JP3410880B2 - 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, it contains a bleaching activator which reacts with hydrogen peroxide to produce an organic peracid, and has a storage stability. An excellent liquid bleach composition.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents, but chlorine-based bleaching agents are limited in the fibers that can be used, and cannot be used in colors and patterns. Oxygen-based bleaching agents, which do not have these disadvantages, have recently become extremely popular due to their non-existence and unique odor. Among the oxygen-based 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-based bleaching agents have a weaker bleaching power than chlorine-based bleaching agents, and usually various bleaching activators are used together. Examples of these bleach activators include O-acetylated compounds represented by glucose pentaacetate (GPAC), N-acylated compounds represented by tetraacetylethylenediamine, and acid anhydrides represented by maleic anhydride. can give. Furthermore, the inventors of the present invention have disclosed JP-A-63-233969 and JP-A-63-3.
As illustrated in Japanese Patent No. 1566, Japanese Patent Application Laid-Open No. 64-68347, Japanese Patent Application Laid-Open No. 1-190654, and the like,
It has been found that a compound that reacts with hydrogen peroxide to form an organic peracid having a quaternary ammonium group is extremely excellent as a bleach activator. Further, examples of organic peracid precursors having an anionic group are illustrated in JP-B-63-12520.

These bleach activators are compounds which react with hydrogen peroxide to produce an organic peracid 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 liquid bleaching compositions, and mixtures of solid persalts with dry particles of these bleach activators to keep them dry. It is generally used as a composition consisting of

A liquid bleaching composition containing a bleaching activator which produces an organic peracid is disclosed in JP-A-62-2308.
Japanese Patent Laid-Open No. 97 discloses a composition obtained by dispersing a solid bleaching activator in an acidic aqueous solution containing hydrogen peroxide, which has excellent storage stability and exhibits activity at low temperatures. However, since the bleach activator was in a dispersed state in this composition, the bleach activator was precipitated and separated during storage, and the appearance of the product was remarkably impaired. 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. Furthermore, since the bleach activator is not dissolved in the composition and is present in a dispersed state in this composition, the bleach activator remains undissolved during actual bleaching, and when it adheres to the bleached substance, its part There was a problem that the dye was decolorized.

[0006] Therefore, the problem to be solved by the present invention is not only alkaline, but also shows high bleaching performance not only under neutral or acidic conditions, but also has extremely excellent storage stability, and further causes decolorization of dyes in fibers. No liquid bleach composition is provided.

[0007]

As a result of intensive studies, the present inventors have found that the above problems can be solved by combining specific components, and completed the present invention. That is, the present invention is the following (a) component 0.3 ~ 30 wt%, (b)
The present invention provides a liquid bleaching composition containing 0.01 to 20% by weight of a component and 0.1 to 30% by weight of a component (c) and containing no cationic surfactant . Component (a): Hydrogen peroxide (b) Component: Bleach activator represented by general formula (I)

[0008]

[Chemical 4]

[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 ⁺ : H or a cation group. n: 0 or 1 is shown. ] (C) Component: Nonionic surfactant represented by the general formula (II)

[0010]

[Chemical 5]

[In the formula, R ^{2 represents a} linear or branched alkyl group or alkenyl group having 5 to 19 carbon atoms. R ³ : represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. R ^4: a linear or branched chain alkylene or hydroxyalkylene group having 1 to 5 carbon atoms. m: Shows a number having an average value of 3 to 100. ]

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

[Component (b)] In the present invention, the bleaching activator represented by the above general formula (I) is used as the component (b). In the general formula (I), R ¹ has the above meaning, but preferably has 5 to 15 carbon atoms.
Is an alkyl group. M ⁺ represents H or a cation group, and examples of the cation group include cations such as alkali metal ions, alkaline earth metal ions, ammonium ions, and alkyl-substituted ammonium ions. An example of this bleach activator is as follows.

[0014]

[Chemical 6]

[0015]

[Chemical 7]

Among these, as the component (b), the compound represented by the general formula (I
It is preferable to use the bleaching activator represented by -1) or (I-2), and it is particularly preferable to use the bleaching activator represented by the general formula (I-1).

[0017]

[Chemical 8]

[Wherein R ¹ , M ⁺ , and n are as defined above. [Component (c)] In the present invention, a nonionic surfactant represented by the above general formula (II) is used as the component (c). This nonionic surfactant having an ester group is generally produced by an esterification reaction of an alkylene oxide adduct of alcohol and a fatty acid, or an alkyl etherification of an alkylene oxide adduct of a fatty acid. be able to. Further, it can be produced by the production method using magnesium oxide as a catalyst described in JP-A-6-220498. In the present invention, a nonionic surfactant having an ester group produced by any of these methods may be used.

In the general formula (II), R ^{2 to} R ⁴ and m have the above-mentioned meanings, but the R ² group is preferably an alkyl group having 9 to 15 carbon atoms, and m is 6 to 50. preferable. Further, the R ³ group is preferably a methyl group, an ethyl group or an isopropyl group, and the R ⁴ group is preferably an ethylene group or a propylene group. Examples of these nonionic surfactants include the following. C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₀ -OCH ₃ , C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₃₀ -OCH ₃ , C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₅₀ -OCH ₃ , C ₁₃ H ₂₇ CO (OC ₂ H ₄ ) ₁₀ -OCH ₃ , C ₁₅ H ₃₁ CO (OC ₂ H ₄ ) ₅₀ -OCH ₃ , C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₀ -OC ₂ H ₅ , C _{11 H 23 CO (OC 2 H 4} ) 10 -O-isoC 3 H 7.

[Liquid bleach composition] The bleach composition of the present invention comprises 0.3 to 30% by weight of the component (a),
Preferably 0.5 to 20% by weight, more preferably 0.5 to 10% by weight, the component (b) 0.01 to 20% by weight, preferably
0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and the component (c) is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight. When the amount of the 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 blending 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 colored pattern tends to be decolorized. If the compounding amount of the component (c) is outside the range of 0.1 to 30% by weight, the storage stability tends to decrease. The weight ratio of the component (b) and the component (c) [(b) component] / [(c) component] is preferably 1/50 to 5/1, more preferably 1/20 to 2/1, It is particularly preferably 1/10 to 2/1.

Further, the liquid bleach composition of the present invention comprises
As the component (d), at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants other than the above component (c) can be blended. The blending amount of this component (d) is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5, with respect to the total amount of the liquid bleaching composition of the present invention.
~ 5% by weight.

The nonionic surfactant used as the component (d) is preferably a compound represented by the general formula (V).

R ¹⁴ -B- (AO) _p -Y (V) [wherein, R ¹⁴ is a linear or branched C 6-22, preferably 8-18, more preferably 10-18 alkyl. Represents a group or an alkenyl group, or represents an aryl group which may be substituted by a linear or branched alkyl group having 1 to 18 carbon atoms, of which the alkyl group is preferable. B represents an -O- group or a -COO- group, preferably an -O- group. A represents a linear or branched alkylene group having 2 to 3 carbon atoms, and p A's may be the same or different. Y is H or 1 to 3 carbon atoms
Is an alkyl group. However, when B is -COO- group, Y is H. p is a number of 3 to 50, preferably 3 to 20, and more preferably 4 to 15, which represents the average number of moles of alkylene oxide added. In the general formula (V), AO represents an alkylene oxide having 2 to 3 carbon atoms, preferably ethylene oxide or propylene oxide, which may be added in a block type or a random type. Good.

Specific examples of the compound represented by the general formula (V) include the following compounds.

C ₁₀ H ₂₁ O (C ₂ H ₄ O) _p -HC ₁₂ H ₂₅ O (C ₂ H ₄ O) _p -H C ₁₄ H ₂₉ O (C ₂ H ₄ O) _p -HC ₁₆ H ₃₃ O (C ₂ H ₄ O) _p -H C ₁₈ H ₃₇ O (C ₂ H ₄ O) _p -HC ₂₀ H ₄₁ O (C ₂ H ₄ O) _p -H C ₁₀ H ₂₁ O (C ₃ H ₆ O) _p -HC ₁₂ H ₂₅ O (C ₃ H ₆ O) _p -H C ₁₄ H ₂₉ O (C ₃ H ₆ O) _p -HC ₁₆ H ₃₃ O (C ₃ H ₆ O) _p -H C ₁₈ H ₃₇ O (C ₃ H ₆ O) _p -HC ₂₀ H ₄₁ O (C ₃ H ₆ O) _p -H C ₉ H ₁₉ COO (C ₂ H ₄ O) _p -HC ₁₁ H ₂₃ COO (C ₂ H ₄ O) _p -H C ₁₃ H ₂₇ COO (C ₂ H ₄ O) _p -HC ₁₅ H ₃₁ COO (C ₂ H ₄ O) _p -H C ₁₇ H ₃₅ COO (C ₂ H ₄ O) _p -HC ₁₉ H ₃₉ COO (C ₂ H ₄ O) _p -H C ₁₀ H ₂₁ O (C ₂ H ₄ O) _p -CH ₃ C ₁₂ H ₂₅ O (C ₂ H ₄ O) _p -CH ₃ C ₁₄ H ₂₉ O (C ₂ H ₄ O) _p -CH ₃ C ₁₆ H ₃₃ O (C ₂ H ₄ O) _p -CH ₃ C ₁₈ H ₃₇ O (C ₂ H ₄ O) _p -CH ₃ C ₂₀ H ₄₁ O (C ₂ H ₄ O) _p -CH _Further , the amphoteric surfactant used as the component (d) is preferably a compound represented by the general formula (IV).

[0026]

[Chemical 9] [In the formula, R ¹⁰ , R ¹¹ and R ¹² are linear or branched alkyl having 6 to 22 carbon atoms, at least one of which may be interrupted by an amide group, an ester group or an ether group. Represents a group or an alkenyl group, and the remaining groups represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ^{13 represents a} linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group. Z ⁻ : indicates SO ₃ − or COO ⁻ . Examples of these amphoteric surfactants include the following compounds.

[0027]

[Chemical 10]

[0028]

[Chemical 11]

Among these, sulfobetaine type amphoteric surfactants are particularly preferable.

Further, the liquid bleach composition of the present invention comprises
A sequestering agent may be added as the component (e). As the sequestering agent, (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-
Diphosphonic acid, phosphonic acid such as methanehydroxyphosphonic acid, or their alkali metal salts or alkanolamine salts (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or their alkali metal salts or alkanolamine salts (4) Aspartic acid, glutamic acid, amino acids such as glycine or their alkali metal salts or alkanolamine salts (5) Nitrilotriacetic acid, Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencoric acid or their alkali metal salts or alkanolamine salts (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, carboxymethyl succinic acid, carboxymethyl tartaric acid, and their alkali metal salts or alkanolamine salts (7) Alkali metal salts of aluminosilicate represented by zeolite A or alkanolamine salts (8) ) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or polyethylenepolyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt. Among these, (2), (5), (6) and
At least one selected from the group consisting of (7) is preferable, and at least one selected from the group consisting of (2) above is more preferable. The amount of such a sequestering agent is 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 bleaching composition of the present invention may contain known components which are usually added in addition to the above components. For example, as the builder, a water-soluble inorganic builder such as sulfate, carbonate, bicarbonate, silicate or phosphate can be used. Further, known magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicates such as sodium silicate are used as stabilizers of peroxides or hydrogen peroxide adducts. be able to. Further, if necessary, anti-redeposition agents such as carboxymethyl cellulose, polyvinylpyrrolidone, and polyethylene glycol can be added.

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

Further, the liquid bleaching composition of the present invention may further contain various compounds. For example,
Phosphoric acid, which is known as a stabilizer of hydrogen peroxide, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, and DL-α-tocopherol, gallic acid derivative, butyl Hydroxyanisole (BHA), 2,6-
Di-tert-butyl-4-methylphenol (BHT) and the like can be added. The addition 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 bleaching composition of the present invention may contain a substance known as an anti-fading agent. Such substances include phenylalanine, histidine,
Amino acids and amino acid salts such as lysine, tyrosine and methionine, and amino or imide compounds such as hydroxyiminodiacetic acid, and one or more of acrylonitrile and acrylonitrile having a quaternary ammonium group and a copolymerizable monomer. Copolymers and the like. Although amino acids have optical isomers, the optical isomers do not participate in the effect of the present invention. Therefore, it is also possible to use chemically synthesized amino acids. Further, the liquid bleaching composition of the present invention, as a fluorescent whitening agent in order to increase the bleaching effect on white fiber, Tinopearl (T
inopal) CBS [manufactured by Ciba-Geigy],
Optical brighteners such as Chino Pearl SWN (manufactured by Ciba Geigy) and color index optical brighteners 28, 40, 61, 71 may be added in an amount of 0 to 5% by weight.

Further, the liquid bleaching composition of the present invention may contain a thickener in an amount of 0 to 20% by weight for the purpose of increasing the viscosity of the composition and improving the usability. As the thickener, generally, a polyacrylic acid salt, a maleic acid acrylic acid copolymer, a carboxymethylcellulose derivative, a synthetic polymer such as methylcellulose or hydroxymethylcellulose, a natural polymer such as xanthan gum, guar gum, or kerzan, montmorillonite, or veegum. Water-swelling clay minerals such as are used.

Further, the liquid bleaching composition of the present invention further comprises colorants such as dyes and pigments, fragrances, silicones, germicides, ultraviolet absorbers, inorganic electrolytes (eg NaCl,
Various trace additives such as Na ₂ SO ₄ and CaCl ₂ ) are added in appropriate amounts (each 0
Up to about 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acid solution is particularly preferable. Further, in the composition of the present invention, in order to improve the bleaching performance, a conventionally known enzyme (cellulase, amylase, protease, lipase, etc.) is optionally added,
It can be blended.

The liquid bleaching composition of the present invention has a pH of 6 or less, preferably 3.5 or less. To adjust the pH, use inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as toluenesulfonic acid and benzenesulfonic acid, or use the above-mentioned sequestering agents and anionic surfactants in acid form. It is advisable to add it by using the above method or adjust it with a caustic alkali such as sodium hydroxide or potassium hydroxide if necessary. Further, the liquid bleaching composition of the present invention can also be used as a mixture with a conventionally known clothing detergent.

[0038]

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

[0039]

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

Examples 1 to 4 and Comparative Examples 1 to 5 (b) The components (b-1) to (b-5) and the component (c) (c-1)
~ (C-2), (d-1) as component (d) ~ (d-2) , and (e-1) as component (e) were used, and liquid bleaching was carried out with the composition shown in Table 1 and Table 2 , respectively. An agent composition was prepared. For the obtained liquid bleach composition, each appearance was observed, bleaching performance,
Storage stability and anti-bleaching property were measured by the following methods. The results are shown in Tables 1 and 2 . In addition, Example 1 and Comparative Examples 1 to 1
2 formulation composition was adjusted to pH2 by 0.5N aqueous solution of sulfuric acid, blend compositions of Examples 2-4 and Comparative Examples 3-5
The pH was adjusted to 2.5 with 0.5N sulfuric acid aqueous solution.

[0041]

[Chemical 12]

[0042]

[Chemical 13]

(1) Storage stability evaluation method <Effective bleach activator residual rate> After the liquid bleach composition was stored under the conditions shown in Tables 1 and 2 , the organic peracid in the sample composition was removed. The amount of the bleach activator produced was measured, and the effective bleach activator residual rate was calculated by the following formula.

[0044]

[Equation 1]

<Hydrogen Peroxide Residual Ratio> After the liquid bleaching composition was stored under the conditions shown in Tables 1 and 2 , the hydrogen peroxide concentration in the sample composition was measured by the iodometry method to obtain hydrogen peroxide. The residual rate was calculated by the following formula.

[0046]

[Equation 2]

(2) Method for measuring bleaching performance 40 ml of the bleaching agent composition shown in Table 1 and Table 2 was added to a 2 liter aqueous solution containing 0.133% commercial detergent solution (pH = 10.2) to prepare as follows. Five pieces of black tea-contaminated cloth ^* were immersed for 15 minutes each. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. The bleaching performance was measured for each of the bleaching agent composition before storage and after storage under the conditions shown in Tables 1 and 2 . * Bleaching rate of tea-contaminated cloth

[0048]

[Equation 3]

The reflectance is NDR-101 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with DP using a 460 nm filter. * Preparation of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) is boiled in 3 liters of ion-exchanged water for about 15 minutes, then rubbed with de-squeezed cotton and soaked in cotton gold cloth # 2003 for about 15 minutes. Boiled for a minute. Remove from heat as it is, let stand for about 2 hours to air dry, wash with water until the washing liquid does not turn, dehydrate,
After pressing, a test piece of 10 cm × 10 cm was prepared and used for the experiment.

(3) Decolorization test method Naphthol dye (underpickling agent; Naphthol A on a petri dish)
S, color developer; Fast Red GBase) cotton cloth (10 cm x 1)
0 cm) is prepared. 0.133% commercial detergent solution (pH = 10.2)
40 ml of the bleaching agent composition shown in Table 1 and Table 2 was added to a 2 liter aqueous solution containing the above, and 5 sheets were immersed for 30 minutes each, and then rinsed with tap water and dried. This operation was repeated 20 times, and the degree of decolorization was evaluated according to the following 4 grades. ◎… No decolorization at all ○… Slightly thin, but not at all △… Partly decolorized ×… Decolorization spreads throughout the cloth

[0051]

[Table 1]

[0052]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takaomi Himo 1334 Minato Minato, Wakayama, Wakayama Kao Co., Ltd. (56) References JP-A-7-82591 (JP, A) JP-A-8-120295 (JP) , A) JP-A-8-188796 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/74 C11D 1/88 C11D 1/94 C11D 3/39 C11D 3/395

Claims (4)

(57) [Claims] 1. It 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 does not contain a cationic surfactant. A liquid bleaching composition comprising: Component (a): Hydrogen peroxide (b) Component: Bleach activator represented by the general formula (I) [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 ⁺ : H or a cation group. n: 0 or 1 is shown. ] (C) Component: Nonionic surfactant represented by the general formula (II) [In the formula, R ^{2 represents a} linear or branched alkyl group or alkenyl group having 5 to 19 carbon atoms. R ³ : represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. R ^4: a linear or branched chain alkylene or hydroxyalkylene group having 1 to 5 carbon atoms. m: Shows a number having an average value of 3 to 100 . ] 2. The liquid according to claim 1, wherein the component (d) contains 0.01 to 20% by weight of at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants other than the component (c). Bleach composition. 3. The liquid bleaching composition according to claim 1, wherein the component (b) is a bleaching activator represented by the general formula (I-1) or the general formula (I-2). [Chemical 3] [In the formula, R ¹ , M ⁺ , and n are as defined above. ] 4. The liquid bleaching composition according to claim 1, which contains a sequestering agent as the component (e).