JPH08120295A - Liquid bleaching agent composition - Google Patents

Abstract

PURPOSE: To obtain a liq. bleaching agent compsn. which is excellent in storage stability and does not decolorize a dye by incorporating a combination of specific bleaching activators with a specific surfactant into the compsn. CONSTITUTION: The compsn. contains hydrogen peroxide, a compd. of formula l [R<1> is a 5-21C alkyl or alkenyl group (optionally interrupted by an ester, amide, or ether linkage or by a group of formula II) or an aryl group (optionally substd. by a 6-20C alkyl or alkenyl group); and X is SO3 M, COOM, SO3 <-> , or COO-(wherein M is H or a cation)], a compd. of formula III [R<2> to R<4> are each a 6-22C alkyl or alkenyl group (optionally interrupted by an ester, amide, or ether group), 1-3C alkyl, or hydroxyalkyl; R<5> is optionally hydroxylated 1-6C alkylene; and Y<-> is SO3 <-> or COO<-> ], and a surfactant of formula IV (R<6> is 1-3C alkyl or hydroxyalkyl; and Z is an anion) or formula V. The compsn. may further contain a nonionic or anionic surfactant.

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 specifically, it contains a bleaching activator which reacts with hydrogen peroxide to produce an organic peracid, and has excellent storage stability and It relates to a liquid bleach composition which does not cause decolorization of dyes.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents. Chlorine-based bleaching agents are limited in the fibers that can be used, and colors and patterns are limited. Oxygen-based bleaches, which are free of these drawbacks, have recently become very popular due to their inability to use and their 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 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. To be Furthermore, the present inventors
JP-A-63-233969, JP-A-63-31566, JP-A-64
As disclosed in, for example, JP-A-68347 and JP-A-1-190654, a compound which reacts with hydrogen peroxide to produce an organic peracid having a quaternary ammonium group is extremely effective as a bleach activator. I found it to be excellent. Further, examples of organic peracid precursors having an anionic group are disclosed in Japanese Examined Patent Publication No. Sho 63-1252.
No. 0 publication is exemplified.

[0004] These bleach activators are compounds that react with hydrogen peroxide under mild conditions of washing conditions to produce organic peracids, and are therefore generally unstable to hydrogen peroxide. For this reason, these bleach activators are usually difficult to use as liquid bleaches, and in order to keep them dry, they are used as compositions consisting of a mixture of solid persalt and dry particles of these bleach activators. It is generally used.

As a liquid bleaching composition containing a bleaching activator which produces an organic peracid, JP-A-62-230897 discloses a solid bleaching activator in an acidic aqueous solution containing hydrogen peroxide. Disclosed is a composition which is excellent in storage stability and is active at low temperature. However, this composition precipitates and separates during storage due to the dispersion of the bleach activator, and significantly detracts from its use. 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, the bleach activator is dispersed and present, and the bleach activator remains undissolved during the actual bleaching. When it adheres to the bleached product, the dye in that part is discolored.

Therefore, as a result of extensive studies on a bleaching agent composition having excellent storage stability, a bleaching agent composition comprising hydrogen peroxide, an amphoteric surfactant and a bleaching activator described in JP-A-6-49487. Provided. However, this composition still has insufficient storage stability, and there is a problem in the decolorizing property of the dye.

The problem to be solved by the present invention is to provide a liquid bleaching agent which is extremely excellent in storage stability and does not cause decolorization of dyes.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the object can be achieved by combining a specific bleaching activator and a specific surfactant. The present invention has been completed.

That is, the present invention provides a liquid bleaching composition containing the following components (a), (b) and (c). Component (a): Hydrogen peroxide (b) Component: Bleach activator represented by general formula (I)

[0010]

[Chemical 6]

[Wherein R ^{1 is an} ester bond, an amide bond, an ether bond or

[0012]

[Chemical 7]

The bond represented by the formula (1) represents an optionally interrupted linear or branched alkyl or alkenyl group having 5 to 21 carbon atoms, or a linear or branched carbon atom having 6 to 20 carbon atoms. Represents an aryl group which may be substituted with an alkyl group or an alkenyl group. X: or indicating a -SO ₃ M or -COOM, or -SO ₃ ^- or -COO ^- shows the. Here, M represents a hydrogen atom or an inorganic or organic cation group. ] (C) component: a surfactant represented by the general formula (II), the general formula (I
II) and at least one selected from the group consisting of surfactants represented by the general formula (IV)

[0014]

Embedded image

[In the formula, at least one of R ² , R ³ , R ⁴ R ² , R ³ and R ⁴ groups may be interrupted by an ester bond, an amide bond or an ether bond. , A straight chain or branched chain alkyl group or alkenyl group having 6 to 22 carbon atoms, and other groups represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. R ⁵ : 1 to 1 carbon atoms, which may be substituted with a hydroxyl group
6 represents an alkylene group. Y ^-: -SO ₃ ^- or -COO ^- shows the. ]

[0016]

[Chemical 9]

[Wherein R ² , R ³ and R ⁴ are as defined above. R ⁶ : represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Z ^-: represents an inorganic or organic anion group. ]

[0018]

[Chemical 10]

[Wherein R ² , R ³ and R ⁴ are as defined above. The present invention will be described in detail below.

[Component (b)] In the present invention, the bleach activator represented by the above general formula (I) is used as the component (b). In the general formula (I), the M group represents an inorganic or organic cation group such as an alkali metal ion (N
a ⁺ , K ^+, etc.), ammonium ion, quaternary ammonium ion and the like. Examples of preferable compounds as the bleaching activator represented by the general formula (I) include the following.

[0021]

[Chemical 11]

[Component (c)] In the present invention, as the component (c), a surfactant represented by the above general formula (II), a general formula (I)
At least one selected from the group consisting of the surfactant represented by II) and the surfactant represented by the general formula (IV) is used. Here, in the general formula (III), Z ⁻ represents an inorganic or organic anion group.
^-, Br ^-, etc.) or _{^{CH 3 SO 4 -, C 2}} H 5 SO 4 - and the like. The following are examples of the surfactant represented by the general formula (II).

[0023]

[Chemical 12]

[0024]

[Chemical 13]

Of these, sulfobetaine is preferred.

Examples of the surfactant represented by the general formula (III) include the following.

[0027]

Embedded image

The following are examples of the surfactant represented by the general formula (IV).

[0029]

[Chemical 15]

[Liquid Bleaching Composition] The bleaching composition of the present invention contains 0.3 to 30% by weight of component (a), preferably 0.5 to 20% by weight, more preferably 0.5 to 10% by weight, and component (b). 0.1 to
20% by weight, preferably 0.1-10% by weight, more preferably
0.5 to 5% by weight is contained. Also, the blending amount of component (c) is
The amount is 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, and further preferably 0.5 to 10% by weight. Further, the weight ratio is [(b) component] / [(c) component] = 1/50 to 5/1, preferably 1/20 to 2/1, more preferably 1/10 to 1/1.

In this case, the component (a) is 0.3% by weight.
If it is less than this, sufficient bleaching performance cannot be obtained. On the other hand, if it exceeds 30% by weight, the storage stability of hydrogen peroxide itself becomes unstable, which is dangerous. If the amount of component (b) is less than 0.1% 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. In addition, the amount of component (c) blended is 0.5
If it is outside the range of up to 30% by weight, the storage stability will decrease.

Then, the weight ratio of the component (b) and the component (c) [(b)
When the ratio of component] / [component (c)] is less than 1/50, sufficient bleaching performance cannot be obtained, while when it exceeds 5/1, the storage stability of component (b) tends to be poor.

In the present invention, in order to improve the bleaching performance, at least one selected from the group consisting of nonionic surfactants and anionic surfactants can be used as the component (d).

In this case, as the nonionic surfactant, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyls are used. Examples thereof include glycosides. Among these, the nonionic surfactant represented by the general formula (V) is particularly preferable. R ⁷ O (R ⁸ O) _n -H (V) [In the formula, R ⁷ is a linear or branched carbon number 10 which may be interrupted by an ester bond, an amide bond or an ether bond.
~ 24 alkyl group or alkenyl group, or an aryl group substituted with a linear or branched alkyl group having 8 to 22 carbon atoms. R ⁸ : Shows a linear or branched alkylene group having 2 to 5 carbon atoms. n: Shows a number having an average value of 3 to 50. ].

The following compounds may be mentioned as specific examples. C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₅ -H, C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₇ -H, C ₁₂ H ₂₅ O
(C ₂ H ₄ O) ₃₀ -H, C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -H, C ₁₈ H ₃₇ O (C ₂ H ₄ O) _15-
H, C ₁₈ H ₃₆ O (C ₂ H ₄ O) ₇ -H _, C 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 -H, C 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.

Alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ethers as anionic surfactants. Examples are carboxylic acid salts and α-sulfo fatty acid esters.

Of these, nonionic surfactants are preferred.
When the component (d) is used in the present invention, the component (b) and
A preferred combination with the component (c) is exemplified by the case where the component (c) is a surfactant represented by the general formula (III) and the component (d) is a nonionic surfactant.

The content of the component (d) is 0 to 30% by weight, preferably 0 to 20% by weight, more preferably 0.5 to 20% by weight. When the content of the component (d) exceeds 30% by weight, the viscosity of the composition increases and it becomes difficult to handle.

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 a builder, sulfate, carbonate, bicarbonate, silicate, water-soluble inorganic builder such as phosphate, other water-insoluble inorganic builder such as zeolite, ethylenediamine tetraacetate, nitrilotriacetic acid salt, tartrate, Organic builders such as citrate can be used. Also known as stabilizers of peroxides or hydrogen peroxide adducts are magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicates such as sodium silicate. Can be used. Further, if necessary, recontamination inhibitors such as carboxymethylcellulose, polyvinylpyrrolidone and polyethylene glycol, enzymes such as protease, lipase, amylase and cellulase, optical brighteners, dyes, pigments and fragrances can be added.

The liquid bleaching composition of the present invention can also be used as a mixture with a conventionally known clothing detergent.

The liquid bleach composition of the present invention is basically a composition prepared by dissolving or dispersing the above-mentioned components (a) to (c) or components (a) to (d) in water. The hydrotrope agent may be added for the purpose of improving the stability and freezing stability of the liquid and preventing the liquid separation at high temperature. As such a hydrotrope, generally, a short-chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol,
Examples thereof include alcohols represented by ethylene glycol, propylene glycol, hexylene glycol, glycerin, and the like, and polyhydric alcohols.

Further, in the present invention, if desired,
A chelating agent can be added as the component (e). As the chelating agent, (1) a phosphoric acid compound such as phytic acid or an alkali metal salt, alkaline earth metal salt, ammonium salt or alkanolamine salt thereof (2) ethane-1,1-diphosphonic acid, ethane-1 , 1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid,
Phosphonic acids such as ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts (3) 2-phosphonobutane- Phosphonocarboxylic acids such as 1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanols. Amine salts (4) Amino acids such as aspartic acid, glutamic acid and glycine or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts (5) Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid Acetic acid, glycol ether diamine tetraacetic acid, hydro Shiechiruimino diacetate,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencoric acid or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, Organic acids such as lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts (7) Alkali metal salt, alkaline earth metal salt, ammonium salt or alkanolamine salt of aluminosilicate typified by zeolite A (8) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or polyethylene Polyamine (methylene phosphonic acid) or its alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts.

Among these, the above (2), (5), (6), (7)
At least one selected from the above is preferable, and in particular,
At least one selected from (2) is preferable.

The amount of such chelating agent is 0.0005 to 5% by weight, preferably 0.01 to 1 based on the liquid bleaching composition.
Weight percent is preferred.

Further, in the present invention, various compounds can be further contained. 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, butylated 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 is usually about 0 to 5% by weight, preferably 0.01 to
It is preferable to contain 3% by weight.

Further, in the present invention, a substance known as an anti-fading agent can be contained. Such substances include phenylalanine, histidine, lysine, tyrosine, amino acid and amino acid salts such as methionine, and amino or imide compounds such as hydroxyiminodiacetic acid,
Further, a copolymer or the like of acrylonitrile and acrylonitrile having a quaternary ammonium group and one or more types of monomers copolymerizable therewith. 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.

In order to enhance the bleaching effect on white fiber, Tinopal CBS is used as a fluorescent whitening agent.
[Manufactured by Ciba-Geigy], Tinopal SWN [manufactured by Ciba-Geigy], and color index fluorescent whitening agents 28, 40, 61,
An optical brightener such as 71 may be added in an amount of 0 to 5% by weight.

In the present invention, it is possible to add 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. Such thickeners are generally
Polyacrylic acid salt, acrylic acid maleic acid copolymer, carboxymethyl cellulose derivative, methyl cellulose,
Examples include synthetic polymers such as hydroxymethyl cellulose, natural polymers such as xanthan gum, guar gum, and kerzan, and water-swelling clay minerals such as montmorillonite and bee gum.

Further, in the present invention, various trace additives such as colorants such as dyes and pigments, fragrances, silicones, bactericides, ultraviolet absorbers, inorganic electrolytes, etc. are added in appropriate amounts (0 to 0 each).
(About 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acid solution is particularly preferable.

Further, in the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be mixed if necessary in order to improve the bleaching performance.

The pH of the liquid bleach composition of the present invention is 6 or less,
It is preferably 3.5 or less. In order 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 chelating agents and anionic surfactants in the acid form. It is advisable to add it or adjust it with a caustic alkali such as sodium hydroxide or potassium hydroxide if necessary. Further, the liquid bleach composition of the present invention comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid, and alkali metal salts thereof and alkaline earth metal salts thereof (for example, NaCl, Na ₂ SO ₄ , H ₃ PO _4, etc.) in an amount of 0 to 5% by weight.

[0052]

According to the present invention, it is possible to provide a liquid bleaching agent which has extremely excellent storage stability and does not cause decolorization of dyes.

[0053]

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

Examples 1 to 9 and Comparative Examples 1 to 3 (b) The following components (b-1) to (b-3) are shown as components.
(c-1) to (c-5) shown below as components (c),
(d) Component (d-1), (d-2) and chelating agent (e-1) shown below were used in the composition shown in Tables 1 and 2 to prepare a liquid bleaching agent and to store each. The stability, the bleaching effect and the anti-bleaching property were measured by the following methods.
The formulations shown in Tables 1 and 2 were adjusted to pH 2 with 0.5N sulfuric acid aqueous solution.

[0055]

Embedded image

[0056]

[Chemical 17]

(I) Evaluation of Storage Stability The amount of the bleach activator which forms an organic peracid in the sample was measured, and the effective bleach activator residual rate was calculated by the following formula.

[0058]

[Equation 1]

(Ii) Method for measuring bleaching performance 40 ml of the bleaching agent composition shown in Tables 1 and 2 was added to a 2 liter aqueous solution containing 0.133% commercially available 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.

* Bleaching rate of black tea-contaminated cloth

[0061]

[Equation 2]

The reflectance is NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd.
At 460 nm using a filter.

* Preparation of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled in 3 l of ion-exchanged water for about 15 minutes, rubbed with bleached cotton that had been shelved, and a cotton gold cloth # 2003 was dipped in this solution. Boiled for about 15 minutes.
It was removed from the heat as it was, left to stand for about 2 hours, naturally dried, washed with water until the washing liquid did not become colored, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used in the experiment.

(Iii) Decolorization test A naphthol dye (underpickling agent; Naphthol A) was added to a petri dish.
S, color developer; Fast Red GBase) cotton cloth (10 cm x 10)
cm). The bleaching composition shown in Tables 1-2 was added to a 2 liter aqueous solution containing 0.133% commercial detergent solution (pH = 10.2).
Add 40 ml and soak the above cotton cloth for 5 minutes each for 30 minutes,
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 bleaching at all ... ◎ ・ A little thin, but not at all ... ○ ・ Partially bleached △: ・ Decoloration spreads over the entire cloth… ×

[0065]

[Table 1]

[0066]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C11D 1:92) (C11D 10/02 3: 395 1:62) (C11D 10/02 3: 395) 1:75)

Claims (5)

[Claims] 1. A liquid bleaching composition comprising the following component (a), component (b) and component (c). Component (a): Hydrogen peroxide (b) Component: Bleach activator represented by general formula (I) [Wherein R ^{1 is an} ester bond, an amide bond, an ether bond, or The bond represented by represents a linear or branched alkyl or alkenyl group having 5 to 21 carbon atoms, which may be interrupted, or a linear or branched carbon atom having 6 to 20 carbon atoms.
Represents an aryl group which may be substituted with an alkyl group or an alkenyl group. X: or indicating a -SO ₃ M or -COOM, or -SO ₃ ^- or -COO ^- shows the. Here, M represents a hydrogen atom or an inorganic or organic cation group. ] (C) component: a surfactant represented by the general formula (II), the general formula (I
At least one selected from the group consisting of the surfactant represented by II) and the surfactant represented by the general formula (IV): [Wherein at least one of R ² , R ³ , R ⁴ : R ² group, R ³ group and R ⁴ group is a linear chain which may be interrupted by an ester bond, an amide bond or an ether bond. Alternatively, a branched chain alkyl group having 6 to 22 carbon atoms or an alkenyl group is shown, and the other group is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ⁵ : 1 to 1 carbon atoms, which may be substituted with a hydroxyl group
6 represents an alkylene group. Y ^-: -SO ₃ ^- or -COO ^- shows the. ] [Chemical 4] [In the formula, R ² , R ³ and R ⁴ are as defined above. R ⁶ : represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Z ⁻ : Indicates an inorganic or organic anion group. ] [Chemical 5] [In the formula, R ² , R ³ and R ⁴ are as defined above. ] 2. The liquid bleaching composition according to claim 1, wherein the component (c) is a surfactant represented by the general formula (II), and in the general formula (II), Y ⁻ is —SO ₃ ^—. Stuff. 3. The liquid bleaching composition according to claim 1, which further contains the component (d). Component (d): at least one selected from the group consisting of nonionic surfactants and anionic surfactants. 4. The liquid bleaching composition according to claim 3, wherein the component (c) is a surfactant represented by the general formula (III) and the component (d) is a nonionic surfactant. 5. The method according to any one of claims 1 to 4, which further comprises the component (e).
The liquid bleaching composition according to any one of 1. (e) Component: Chelating agent.