JP2736040B2 - Liquid bleach composition - Google Patents

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, and more particularly, to a bleaching activator which reacts with hydrogen peroxide to produce an organic peracid, thereby improving storage stability. It relates to an excellent liquid bleach composition.

[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 which do not have these drawbacks have recently become very popular because of their unique 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 bleaching agent.

However, these oxygen bleaching agents have a weak bleaching power as compared with chlorine bleaching agents, and various bleaching activators are usually used in combination. Examples of these bleach activators include O-acetylated compounds such as glucose pentaacetate (GPAC), N-acylated compounds such as tetraacetylethylenediamine, and acid anhydrides such as maleic anhydride. can give. Furthermore, the present inventors have JP 63-233969, JP Sho 63- 3
As exemplified in JP-A-15666, JP-A-64-68347, JP-A-1-190654, etc., an organic peracid having a quaternary ammonium group is produced by reacting with hydrogen peroxide. The compounds have been found to be very good as bleach activators. Further, an example of an organic peracid precursor having an anionic group is exemplified in JP-B-63-12520.

[0004] These bleach activators are compounds which react with hydrogen peroxide to generate organic peracids even under relatively mild conditions such as washing conditions. Unstable. For this reason, it is usually difficult to use these bleach activators as components of a liquid bleach composition, and to maintain a dry state, a mixture of solid persalt and dry particles of these bleach activators It is generally used as a composition consisting of

A liquid bleaching composition containing a bleaching activator for producing an organic peracid is disclosed in JP-A-62-2308.
No. 97 discloses a composition having excellent storage stability and exhibiting activity at a low temperature obtained by dispersing a solid bleaching activator in an acidic aqueous solution containing hydrogen peroxide. However, in this composition, since the bleaching activator is in a dispersed state, the bleaching activator precipitates and separates during storage, which significantly impairs the appearance of the product. Further, this composition has a problem that the bleaching activator is gradually decomposed by being stored in an aqueous solution, and a satisfactory bleaching power cannot be obtained at the time of use. Further, in this composition, since the bleaching activator is not dissolved in the composition but is present in a dispersed state, the bleaching activator remains dissolved during actual bleaching, and when it adheres to the bleached material, the bleaching activator is removed. There was a problem that the dye was decolorized.

Accordingly, an object of the present invention is to exhibit high bleaching performance not only under alkaline conditions but also under neutral or acidic conditions, and exhibit extremely excellent storage stability, and further cause decolorization of fiber dyes. There is no liquid bleach composition.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by combining specific components, and have completed the present invention. That is, the present invention provides the following component (a) in an amount of 0.3 to 30% by weight,
Component (c) is contained in an amount of 0.01 to 20% by weight and component (c) is contained in an amount of 0.1 to 30% by weight.
(c) there is provided a component] = 1 / 50-5 / 1 der liquid bleach composition characterized Rukoto. (a) Component: hydrogen peroxide (b) Component: Bleaching activator represented by general formula (I)

[0008]

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[In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms. Y ^-: SO ₃ ^- or COO ^- shows the. M ⁺ : represents a cationic group. n indicates 0 or 1. Component (c): quaternary ammonium salt represented by general formula (II)

[0010]

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[Wherein, R ² , R ³ , R ⁴ , R ⁵ : at least one of them represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms; It represents an alkyl group having 1 to 3 carbon atoms which may be substituted with one or more hydroxyl groups. R ^{6 represents a} linear or branched C1-C20 alkyl or alkenyl group, or a linear or branched C1-C18 aryl group optionally substituted with an alkyl group; . _{^{X -: -OSO 3 -, -SO}} 3 - shows the ^- or -COO. ]

[0012]

Embodiments of the present invention will be described below in detail. [Component (b)] In the present invention, the bleaching activator represented by the general formula (I) is used as the component (b). In the general formula (I), R ¹ has the above meaning, but is preferably an alkyl group having 5 to 15 carbon atoms, more preferably 8 to 14 carbon atoms. If the carbon number of R ¹ is less than 5, the bleaching power against lipophilic stains is not sufficient, and if the carbon number of R ¹ exceeds 21, the production rate of the organic peracid becomes slow, and the bleaching performance decreases. M ⁺ represents a cation group, and as the cation group, H ⁺ ,
Cations such as alkali metal ions, alkaline earth metal ions, ammonium ions, and alkyl-substituted ammonium ions are exemplified. To illustrate this bleach activator,
It is as follows.

[0013]

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[0014]

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Among them, the component (b) is represented by the general formula (I)
It is preferable to use a bleaching activator represented by -1), among which, n = 0.

[0016]

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[Wherein, R ¹ , M ⁺ , n: have the above meanings. [Component (c)] In the present invention, a quaternary ammonium salt represented by the general formula (II) is used as the component (c). The quaternary ammonium salt represented by the general formula (II) is characterized in that the counter ion is an organic acid anion, and the quaternary ammonium salt in which the counter ion is a halide ion according to the present invention ( c) When used in place of the component, hydrogen peroxide is decomposed and the bleaching performance deteriorates.

In the general formula (II), R ^{2 to} R ⁶ have the above meanings, but at least one of R ² , R ³ , R ⁴ and R ⁵ is an alkyl group having 8 to 18 carbon atoms. Is preferred. Also,
R ^2, R ^3, total the total number of carbon atoms of R ⁴ and R ⁵ is preferably 11 to 40, 16
~ 38 is more preferable. If the total number of carbon atoms is less than 11, the stabilizing effect of the bleach activator is reduced. If the total number is more than 40, a precipitate is deposited on the composition, which tends to impair the appearance of the product. From the viewpoint of stability, the total number of carbon atoms is preferably 16 or more. R ⁶ is preferably an alkyl group having 1 to 14 carbon atoms. An example of the component (c) is as follows.

[0019]

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[0020]

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[Liquid bleach composition] The bleach composition of the present invention contains the component (a) in an amount of 0.3 to 30% by weight, preferably 0.5 to 20% by weight.
% By weight, more preferably 0.5 to 10% by weight, 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight of the component (b), and 0.1 to 5% by weight of the component (c). ~ 30
% By weight, preferably 0.1-20% by weight, more preferably
It contains 0.1 to 10% by weight. If the amount of component (a) is less than 0.3% by weight, sufficient bleaching performance cannot be obtained. on the other hand,
If it exceeds 30% by weight, it is dangerous because the storage stability of hydrogen peroxide itself becomes unstable. If the amount of the component (b) is less than 0.01% by weight, sufficient bleaching performance cannot be obtained. On the other hand, if it exceeds 20% by weight, the color pattern tends to be bleached. If the amount of the component (c) is out of the range of 0.1 to 30% by weight, the storage stability tends to decrease.

The weight ratio of the component (b) to the component (c) [(b)
Component] / [(c) component] is preferably 1/50 to 5/1,
More preferably 1/20 to 2/1, particularly preferably 1/10
２2/1.

In the composition of the present invention, (d) component
At least one selected from the group consisting of nonionic surfactants and amphoteric surfactants can be blended. Such nonionic surfactants include polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides, sucrose fatty acid esters, alkyl glycosides, glycerin higher fatty acid esters, polyoxyethylene And ethylene higher fatty acid esters. Among them, particularly preferred are polyoxyethylene alkyl (or alkenyl) ethers represented by the following general formula (III).

R ¹⁰ -O- (R ¹¹ O) _p -H (III) wherein R ^{10 is} a total straight or branched carbon atom which may be interrupted by an amide group, an ester group or an ether group. It represents an alkyl group or alkenyl group having several tens to 24 atoms, or an aryl group substituted with a linear or branched alkyl group having 8 to 22 carbon atoms. R ^{11 represents a} linear or branched alkylene group having 2 to 3 carbon atoms. p: The average value shows the number of 3-50. Examples of the polyoxyethylene alkyl (or alkenyl) ether represented by the general formula (III) are as follows.

C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₅ −H, C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₇ −HC ₁₂ H ₂₅ O (C ₂ H ₄ O) ₃₀ −H, C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ −HC ₁₂ H ₂₅ O (C ₂ H ₄ O) ₈ −H, C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₀ −HC ₁₈ H ₃₇ O (C ₂ H ₄ O) ₁₅ −H, C ₁₈ H ₃₇ O (C ₂ H ₄ O) ₇ −HC ₁₁ H ₂₃ COOC ₂ H ₄ O (C ₂ H ₄ O) ₁₅ −H, C ₁₁ H ₂₃ CONHC ₂ H ₄ O (C ₂ H ₄ O) ₁₅ −HC ₁₁ H ₂₃ COOC ₂ H ₄ O (C ₂ H ₄ O) ₇ −H, C ₁₁ H ₂₃ CONHC ₂ H ₄ O (C ₂ H ₄ O) ₇ −H The amphoteric surfactant to be blended as the component (d) includes a compound represented by the following general formula (IV).

[0026]

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Wherein R ¹² , R ¹³ , R ¹⁴ : at least one of which may be interrupted by an amide group, ester group or ether group (preferably not interrupted), linear or It represents an alkyl group or alkenyl group having a total of 6 to 22, preferably 10 to 22 carbon atoms in the branched chain, and the remaining groups represent an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. R ¹⁵ : carbon number 1 which may be substituted with a hydroxyl group
And 6 to 6 alkylene groups. Z ⁻ : represents —SO ₃ ^— or —COO ⁻ , preferably —SO ₃ ^— . Examples of the amphoteric surfactant represented by the general formula (IV) are as follows.

[0028]

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[0029]

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The component (d) is contained in the composition of the present invention in an amount of 0%.
-30% by weight, preferably 0.1-20% by weight, more preferably 0.5-15% by weight. When the amount of the component (d) exceeds 30% by weight, the viscosity of the composition increases,
It is difficult for consumers to handle.

Further, the liquid bleach composition of the present invention includes:
(e) A sequestering agent can be blended as a component. Examples of the sequestering agent include (1) a phosphoric acid compound such as phytic acid or an alkali metal salt or an alkanolamine salt 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 acids such as triethylenetetramine hexaacetic acid and diencoric acid, or alkali metal salts or alkanolamine salts thereof (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid Organic acids such as oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, 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 an alkali metal salt or alkanolamine salt thereof, and polyethylene polyamine poly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof. Among them, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferable, and at least one selected from the group consisting of the above (2) is more preferable.
The amount of such a sequestering agent is desirably 0.0005 to 5% by weight, preferably 0.01 to 1% by weight, based on the liquid bleaching composition of the present invention.

The liquid bleach composition of the present invention may contain known components which are usually added in addition to the above components. For example, water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates and phosphates can be used as builders. In addition, as a stabilizer for peroxides or hydrogen peroxide adducts, known magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium salts such as magnesium hydroxide, and silicates such as sodium silicate are used. be able to. Further, if necessary, a redeposition inhibitor such as carboxymethylcellulose, polyvinylpyrrolidone, or polyethylene glycol can be added.

The liquid bleach composition of the present invention basically comprises the above components (a) to (C) or components (a) to (e),
Although dissolved or dispersed in water, a hydrotrope agent may be added for the purpose of improving the stability of the liquid at low temperatures and improving the freeze-recoverability and preventing the liquid separation at high temperatures. As such a hydrotrope, generally, a short-chain alkyl benzene sulfonate represented by toluene sulfonate, xylene sulfonate and the like,
Examples include alcohols and polyhydric alcohols represented by ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin and the like. The hydrotrope can be added in an amount of about 0 to 30% by weight in the liquid bleach composition of the present invention.

Further, the liquid bleaching composition of the present invention can further contain various compounds. For example,
Phosphoric acid, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline, phenacetin and the like, and DL-α-tocopherol, gallic acid derivatives, butyl known as hydrogen peroxide stabilizers Hydroxyanisole (BHA), 2,6-
Di-tert-butyl-4-methylphenol (BHT) and the like can be added. The amount of these stabilizers depends on the concentration of hydrogen peroxide, but it is usually about 0 to 5% by weight, preferably 0.01 to 3% by weight, in the composition of the present invention.

Further, the liquid bleach composition of the present invention may contain a substance known as an anti-fading agent. Such substances include phenylalanine, histidine,
Lysine, tyrosine, amino acids such as methionine and amino acid salts, and amino or imide compounds such as hydroxyiminodiacetic acid, and acrylonitrile and one or two or more monomers copolymerizable with acrylonitrile having a quaternary ammonium group And copolymers. 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. In addition, the liquid bleach composition of the present invention contains Tinopearl (T) as a fluorescent whitening agent to increase the bleaching effect on white fiber.
inopal) CBS (manufactured by Ciba-Geigy),
A fluorescent whitening agent such as Tinopearl SWN (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% by weight.

Further, a thickener may be added to the liquid bleaching composition of the present invention in an amount of 0 to 20% by weight for the purpose of increasing the viscosity of the composition and improving usability. As the thickener, generally, polyacrylates, acrylic acid-maleic acid copolymer, carboxymethylcellulose derivatives, methylcellulose, synthetic polymers such as hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum, kelzan, montmorillonite, veegum Water-swellable clay minerals are used.

The liquid bleach composition of the present invention further comprises a coloring agent such as a dye or a pigment, a fragrance, silicones, a bactericide, an ultraviolet absorber, an inorganic electrolyte (for example, NaCl,
Na ₂ SO ₄ , CaCl ₂ ) and other various trace additives in appropriate amounts (each 0
To about 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acidic solution is particularly preferable. In the composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) may be used, if necessary, in order to improve the bleaching performance.
Can be blended.

It is desirable that the pH of the liquid bleach composition of the present invention is 6 or less, preferably 3.5 or less. In order to adjust the pH, use an inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as toluenesulfonic acid or benzenesulfonic acid, or use the above-described metal-sequestering agent or anionic surfactant in an acid form. Or, if necessary, by using a caustic such as sodium hydroxide or potassium hydroxide. Further, the liquid bleach composition of the present invention can be used by mixing with a conventionally known clothing detergent.

[0039]

According to the present invention, liquid bleaching exhibits high bleaching performance not only under alkaline conditions but also under neutral or acidic conditions, has extremely excellent storage stability, and does not cause decolorization of dyes on fibers. An agent composition can be provided.

[0040]

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.

Examples 1 to 12 and Comparative Examples 1 to 4 (b-1) to (b-4) as components (b) and (c-1) as component (c)
(C-4), (d-1) to (d-4) as components (d) and (e-1) as component (e), and the composition shown in Tables 1, 2 and 3 respectively. To prepare a liquid bleach composition. With respect to the obtained liquid bleaching agent compositions, the bleaching performance, storage stability and anti-bleaching properties were measured by the following methods, and the results are shown in Tables 1, 2 and 3. Further, as a comparative example, the result of using the following (f-1) instead of the component (c) is also shown. In addition, the composition shown in Table 1, Table 2, and Table 3 is:
The pH was adjusted to 2 with a 0.5N aqueous sulfuric acid solution.

[0042]

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[0043]

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(1) Method of evaluating storage stability <Remaining ratio of effective bleach activator> After storing the liquid bleach composition under the conditions shown in Tables 1, 2 and 3, the organic bleaching composition in the sample composition was The amount of the bleaching activator producing peracid was measured, and the effective bleaching activator residual ratio was calculated by the following equation.

[0045]

(Equation 1)

<Residual rate of hydrogen peroxide> Tables 1, 2 and 3
After storing the liquid bleach composition under the conditions shown in (1), the concentration of hydrogen peroxide in the sample composition was measured by an iodometry method, and the residual ratio of hydrogen peroxide was determined by the following equation.

[0047]

(Equation 2)

(2) Method for measuring bleaching performance 40 ml of the bleaching compositions shown in Tables 1, 2 and 3 were added to a 2 liter aqueous solution containing a 0.133% commercially available detergent solution (pH = 10.2).
5 pieces of black tea-stained cloth ^*
Soaked for 15 minutes. Thereafter, it was rinsed with tap water, dried and the bleaching ratio was calculated by the following equation. The bleaching performance of each of the bleaching compositions before storage and those after storage under the conditions shown in Tables 1, 2 and 3 was measured. * Bleaching rate of black tea cloth

[0049]

(Equation 3)

The reflectance is NDR-101 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with DP using a 460 nm filter. * Preparation method of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) is boiled with 3 liters of ion-exchanged water for about 15 minutes, rubbed with bleached cotton after desizing, and dipped in cotton cloth # 2003 in this liquid. Boil for a minute. Remove from the heat as it is, leave it for about 2 hours and let it dry naturally.
After pressing, a test piece of 10 cm × 10 cm was used for the experiment.

(3) Decolorization test method: Naphthol dye (dipping agent; Naphthol A)
S, developer: cotton cloth (10cm × 1) dyed with Fast Red GBase
0cm). 0.133% commercial detergent solution (pH = 10.2)
40 ml of the bleaching compositions shown in Tables 1, 2 and 3 were added to a 2 liter aqueous solution containing
Then rinsed with tap water and dried. This operation was repeated 20 times, and the degree of bleaching was evaluated on the following four scales. ◎… not decolored at all ○… slightly faint, but not bothersome △… partially decolorized ×… decolorization spread over the entire cloth

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-7218 (JP, A) JP-A-6-49487 (JP, A) JP-A-63-12520 (JP, A)

Claims (8)

(57) [Claims] 1. The composition contains 0.3 to 30% by weight of the following component (a), 0.01 to 20% by weight of the component (b) and 0.1 to 30% by weight of the component (c).
And the weight ratio of component (b) to component (c) is [component (b) / (c)
Components] = 1 / 50-5 / 1 der liquid bleach composition characterized Rukoto. (a) Component: hydrogen peroxide (b) Component: Bleaching activator represented by the general formula (I) [Wherein, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms. Y ^-: SO ₃ ^- or COO ^- shows the. M ⁺ : represents a cationic group. n indicates 0 or 1. Component (c): a quaternary ammonium salt represented by the general formula (II): [Wherein, R ² , R ³ , R ⁴ , R ⁵ : at least one of them represents a straight-chain or branched-chain alkyl or alkenyl group having 6 to 20 carbon atoms, and the remaining group is one or more. A C 1-3 alkyl group which may be substituted with a hydroxyl group. R ^{6 represents a} linear or branched C1-C20 alkyl or alkenyl group, or a linear or branched C1-C18 aryl group optionally substituted with an alkyl group; . _{^{X -: -OSO 3 -, -SO}} 3 - shows the ^- or -COO. ] 2. The liquid bleach composition according to claim 1, wherein the component (b) is a bleach activator represented by the general formula (I-1). Embedded image [Wherein, R ¹ , M ⁺ , n: has the above meaning. ] 3. The liquid bleach composition according to claim ¹ , wherein R ^{1 of} component (b) is a linear or branched alkyl group having 5 to 15 carbon atoms. 4. The liquid bleach composition according to claim 3, wherein R ^{1 of} component (b) is a linear or branched alkyl group having 8 to 14 carbon atoms. 5. The liquid bleach composition according to claim 1, wherein the total carbon number of component (c) R ² , R ³ , R ⁴ and R ⁵ is 11 to 40. 6. The liquid bleach composition according to claim ⁵ , wherein the total total number of carbon atoms of component (c) R ² , R ³ , R ⁴ and R ⁵ is 16 to 38. 7. The liquid bleaching composition according to claim 1, which comprises at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants as the component (d). 8. The liquid bleaching composition according to claim 1, which contains a sequestering agent as the component (e).