JPH1180794A - Liquid bleaching composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid bleaching composition that causes no deterioration in quality even when it is filled in a plastic vessel and exposed to natural light for a prolonged period of time. SOLUTION: This liquid bleaching composition contains hydrogen peroxide, a nonionic surfactant and a sequestering agent. The nonionic surfactant is made into an aqueous solution with a pH of 3 by including 5 wt.% of the nonionic surfactant, 5 wt.% of hydrogen peroxide and the balance of ion- exchanged water. The solution is charged in a screwed glass tube of 100 cc capacity by an amount of 40 ml and allowed to stand under natural light until the tube is exposed to natural light of 10,000 MJ/m<2> according to the accumulated illuminometer. Even after the exposure, (a) the solution causes no phase separation and occurs no turbidity and (b) the residue of the hydrogen peroxide is >=50 % in the solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleaching composition which, when stored in an appropriate light-shielded state, has no change in appearance even when exposed to natural light and can maintain excellent bleaching power.

[0002]

2. Description of the Related Art 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. Oxygen bleaching agents which do not have these drawbacks have been widely used recently. Among these oxygen bleaching agents, sodium percarbonate and sodium perborate are used as powder oxygen bleaching agents, and hydrogen peroxide is used as liquid oxygen bleaching agents. Further, a nonionic surfactant is usually added to the liquid oxygen-based bleaching agent together with hydrogen peroxide in order to impart detergency.

[0003] In this liquid oxygen bleaching agent, the stability of hydrogen peroxide used as a bleaching active species is poor, and oxygen gas is generated during storage. For this reason, a container having a strong structure as disclosed in JP-A-4-220499 has been used as a container for the liquid oxygen-based bleaching agent. Recently, however, there has been a demand for resource saving and reduction of plastic waste. In view of the above problems, a liquid bleach for refilling packed in a thin plastic film pouch has been desired. Such a refillable plastic bag-shaped packaging container is disclosed in
JP-A-505322 and JP-A-3-123847.

[0004]

The above-mentioned liquid oxygen-based bleach is placed in a plastic container and stored outdoors, for example, before shipping, because an indoor storage place cannot be secured, or when the product is sold outside the store. When left under natural light, problems such as separation of the liquid bleach, turbidity, and swelling of the container may occur. It is presumed that this problem is caused by the oxidative decomposition of non-ionic surfactants by light activated hydrogen peroxide. In this case, the decomposition of hydrogen peroxide is accelerated by the oxidized and decomposed nonionic surfactant, which not only exacerbates the problem but also reduces the bleaching power.

In order to prevent such a problem from occurring, a plastic container has a multilayer structure, and a metal layer such as an aluminum foil layer is formed as an intermediate layer, or a gray ink layer is formed. A method of providing light-shielding properties can be considered. However, by this method, if the above problem is to be solved including, for example, a case where the device is exposed to natural light for a long period of time, the production cost of the container itself increases, which leads to an excessive increase in product price, It can also disadvantage consumers.

Accordingly, the present invention provides a liquid bleaching composition which uses a conventional refillable plastic container and does not change the contents or the container even when exposed to natural light for a long period of time. The purpose is to provide things.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned object. As a result, even in a natural light exposure test under predetermined conditions, a specific non-ionic The inventors have found that a bleach solution containing a surfactant and a bleaching component is stable for a long period of time, and completed the present invention.

[0008] That is, the present invention is a liquid bleach composition containing hydrogen peroxide, a nonionic surfactant and a sequestering agent, wherein the nonionic surfactant is a nonionic surfactant 5
Weight solution, 5% by weight of hydrogen peroxide and ion-exchanged water as a balance at pH = 3, and put 40 ml of the solution in a 100 cc screw tube made of transparent glass. Even when exposed to natural light of 000 MJ / m ^2, the following requirements must be satisfied: (a) no separation of the solution and no turbidity; and (b) a residual ratio of hydrogen peroxide in the solution of 50% or more. A liquid bleaching composition characterized by being filled.

In the natural light exposure test, which is a prerequisite for the requirements (a) and (b) in the present invention, the transparent screw tube containing the test solution having the above-mentioned predetermined composition is placed in a place where the sunshine is good and there is no shade. It is installed facing toward the south with a 45 ° inclination, and a predetermined integrated illuminance is measured by an integrated illuminometer. In addition, p of the test solution of the above-mentioned predetermined composition
H is 3, which is the pH in the natural light exposure test.
However, the pH of the liquid bleach composition of the present invention is not limited to this.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hydrogen peroxide used in the present invention is a bleaching active species, and the content of hydrogen peroxide in a liquid bleaching agent composition prevents blistering of a container and provides a sufficient bleaching effect. , Preferably 0.1 to 10% by weight
And particularly preferably 0.5 to 6% by weight, and more preferably 1 to 6% by weight.

The nonionic surfactant used in the present invention satisfies the requirements (a) and (b) in the natural light exposure test under the predetermined conditions as described above. It is preferable that the composition satisfy requirements (a) and (b) even when exposed to natural light of 20,000 MJ / m ² . In addition, the requirement (b) is a 10,000 or 20,000 MJ
/ M ² of natural light, the residual ratio of hydrogen peroxide in the solution is preferably 70% or more, particularly preferably 90% or more.

[0012] Such nonionic surfactants include:
The following general formula (I): R- (AO) n (BO) m-X (I) [wherein, R represents an alkyl group having 8 to 20 carbon atoms, A represents an ethylene group, and B represents a branched group. AO and BO may be arranged in a block or random form, and n and m each represent 0 to 3
N represents a number of 0, n + m represents a number of 4 to 50, and X represents a hydrogen atom or a methyl group. ] Can be mentioned.

In the general formula, R is preferably an alkyl group having 6 to 20 carbon atoms. n and m each preferably represent a number of 1 to 20, and n + m preferably represents a number of 4 to 20. Further, n and m are preferably numbers that satisfy the relationship of n / m = 10/1 to 1/10.

Examples of the nonionic surfactant represented by the general formula (I) include C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₂ (OC ₃ H ₆ ) ₄ —OH C ₁₂ H ₂₅ (OC _{3 H 6) 4 (OC 2 H} 4) 8 -OH C 18 H 37 (OC 2 H 4) 10 (OC 3 H 6) 10 -OCH 3 C 12 H 25 (OC 2 H 4) 15 (OC 3 H 6 ) _3- OH and the like.

[0015] The content of the nonionic surfactant in the liquid bleach composition is preferably 1 to 50% by weight, particularly preferably 1 to 50% by weight, in order to maintain stability against light and to provide sufficient detergency. 1 to 30% by weight.

The sequestering agent used in the present invention includes pK
Those with _Ca > 4 are preferred, and those with pK _Ca > 5 are particularly preferred. pK _Ca was measured using a calcium ion electrode at 0.1% by weight of a chelating agent at pH 10 and 25 ° C.
It is measured using a _{1M-NH 4 Cl-NH 4} OH buffer.

Examples of such a sequestering agent include aminoacetic acid-based sequestering agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and hydroxyethyliminodiacetic acid, 1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1 Sequestrants such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, carboxylic acid polymers such as acrylic acid / maleic acid copolymer, and tripolyphosphoric acid And the like. Among these, a phosphonic acid-based sequestering agent is preferable.

The content of the sequestering agent in the liquid bleaching composition is preferably 0.01 to 5% by weight, particularly preferably 0.05 to 5% by weight, in order to prevent swelling of the container in consideration of economy. ~ 2% by weight.

In order to improve the bleaching power, the liquid bleaching composition of the present invention contains, in addition to the above components, a compound represented by the general formula (II) or (II)
The bleaching activator represented by I) can be blended.

[0020]

Embedded image

Wherein M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R ¹ and R ² represent an alkyl or alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Represents an aryl group which may be substituted].

Among the bleaching activators represented by the general formula (II) or (III), sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, 3 5,5,5-Trimethylhexanoyloxybenzoic acid is preferred.

The amount of such a bleach activator in the liquid bleach composition is preferably 0.01 to 10 to prevent precipitation or increase in viscosity and to enhance the bleaching effect. %, Particularly preferably 0.1% by weight.
To 5% by weight, more preferably 0.1 to 3% by weight.
It is.

The liquid bleach composition of the present invention may further contain one or more selected from anionic surfactants, amphoteric surfactants and cationic surfactants. Examples of the anionic surfactant include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylate salts. , Α-sulfo fatty acid salts, α-sulfo fatty acid esters and the like. Examples of the amphoteric surfactant include amine oxide, sulfobetaine, carbobetaine and the like. And quaternary ammonium salts.
Of these, alkyl benzene sulfonates (C ₁₀ -C ₂₀ ), alkyl or alkenyl sulfates (C _10
10 -C _20), alkyl or alkenyl ether sulfates (C ₁₀ ~C _20), at least one of carbon number C ₁₀ -C ₂₀
Particularly preferred are quaternary ammonium salts having an alkyl group. The amount of these surfactants is preferably 0.1 to 0.1.
The content is 1 to 50% by weight, particularly preferably 0.5 to 30% by weight, and further preferably 0.5 to 20% by weight.

The liquid bleaching composition of the present invention can be blended as a flavor component with one or more selected from aldehyde components and ester components. The aldehyde components include lilial (4-tert-butyl-α-methylhydrocinnamic aldehyde), florarozone (2-methyl-3- (p-methoxyphenyl) -propanol), and aldehyde C-111 len (10-undecene-). 1
Ol), rigstral (2,4-dimethyl-3-cyclohexenylcarboxaldehyde), bougeonal (3- (p
-tert-butyl-phenyl) -propanol), helional (2-methyl-3- (3,4-methylene-dioxy-phenyl) -propanol), cuminaldehyde (4-isopropylbenzaldehyde), cyclamenaldehyde (2-methyl -3- (4-isopropylphenyl) -propanol), benzaldehyde and hexylcinnamic aldehyde (α-methylhydrocinnamic aldehyde). As the ester component, tricyclodecenyl acetate (hexahydro-4,7-methanoindene-5 (or 6) -yl acetate), fluitate (ethyltricyclo [5,2,1,0 ^2.0 ] decan-2-yl) Carboxylate), benzyl salicylate, pt-butylcyclohexyl acetate, hedione (methyl (3-oxo-2-pentylcyclopentyl) acetate), allyl amyl glycolate (allyl-2-pentyloxyglycolate), allyl cyclohexane propio Nate, o-
Examples thereof include t-butylcyclohexyl acetate, terpinyl acetate, phenylethyl iso-butyrate, phenylethyl acetate, phenylethyl formate, phenylethylphenyl acetate, and n-bornyl acetate. The content of the fragrance component in the liquid bleach composition of the present invention is preferably 0.01 to 1% by weight, particularly preferably 0.1 to 0.5% by weight, in order to impart a sufficient scent. It is.

The liquid bleaching composition of the present invention may further contain other sequestering agents. As the sequestering agent, acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, glycolic acid,
Organic carboxylic acids such as lactic acid, succinic acid, citric acid, fumaric acid, benzoic acid, salicylic acid, phthalic acid, terephthalic acid, and trimetic acid; percarboxylic acids such as dodecanediperacid, monoperphthalanolic acid; Polycarboxylic acids such as homopolymers or copolymers obtained from unsaturated carboxylic acids such as maleic acid; alkyl sulfates, alkyl ether sulfates, α-
Organic sulfonic acids and organic sulfates such as sulfo fatty acids, α-sulfofatty acid esters, alkyl benzene sulfonic acids, p-toluene sulfonic acids, p-hydroxy sulfonic acids; sulfuric acid, phosphoric acid, hydrochloric acid, polyphosphoric acid, nitric acid, silicic acid, etc. Inorganic acids can be mentioned. The compounding amount of these sequestering agents is preferably 0.01 to 5% by weight.

[0027] The liquid bleach composition of the present invention has a pH of 1. 1 with an acid or an alkali to enhance the stability of the composition.
It is preferable to adjust so as to be 5 to 5.

In the liquid bleach composition of the present invention, since hydrogen peroxide as a bleaching component is unstable to light, it is stored in a dark place or stored in a light-shielding container when stored after production. Fill and save. In the case of shipment as a product, it is filled in a light-shielding container and shipped. As such a light-shielding container, for example, the light transmittance of 200 to 800 nm is preferably 30% or less, particularly preferably 20% or less, and more preferably 10% or less.
A 00 μm plastic container can be used.

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Test Example 1 (Natural light exposure test)
Were tested to determine if each of the nonionic surfactants listed in (1) satisfies requirements (a) and (b). However, as a screw tube, a screw tube No. 8 manufactured by Maruem Co. (capacity 1
00 cc), and a model PH-11-UT manufactured by Suga Test Instruments Co., Ltd. was used as an integrated illuminometer. Table 1 shows the results.

[0031]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 10 Hydrogen peroxide, nonionic surfactants b-1 to b-4 shown in Table 1, and nonionic surfactants b'-1 to comparative examples
b'-3, a sequestering agent of c-1 to c-5 shown below, d
Using a bleach activator -1 to d-3 and a surfactant e-1 and e-2, the pH was adjusted to 2.5 with 0.1N sulfuric acid or 0.1N sodium hydroxide. And the liquid bleach composition shown in Table 3 was obtained. For these compositions,
The following tests were performed.

C-1: Nippon Monsanto Dequest 2010CS (pKCa
C-2: Ethylenediaminetetraacetic acid (pKCa = 12.0) c-3: Acrylic acid / maleic acid copolymer (Sokalan CP-6 manufactured by BASF, molecular weight 70,000, monomer ratio 7/3, pKCa = 5.0 c-4: poly) Sodium acrylate (molecular weight 8,000, pKCa = 3.
2) c-5: sodium citrate (pKCa = 3.2)

[0034]

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E-1: alkylbenzene sulfonic acid e-2: N-ethyl-N, N-dimethyl-N-tetradecylammonium ethyl sulfate.

(Test Method) A 450 ml liquid bleaching composition shown in Tables 2 and 3 was used as a standing pouch (having a thickness of 166 μm, 2 m2) for Emal home cleaning manufactured by Kao Corporation.
(Light transmittance of about 00 to 800 nm of about 40%), the opening was heat-sealed and sealed, and stored for one month (May to June 1997, 1997) on the roof of a 6-story building (Wakayama City). (Integrated illuminance about 200,000 MJ / m ² ). Thereafter, the appearance of the composition and the state of the container were visually observed according to the following criteria, and the stability of hydrogen peroxide was evaluated. The results are shown in Tables 2 and 3.

(Separation of the composition and white turbidity) 5: Almost no change 4: Slightly white turbidity 3: White turbidity 2: Severe white turbidity 1: The composition is separated ( (Condition of container) 5: Almost no change 4: Slight swelling of container 3: Swelling of container 2: Swelling of container 1: Severe damage of container (hydrogen peroxide) Stability) The concentration of hydrogen peroxide was determined by titration using a 0.1 N potassium permanganate standard solution, and the residual ratio of hydrogen peroxide was determined by the following equation.

[0038]

(Equation 1)

[0039]

[Table 2]

[0040]

[Table 3]

The liquid bleach compositions of Examples 1 to 8 showed almost no change in the appearance of the compositions and the containers, and showed very little decomposition of hydrogen peroxide. Therefore, it has become clear that the quality of the liquid bleaching composition of the present invention does not change even when the container is exposed to natural light for a short period, as well as when stored in an appropriate light-shielded state. Comparative Examples 1 to 4 containing no sequestering agent and Comparative Examples 5-1
In addition, those containing a nonionic surfactant different from that of the present invention in Comparative Example No. 0 were different in the appearance of the composition and the container, and the decomposition of hydrogen peroxide was large. Therefore, it has been clarified that the quality may be degraded and the product may be defective due to storage outdoors by the manufacturer, display outside the store at the time of sale, or leaving at home in a place exposed to natural light.

In Comparative Examples 1 to 10, although the stability of hydrogen peroxide is impaired by the oxidative decomposition of the nonionic surfactant, it is clear that the bleaching performance decreases after the test is completed. After completion, using the compositions of Examples 1 to 8, acrylic, polyester, and synthetic fiber garments such as polyamides were washed with a commercially available washing machine.
Excellent bleaching and washing effect was exhibited.

[0043]

According to the liquid bleach composition of the present invention, even when exposed to natural light for a long period of time, there is no change in the appearance and the container of the composition, and the excellent bleaching power at the beginning of production can be maintained for a long period of time. In addition, it is easy for the manufacturer to store and ship the product, and it is possible to reduce the occurrence of defective products after manufacturing and before shipping, so that the product yield can be improved. In addition, since the quality is stable even during normal use, the bleaching detergency at the beginning of purchase can be ensured for a long time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3:36) (72) Inventor Kazuyoshi Ozaki 1334 Minato, Wakayama City, Wakayama Pref. Kao Corporation Research Center (72) Inventor Masataka Maki Wakayama 1334 Minato, Wakayama, Japan Kao Research Laboratory

Claims (5)

[Claims] 1. A liquid bleach composition comprising hydrogen peroxide, a nonionic surfactant and a sequestering agent, wherein the nonionic surfactant is composed of 5% by weight of a nonionic surfactant, 5% by weight of hydrogen peroxide, A solution having a pH of 3 consisting of weight percent and ion-exchanged water as balance was prepared,
Even when 40 ml is put in a cc screw tube and left under natural light and exposed to natural light of 10,000 MJ / m ² with an integrated illuminometer, (a) no separation of the solution and no turbidity occurs, and (b) the solution A liquid bleaching composition, which satisfies the requirement that the residual ratio of hydrogen peroxide therein is 50% or more. 2. The nonionic surfactant has the following general formula (I): R- (AO) n (BO) m-X (I) wherein R is an alkyl group having 8 to 20 carbon atoms. A represents an ethylene group, B represents a propylene group which may be branched, AO and BO may be arranged in a block or random form, and n and m each represent 0 to 3
N represents a number of 0, n + m represents a number of 4 to 50, and X represents a hydrogen atom or a methyl group. The liquid bleach composition according to claim 1, which is represented by the following formula: 3. A liquid bleach composition according to claim 1, wherein the sequestering agent has a pK _Ca > 4. 4. The liquid bleach composition according to claim 1, wherein the sequestering agent is phosphonic acid or a salt thereof. 5. A compound of the following general formula (II) or (III):[Wherein M is a hydrogen atom, an alkali metal atom or an alkali
Represents an earth metal atom; ¹And R^TwoRepresents an atom having 7 to 18 carbon atoms.
Alkyl group or alkenyl group or an alkyl group having 1 to 12 carbon atoms
An aryl group which may be substituted with a alkyl group is shown. ]
A bleaching activator represented by the formula:
A liquid bleach composition according to any one of the preceding claims.