agents that do not have these disadvantages have recently become very popular because of their inherent odor. Among these oxygen bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid oxygen bleaching agent.

[0003] Liquid bleaches are usually stored under acidic conditions due to the stability of hydrogen peroxide. When a metal or the like is mixed, the metal acts as a catalyst for decomposing hydrogen peroxide. Therefore, a sequestering agent or the like is usually added.

However, since the liquid bleach is generally used in combination with a detergent, when the liquid bleach is introduced, the washing liquid splashes or the powder detergent is scattered, so that the bleach is introduced into the bleach container. There is a possibility that detergent or tap water may be mixed into the container from the mouth, and storage stability may be significantly reduced. To prevent this, the shape of the spout of the container has been devised at present. However, the shape of the spout is restricted by devising the spout to prevent it from being mixed.For containers with a dripping prevention function, for example, a container equipped with a cap with improved ease of use of the spout such as a cap with a dripping prevention function It was difficult to apply.

Accordingly, an object of the present invention is to provide a liquid bleach composition which can improve these drawbacks and can maintain storage stability even when tap water or detergent is mixed.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above-mentioned problems by adding a specific amount of an acidic substance to a liquid bleach composition containing hydrogen peroxide as a bleaching component. They have found that they can do this and have completed the present invention.

That is, the present invention is directed to a container having a dripping prevention function having a pH of 6.0 or less containing hydrogen peroxide and an acidic substance.
A liquid bleach composition to be loaded , wherein said acidic substance is
The amount of the N / 10 NaOH aqueous solution necessary for bringing the liquid bleach composition 1000 ml to pH 6.0 (20 ° C.) is from 100 ml to 1000 ml.
The present invention provides a liquid bleaching composition characterized in that it is blended in an amount of ml . Hereinafter, the present invention will be described in detail.

In the present invention, an acidic substance is added to a liquid bleach composition containing hydrogen peroxide as a bleaching component. As the acidic substance, those whose pH of a 1% aqueous solution becomes 6.0 or less are preferably used. For an acidic substance having a pH of 1% aqueous solution exceeding 6.0, the pH of the whole composition becomes high, which may affect the stability of hydrogen peroxide. PH of 1% aqueous solution is 6.
Specific examples of the acidic substance of 0 or less include acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, glycolic acid, lactic acid, succinic acid, and citric acid Organic carboxylic acids such as fumaric acid, benzoic acid, salicylic acid, phthalic acid, terephthalic acid, and trimellitic acid Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid Polycarboxylic acids such as homopolymer or copolymer obtained from alkyl sulfate, alkyl ether sulfate, α-sulfofatty acid, α-sulfofatty acid ester,
Organic sulfates and organic sulfonic acids such as alkylbenzenesulfonic acid, p-toluenesulfonic acid, p-hydroxysulfonic acid, etc. ethane-1,1-diphosphonic acid, ethane-1,1,1
2-triphosphonic acid, ethane-1-hydroxy-1,1
-Phosphonic acids such as diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid and methanehydroxyphosphonic acid; and inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, nitric acid and silicic acid. Among these, organic carboxylic acids, percarboxylic acids, polycarboxylic acids, phosphoric acid, polyphosphoric acids, sulfuric acid, phosphonic acids, and sulfonic acids are particularly preferred.

[0009] These acidic substances include liquid bleach composition 1000
N / 10 NaOH required to bring the pH to 6.0 (20 ° C)
The aqueous solution is added so as to have a volume of 100 ml to 1000 ml.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid bleach composition of the present invention contains hydrogen peroxide as a bleaching component and contains a specific amount of the above-mentioned acidic substance. d)
Liquid bleach compositions having a composition such as The balance is usually water and optional components. (A) 0.5 to 10% by weight of hydrogen peroxide (b) 0.5 to 30% by weight of a nonionic surfactant (c) 0.1 to 20% by weight of at least one selected from an anionic surfactant or a cationic surfactant ( d) The amount of the aqueous N / 10 NaOH solution required to bring the liquid bleach composition 1000 ml to pH 6.0 (20 ° C.) is from 100 ml to
Here the amount of acidic substance to be 1000 ml, the compound represented by the general formula (2) is preferable as the nonionic surfactant of component (b). R ² -X- (AO) _m -Y (2) [wherein, R ^{2 represents a} straight-chain or branched-chain carbon number of 6 to 22, preferably 8;
To 18, particularly preferably an alkyl group or alkenyl group having 10 to 18 or an aryl group which may be substituted by a linear or branched alkyl group having 1 to 18, preferably 6 to 18 alkyl groups Is shown. Particularly, an alkyl group is preferable. X: -O- or -COO-, preferably -O-. A: represents a linear or branched alkylene group having 2 to 3 carbon atoms. Y: H or an alkyl group having 1 to 3 carbon atoms. m: Average number is 3 to 50, preferably 3 to 20, particularly preferably 4 to 15. In the general formula (2), the group A represents an ethylene group or a propylene group (preferably a branched propylene group), which may be added to a block type or a random type. . Specific examples of these nonionic surfactants include the following compounds.

[0011]

[Table 1]

It is desirable that the liquid bleaching composition of the present invention contains at least one selected from anionic surfactants and cationic surfactants as component (c) in an amount of 0.1 to 20% by weight. Examples of the anionic surfactant include an alkylbenzene sulfonate having an average carbon number of 8 to 22, an alkyl or alkenyl ether sulfate, an alkyl or alkenyl sulfate, an α-olefin sulfonate, a saturated or unsaturated fatty acid salt, and an N-acyl amino acid. Surfactants, alkyl or alkenyl ether carboxylates, amino acid surfactants, alkyl or alkenyl phosphate salts, and the like. Of these, alkylbenzene sulfonates are particularly preferred. As the component (c), a cationic surfactant may be blended in addition to the anionic surfactant. As the cationic surfactant, a compound represented by the general formula (3) is preferable.

[0013]

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[In the formula, at least one of R ³ , R ⁴ , R ⁵ , and R ⁶ is an alkyl group or alkenyl group having 6 to 20, preferably 8 to 18 carbon atoms, and among these, an alkyl group is preferable. The remainder is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, of which an alkyl group is preferred. Y represents an organic or inorganic anion. Specific examples thereof include the following compounds.

[0015]

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Of these, dioctyl dimethyl ammonium salt, didecyl dimethyl ammonium salt, didodecyl dimethyl ammonium salt, dodecyl trimethyl ammonium salt, tetradecyl trimethyl ammonium salt, and hexadecyl trimethyl ammonium salt are particularly preferred.
In addition, as the component (c), a cationic surfactant is particularly preferable.

In the liquid bleach composition containing the above components (a) to (d), the amount of each component is as follows:
The component (a) is 0.5 to 10% by weight, preferably 1 to 10% by weight, more preferably 1 to 6% by weight, and the component (b) is
It is 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight. Component (c) is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1.0 to 10% by weight.
10% by weight can be blended. The acidic substance of the component (d) is as described above. If the amount of the component (a) is less than 0.5% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 10% by weight, the storage stability of hydrogen peroxide is significantly reduced. If the component (b) is less than 0.5% by weight, sufficient bleaching performance cannot be obtained.
If it exceeds 30% by weight, the viscosity increases, which causes a problem that handling becomes difficult. If the amount of the component (c) is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 20% by weight, the viscosity of the composition increases, making it difficult to handle. When the amount of the component (d) is out of the range of the present invention, the stability of hydrogen peroxide is significantly reduced when detergent or tap water is mixed into the liquid bleach composition.

The liquid bleach composition of the present invention basically contains hydrogen peroxide and a specific acidic substance as essential components. For example, the components (a) to (d) are mixed in water at the above ratio. However, a hydrotrope may be added for the purpose of stabilizing the liquid at low temperatures and improving the freeze-recoverability, or preventing liquid separation at high temperatures. As such a hydrotrope, generally, a short chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol, ethylene glycol, propylene glycol,
Alcohols represented by hexylene glycol, glycerin and the like, and polyhydric alcohols are exemplified. The hydrotrope can be incorporated in the bleaching composition in an amount of about 0 to 30% by weight.

Further, the liquid bleach composition of the present invention includes:
As the component (e), a bleaching activator represented by the following general formula (1) can be blended.

[0020]

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[Wherein R ¹ has 5 to 19 carbon atoms, preferably 7 carbon atoms.
And 15 to 15 alkyl groups or alkenyl groups, of which an alkyl group is preferable. Z represents a -SO ₃ M or -COOM, -SO ₃ M among these is preferred. M is an organic or inorganic cation. Specific examples of such bleach activators include, for example, the following compounds.

[0022]

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The liquid bleaching composition of the present invention may further contain a sequestering agent as component (f).
The following compounds are preferred as sequestering agents.

(1) Phosphoric acid compounds such as phytic acid or alkali metal salts or alkanolamine salts thereof (2) Ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1 -Hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-
Triphosphonic acid, ethane-1,2-dicarboxy-1,2-
Phosphonic acid such as diphosphonic acid, methanehydroxyphosphonic acid or an alkali metal salt or alkanolamine salt thereof (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or alkali metal salts or alkanolamine salts thereof (4) aspartic acid, glutamic acid, amino acids such as glycine or alkali metal salts or alkanolamine salts thereof (5) nitrilotriacetic acid, Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid, diencoric acid or the like or an alkali metal salt or alkanolamine salt thereof Organic acids such as oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, and carboxymethyltartaric acid; or alkali metal salts or alkanolamine salts thereof. (7) Alkali metal salts or alkanolamine salts of aluminosilicate represented by zeolite A (8 Examples thereof include aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, and polyethylene polyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt. Of these, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferred, and at least one selected from the group consisting of the above (2) is more preferred. Such sequestering agents are present in the liquid bleach compositions of the present invention in an amount of from 0.0005% to 5% by weight, preferably
0.005 to 5% by weight, more preferably 0.01 to 1% by weight.

The liquid bleach composition of the present invention may further contain various compounds. For example, a substance known as an anti-fading agent can be included. Examples of such a substance include amino acids and amino acid salts such as phenylalanine, histidine, lysine, tyrosine, and methionine; and amino or imide compounds such as hydroxyiminodiacetic acid, and further copolymerized with acrylonitrile and acrylonitrile having a quaternary ammonium group. And copolymers with one or more of the possible monomers. Although amino acids have optical isomers, optical isomers do not participate in the effects of the present invention. Therefore, it is also possible to use chemically synthesized amino acids.

Tinopal CBS is used as a fluorescent whitening agent to enhance the bleaching effect on white fiber.
(Manufactured by Ciba-Geigy), Tinopearl SW
A fluorescent whitening agent such as N (manufactured by Ciba-Geigy) or a color index fluorescent whitening agent 28, 40, 61, 71 may be added in an amount of 0 to 5%.

Further, a thickener may be added in an amount of 0 to 20% for the purpose of increasing the viscosity of the composition and improving the usability. Generally, synthetic polymers such as polyacrylates, acrylic acid-maleic acid copolymers, carboxymethylcellulose derivatives, methylcellulose and hydroxymethylcellulose; natural polymers such as xanthan gum, guar gum and kelzan; and water-swellable clay minerals such as montmorillonite and veegum And so on. Also, JP-A-1-319
It is also possible to impart viscoelastic rheological properties by combining an amphoteric surfactant and an anionic surfactant as described in JP-A-600.

The liquid bleach composition of the present invention may further comprise a coloring agent such as a dye or a pigment, a fragrance, silicones,
An appropriate amount (each about 0 to about 2%) of various trace additives such as a bactericide, an ultraviolet absorber, and an inorganic electrolyte can be blended. As the dye, an acid dye having resistance to hydrogen peroxide in an acidic solution is particularly preferable.

Further, in the composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be blended as required to improve the bleaching performance.

The pH of the liquid bleach composition of the present invention is 6 or less, preferably 3.5 or less.

The liquid bleach composition of the present invention has good storage stability of hydrogen peroxide even when detergent or tap water is mixed in the container at the time of use. The mouth can be made more convenient. As a specific example, a container with a liquid dripping prevention function, for example, a container in which a cap with a liquid dripping prevention function is attached to a spout of the container can be mentioned. Examples of these caps with a dripping prevention function are disclosed in Japanese Utility Model Laid-Open Nos. 64-51043, 64-11971 and 64-1.
1971, Japanese Utility Model Laid-Open No. 2-69855, and the like. Here, the “cap with anti-dripping function” is a cap provided for a bottle or other container, regardless of its shape, after discharging the liquid inside, and then leaking the liquid passing through the wall surface of the cap to the outside. It means a cap having a function not to be affected. As such a cap, a cap provided with a liquid dripping prevention function as shown in FIG. 1 is particularly preferable. FIG. 1A is a plan view of a cap with a liquid dripping prevention function, and FIG.
FIG. 4A is a cross-sectional view taken along line A, and FIG. 4C is a schematic cross-sectional view showing a state where a cover (a) is attached. FIG. 2 is a schematic cross-sectional view showing the state of weighing with the lid (a).

[0032]

The liquid bleach composition of the present invention is excellent in storage stability of hydrogen peroxide even when detergent or tap water is mixed. For this reason, it is possible to use a container that is highly likely to be mixed with detergent or tap water in an actual use situation, and in particular, it is possible to use a container with a function of preventing dripping.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Using the following components, liquid bleach compositions shown in Table 2 were prepared, and the required amount of an N / 10 NaOH aqueous solution was measured by the following method. Component (a); H ₂ O ₂ (b) _{component; C 12 H 25 O (OC} 2 H 4) 10 -OH (b-1) C 10 H 21 O (OC 2 H 4) 6 -OCH 3 (b _{-2) C 11 H 23 CO (} OC 2 H 4) 15 -OH (b-3)

[0035]

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(D) component: phosphoric acid (pH of 1% aqueous solution (20 ° C.) = 1.6) citric acid (pH of 1% aqueous solution (20 ° C.) = 2.2) polyacrylic acid (average molecular weight 8000, 1% aqueous solution pH
(20 ° C.) = 3.2, adjusted to this pH value by partially neutralizing with sodium hydroxide. ) LAS-S (linear alkyl (C ₁₂ ) benzenesulfonic acid,
PH of 1% aqueous solution (20 ° C) = 1.8)

[0037]

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<Measurement of required amount of N / 10 NaOH aqueous solution>
1000 ml of the liquid bleach composition was charged into a 1-liter glass beaker and stirred with a magnetic stirrer (confirmed 20 ° C.). While confirming the pH with a pH meter, an aqueous solution of N / 10 NaOH was gradually added, and when the pH reached 6.0, the amount of the aqueous solution of N / 10 NaOH was determined.
Table 2 shows the results.

[0039]

[Table 2]

<Confirmation of Storage Stability> 800 ml bottle (Kao Corporation) equipped with a cap with a liquid dripping prevention function shown in FIG.
The humming 1/3 bottle was drained, washed with a neutral detergent, rinsed well with ion-exchanged water, and dried before use, and 800 ml of the liquid bleaching composition shown in Table 2 was added. The detergent and tap water in the amounts shown in Table 3 were added thereto, and stored under predetermined conditions. After storage, the residual ratio of available oxygen and the shape of the bottle were measured by the following methods. Table 3 shows the results. (Effective oxygen remaining ratio) 0.3 g of liquid bleach composition in a 50 ml tall beaker containing a magnetic stirrer piece
Weigh precisely and add 10 ml of 20% aqueous sulfuric acid solution. Then N / 10
It was titrated with sodium permanganate. The effective oxygen remaining rate was determined by the following equation.

[0041]

(Equation 1)

(Bottle Shape) Judgment was made according to the following evaluation criteria. ○… The shape of the bottle has not changed at all. Δ: Some swelling of the bottle is observed. ×: The bottle is significantly swollen. XX: The bottle is bursting.

[0043]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a view showing an example of a cap with a dripping prevention function attached to a container for filling the liquid bleach composition of the present invention.

FIG. 2 is a schematic sectional view showing a use state of the cap with a liquid dripping prevention function of FIG. 1;

[Explanation of symbols]

 (B) Lid for measurement

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C11D 3/36 C11D 3/36 3/395 3/395 (72) Inventor Kasumi Maeda 1334 Minato, Wakayama-shi, Wakayama Pref. (72) Inventor Muneo Aoyagi 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-7-82592 (JP, A) JP-A-4-213400 (JP, A) JP-A-3-3 188198 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C11D 3/39-3/395 C11D 3/04-3/06 C11D 3/20 C11D 3/34-3/36 WPI / L (QUESTEL)

Claims (7)

(57) [Claims] 1. p-containing hydrogen peroxide and an acidic substance
A liquid bleaching composition filled in a container having a function of preventing dripping of H 6.0 or less, wherein the acidic substance contains N / N required to bring 1000 ml of the liquid bleaching composition to pH 6.0 (20 ° C.). A liquid bleach composition, wherein the amount of the 10NaOH aqueous solution is 100 ml to 1000 ml. 2. The method according to claim 1, further comprising hydrogen peroxide and an acidic substance.
Prevention of dripping, adjusted to pH 6.0 or less with acidic substances
A liquid bleach composition filled in a container with a function,
The acidic substance, pH 1000ml of the liquid bleach composition
N / 10 NaOH aqueous solution required to reach 6.0 (20 ° C)
The amount is 100ml to 1000ml.
Liquid bleach composition to be characterized. 3. The pH (20 ° C.) of a 1% aqueous solution of an acidic substance is
3. The liquid bleach composition according to claim 1, wherein the composition is 6.0 or less. Wherein the acidic substance, carboxylic acids, percarboxylic acids, polycarboxylic acids, phosphoric acid, polyphosphoric acids, according to claim 1 to 3 or 1 is at least one selected from sulfuric acid, phosphonic acids, and sulfonic acids Item 18. The liquid bleach composition according to Item 8. 5. A pH containing the following components (a) to (d):
A liquid bleach composition filled in a container with a dripping prevention function of 6.0 or less. (A) 0.5 to 10% by weight of hydrogen peroxide (b) 0.5 to 30% by weight of a nonionic surfactant (c) 0.1 to 20% by weight of at least one selected from an anionic surfactant or a cationic surfactant ( d) The amount of the aqueous N / 10 NaOH solution required to bring 1000 ml of the liquid bleach composition to pH 6.0 (20 ° C.) is from 100 ml to
1000ml of acidic substance 6. any one liquid bleach composition according to claim 1-5, containing a bleach activator 0.1 to 10% by weight. 7. The liquid bleach composition according to claim 6, wherein the bleach activator is represented by the following general formula (1). Embedded image [In the formula, R ¹ represents an alkyl group or an alkenyl group having 5 to 19 carbon atoms, and Z represents —SO ₃ M or —COOM. M is an organic or inorganic cation. ]