JP2801071B2 - Liquid bleach composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an acidic liquid bleach composition, and more particularly, to a liquid bleach composition having an appropriate viscosity under acidic conditions and excellent storage stability. About things.

[Conventional technology]

BACKGROUND ART Conventionally, oxygen-based bleaching agents have been widely accepted because of their advantages that they can be used easily and safely and can be widely used in clothing.

In recent years, more convenient liquid oxygen bleaching agents have been commercialized. In general, hydrogen peroxide is mixed with liquid oxygen-based bleach, but decomposition of hydrogen peroxide is promoted in the alkaline region, gas is generated, and blistering of the bottle is caused,
It loses significant value as a product. Therefore, the pH of the liquid is generally adjusted to an acidic range in order to maintain safety.

Studies have been made to improve the storage stability of liquid bleaches containing hydrogen peroxide. For example,
No. 7774 discloses a storage-stable weakly acidic liquid bleach using sodium acid pyrophosphate, neutral sodium pyrophosphate and neutral potassium pyrophosphate in combination, and JP-A-49-52784 discloses alkylidene diphosphonic acid, ethylenediamine. A stable liquid bleach having a pH of 0.5 to 7 containing an organic acid selected from tetraacetic acid, diethylenetriaminepentaacetic acid and nitrilotrimethylenephosphonic acid, a soluble tin salt and an ammonium salt is disclosed in
In JP-A-2-103386, a hydrogen peroxide stabilizer comprising poly-α-hydroxyacrylic acid is disclosed, and in JP-A-54-10309, a magnesium compound and an acid are complexed by adding water to a neutralization reaction. The liquid material with hydrophilicity is pH 4 ~
6, the decomposition of hydrogen peroxide can be suppressed.
No. 8500 discloses an organic acid, phosphoric acid, a stable liquid bleach having a pH of 1.8 to 5.5 containing an acid selected from boric acid and a nitrogen-containing compound, and Japanese Unexamined Patent Publication No. 55-76161 discloses a condensed phosphoric acid. JP-A-57-154457 discloses that a synergistic stabilizing effect can be exhibited by blending poly-α-hydroxyacrylate in an alkaline hydrogen peroxide bleaching system using a salt as a stabilizer. Stabilizing aids for hydrogen peroxide bleach comprising a copolymer of acrylic acid ester and / or polyethylene glycol methacrylate are disclosed in JP-A-62-185797. And hydrogen peroxide bleach stabilizers.

In particular, liquid bleaching agents can be applied to detergents and stains of clothing by taking advantage of their properties, then thrown into detergent solution, and washed and bleached in the same manner as ordinary washing machine washing to improve the washing bleaching effect. It is also known. At that time, in order to exhibit the bleaching effect efficiently, it is desirable that the bleaching agent is a thickening type bleaching agent which keeps the coating solution on clothing for a certain period of time.

Studies on the thickening of liquid bleaches have also been made. For example, JP-A-64-36699 discloses a method for producing a thickened bleaching composition comprising a combination of a surfactant of the kaotin type and an organic counter ion, and JP-A-63-189491 discloses an acid and an amine. A liquid bleaching agent comprising a thickened aqueous acidic solution in combination with a thickened liquid detergent composition comprising a partially crosslinked polyacrylic acid and an inorganic alkali acid disclosed in JP-A-53-36198. However, JP-A-56-90897 discloses a liquid concentrated bleach composition comprising a combination of a tertiary amine oxide and a saturated fatty acid soap. JP-A-60-35100 discloses a smectite-type clay and an aminopolycarboxylate. JP-A-57-16899 discloses a viscous sterilizing detergent composition comprising an activator comprising diphenyl ether disulfonate and an alkaline substance, a swelling clay mineral such as montmorillonite. Disclosure Have been.

[Problems to be solved by the invention]

Hydrogen peroxide bleach using these stabilizers does not have sufficient storage stability at high temperatures, does not have the thickening effect expected when used in acidic systems, and has a high viscosity during long-term storage. However, the desired properties could not be realized.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above problems, and found that a specific surfactant and a polycarboxylic acid having a specific molecular weight or a salt thereof and a water soluble solution selected from at least one of sulfates, nitrates and hydrochlorides. The stability at the time of high temperature storage is remarkably improved by the addition of the acidic inorganic salts, and furthermore, it is possible to obtain an acidic hydrogen peroxide bleach composition which is transparently thickened in an acidic region and does not decrease in viscosity even during long-term storage. As a result, the present invention has been completed.

That is, the present invention provides: (a) 0.5 to 10% by weight of hydrogen peroxide; (b) 0.1 to 20% by weight of an anionic surfactant; (c) 0.1 to 20% by weight of a nonionic surfactant; (E) at least one of sulfate, nitrate and hydrochloride
It is intended to provide a liquid bleaching composition containing 0.1 to 10% by weight of a water-soluble inorganic salt selected from the group consisting of water and a pH in the range of 1.5 to 6.

In the present invention, hydrogen peroxide (a) as a bleaching base is incorporated in the composition in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight.

Examples of the anionic surfactant (b) used in the present invention include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates,
Alkane sulfonates, saturated or unsaturated fatty acid salts and the like, and the nonionic surfactant (c) includes polyoxyalkylene alkyl or alkenyl ether,
Polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, fatty acid glycerin monoester, alkylamine oxide, pluronic surfactant, sorbitan fatty acid ester or an ethylene oxide adduct thereof, and the like. .

The anionic surfactant (b) and the nonionic surfactant (c) are contained in the composition in a total amount of (b) + (c) of 0.1 to 2%.
0% by weight, preferably 3 to 15% by weight. The weight ratio of the component (b) to the component (c) is 1 / (b) / (c).
It is 5 to 5/1, preferably 1/3 to 3/1. Particularly preferred anionic surfactants (b) are linear alkyl (C ₈ -C ₁₈ ) benzenesulfonate, alkyl (C ₈ -C ₁₈ ) ether (ethylene oxide addition mole number 1-10) sulfate, α-
Olefins (C ₁₂ ~C ₁₈₎ sulfonates, alkyl (C ₈ ~
C ₁₈ ) sulfate, etc., and particularly preferred nonionic surfactant (c) is polyoxyethylene (addition mole number 1 to 1).
30) It is an alkyl ether.

Incidentally, it is not preferable that the components (b) and (c) are blended alone. This is because the use of an anionic surfactant alone may cause precipitation of the metal salt of the anionic surfactant, impairing the appearance and causing poor storage stability, and the use of a nonionic surfactant alone may cause water solubility. This is because the salt dissolves transparently, but causes problems such as an inability to obtain a thickening effect.

The carboxylic acid-based polymer used as the component (d) in the present invention is water-soluble and has a repeating unit represented by the following general formula (I). Among them, polyacrylic acid (salt) or maleic acid-based polymer is preferable.

[Wherein, X: -OH or -HY: -COOM or -HM: an alkali metal atom or Hp, q: 0 to 1]. The carboxylic acid polymer has an average molecular weight of 1,000 to 100,000,
Preferably, those in the range of 2,000 to 20,000 are suitable. If the average molecular weight is less than 1,000 or exceeds 100,000, the storage stabilizing effect is reduced. In addition, a carboxylic acid-based polymer having an average molecular weight of more than 100,000 has the ability to increase the viscosity with a small amount, but also has problems such as poor liquid drainage. Carbopol, which is often used as a thickener in hydrogen-based acidic liquid bleaches, is a polyacrylic acid having a very high molecular weight and being partially cross-linked, and the non-cross-linked polyacrylic acid used in the present invention. Is another.

Examples of the maleic acid polymer include maleic acid homopolymer or a copolymer of maleic acid and another vinyl monomer (including these partially and completely neutralized salts). Examples of the copolymer include a copolymer of maleic acid with a vinyl monomer selected from acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, vinyl acetate and the like. Of these, copolymers of acrylic acid or methacrylic acid and maleic acid are preferred. The monomer ratio between maleic acid and other monomers is maleic acid / monomer =
Desirably, it is in the range of 90/10 to 40/60. The polymer of component (d) is incorporated in the composition in a total amount of 0.01 to 10% by weight, preferably 0.5 to 3% by weight. The amount of polymer is 0.01
If the content is less than 10% by weight, a sufficient effect cannot be obtained. If the content is more than 10% by weight, a problem of polymer separation may occur.

As the water-soluble inorganic salts selected from at least one of sulfates, nitrates and hydrochlorides used in the component (e) of the present invention, magnesium sulfide, sodium sulfide, calcium chloride, sodium chloride and the like are particularly preferable. It is listed as. Regarding thickening, other polymeric thickeners such as carboxymethylcellulose, guar gum, polyvinyl alcohol, etc. can also achieve thickening, but the viscosity may decrease during storage of the product and is not a suitable thickener. . In the present invention, the water-soluble inorganic salt (e) is contained in the composition in an amount of 0.
1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 5% by weight, and the viscosity of the composition is preferably adjusted to 10 to 100 cps.

The composition of the present invention is usually balanced by adding water to the above-mentioned components (a) to (e). In addition, alcohols such as ethanol, isopropanol and ethylene glycol, thickeners, fragrances, dyes, fluorescent dyes, A chelating agent such as EDTA, NTA, phosphonic acid, or polyphosphoric acid, a radical scavenger, an enzyme, and the like may be blended as necessary.

The pH of the stock solution of the composition of the present invention is an inorganic acid such as hydrochloric acid or sulfuric acid,
Using organic acids such as p-toluenesulfonic acid and citric acid
It is adjusted to 1.5 to 6, preferably 2.0 to 4.5. Composition p
When H exceeds 6, the storage stability is significantly reduced.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 A bleaching composition having the composition shown in Table 1 was prepared and subjected to the following tests.

(1) Appearance of blended composition The bleaching compositions shown in Table 1 were blended, and the appearance was visually observed at 20 ° C.

 The evaluation criteria for the appearance are as follows.

 ：: Transparently dissolved.

 Δ: slightly turbid, but no precipitate.

 X: Precipitation has occurred.

(2) Thickening Effect The bleaching compositions shown in Table 1 were blended, and the viscosity was measured at 20 ° C. The viscosity was measured for the sample immediately after blending and after storage at 50 ° C. for 2 weeks after blending, and the results are shown in Table 1.

The viscosity was measured using a B-type viscometer at 20 ° C., 60 ppm, and 60 seconds.

(3) Storage stability (bottle appearance) Evaluation method The bleaching compositions shown in Table 1 were polyethylene cylinder bottles as shown in FIG.
l, bottom wall thickness 0.6 mm), sealed 600 ml, stored at 50 ° C for 14 days, taken out, and visually observed the swelling of the cylinder bottle. FIG. 1 (A) shows a bottle in a normal state, and the bottom is in a concave state inward. Also the first
FIG. (B) shows the swelled cylinder bottle 1 and shows an example in which the bottom is bulged outward. Here, the evaluation criteria for the swelling of the bottle are as follows. Each test was performed with 10 bottles, and indicated by the number of ○, Δ, and ×.

Evaluation criteria ：: No change [Fig. 1 (A)] ：: The bottom of the bottle swells slightly and the sitting of the bottle deteriorates.

×: The bottom of the bottle swells and the bottle falls down (note that
This state is achieved at an internal pressure of 6 kg / cm ² or more. (FIG. 1 (B)) The results are shown in Table 1.

Note) * 1 Nonionic surfactant; polyoxyethylene (EO added mole number alkyl (R =
C _{12 to 13)} ether * 2 anionic surfactant; straight Ben diesel sodium sulfonate (R = C ₁₂₎ * 3 carboxylic acid polymer I; Na salt of acrylic acid polymer (average molecular weight 8000) * 4-carboxylic acid -Based polymer II; maleic acid / acrylic acid polymer (Na salt having a monomer ratio of 10/1 and an average molecular weight of 70,000) * 5 carboxymethylcellulose; "CMC 1120" manufactured by Daicel Chemical Industries, Ltd. * 6B;

[Brief description of the drawings]

FIG. 1A is a cross-sectional view of a cylinder bottle in a normal state, and FIG. 1B is a cross-sectional view of an expanded cylinder bottle. 1 ... bottle 2 ... bottom

Claims (2)

(57) [Claims] (A) Hydrogen peroxide 0.5 to 10
% By weight (b) 0.1 to 20% by weight of anionic surfactant (c) 0.1 to 20% by weight of nonionic surfactant (d) Average molecular weight of 1000 to 10 having a repeating unit represented by the following general formula (I) 10,000 carboxylic acid polymers 0.
01-10% by weight [Wherein X: -OH or -HY: -COOM or -HM: an alkali metal atom or Hp, q: 0 to 1]. (E) at least one of sulfate, nitrate and hydrochloride
A liquid bleach composition containing 0.1 to 10% by weight of a water-soluble inorganic salt selected from the group consisting of at least one selected from the group consisting of: 2. An anionic surfactant (b) and a nonionic surfactant (c) in a weight ratio of (b) / (c) of 1/5 to 5
The liquid oxygen-based bleach composition according to claim 1, wherein the composition contains 0.1 to 20% by weight in total of (b) + (c) / 1.