JPH0835170A - Liquid bleaching agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in storage stability without causing the decoloration of a dye by blending hydrogen peroxide with a specific bleaching activator and a surfactant as essential components at a specific weight ratio. CONSTITUTION:This liquidbleaching agent composition is obtained by blending (A) 0.3-30wt.% hydrogen peroxide with (B) 0.1-20wt.% bleaching activator, preferably represented by the formula [R<4> is a 1-24C alkyl or alkenyl which may have an amide, an ester, an ether, etc., or phenyl unsubstituted or substituted with a 1-20C alkyl or alkenyl; G is an eliminative group containing an anionic group; (p) is 0 or 1], reactive with the hydrogen peroxide and producing an organic peracid, (C) 0.01-10wt.% surfactant represented by the formula, R<1>O(AO)3 R<2> {R<1> is a 1-22C alkyl, etc, or phenyl having a substituent group; R<2> is a 1-22C alkyl, etc., or a group represented by the formula, R<3>COOM [R<3> is a 1--10C alkylene; M is H or a cation; A is a 2-3C alkylene; (n) is 1-50]} and (D) one kind selected from nonionic, anionic, cationic and amphoteric surfactants at (1/50) to (5/1) weight ratio of the components (B)/(D) and regulating the pH to <=3.5.

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, a liquid containing a bleaching activator which reacts with hydrogen peroxide and has an excellent storage stability to produce an organic peracid. Bleach composition.

[0002]

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 drawbacks, have recently become extremely popular due to their unique 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 weaker bleaching power than chlorine-based bleaching agents, and various bleaching activators are used together. Examples of these bleach activators include O-, which is represented by glucose pentaacetate (GPAC).
Examples thereof include acetylated products, N-acylated products represented by tetraacetylethylenediamine, and acid anhydrides represented by maleic anhydride. Furthermore, the inventors of the present invention have disclosed JP-A 63-233969, JP-A 63-31566, and JP-A 63-31566.
As disclosed in JP-A-64-68347 and JP-A-1-190654, a compound which reacts with hydrogen peroxide to produce an organic peracid having a quaternary ammonium group is used as a bleach activator. It was found to be extremely excellent. further,
An example of an organic peracid precursor having an anionic group is JP-B-63-12.
It is disclosed in Japanese Patent No. 520.

These bleach activators are compounds which react with hydrogen peroxide to form an organic peracid under mild conditions such as washing conditions, and are therefore generally unstable to hydrogen peroxide. For this reason, it is usually difficult to use these bleach activators as liquid bleaching agents, and as a composition comprising a mixture of solid persalts and dry particles of these bleaching activators in order to keep them dry. It is commonly 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, since the bleaching activator was dispersed in this composition, it was precipitated and separated during storage, and the use was remarkably impaired. Further, this composition has a problem that when the bleach activator is stored in an aqueous solution, it is gradually decomposed and a satisfactory bleaching power cannot be obtained at the time of use. Further, this composition had a bleaching activator dispersed therein, and the bleaching activator remained undissolved during actual bleaching, and when it adhered to the bleached substance, the dye in that part was decolorized. ..

[0006] Therefore, 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 a dye.

[0007]

[In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or represents a phenyl group substituted with the alkyl group or the alkenyl group. R ² : represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or represents a group represented by —R ³ —COOM. Here, R ³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and M is H or a cation group. A: Shows an optionally branched alkylene group having 2 to 3 carbon atoms. n: 1 to 50 is shown, and n A's may be the same or different. ]

Component (d): a group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant (excluding the surfactant represented by the general formula (I) At least one surfactant selected from the group consisting of.

The present invention will be described in detail below. [Component (b)] As the bleach activator of the component (b) used in the composition of the present invention, a compound represented by the general formula (II) is preferable.

[0009]

[Chemical 2]

[Wherein R ⁴ is a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may have an amide group, an ester group, an ether group or a quaternary ammonium group. Or an aryl group which may be substituted with an alkyl group or an alkenyl group having 1 to 20 carbon atoms. G: Indicates a leaving group containing an anionic group. p: 0 or 1 is shown. Examples of the G group in the general formula (II) include the following.

[0011]

[Chemical 3]

-OR ⁵ -SO ₃ ^- , -OR ⁵ -SO ₃ J, -OR ⁵ -OSO ₃
^— , —OR ⁵ —OSO ₃ J [In the formula, R ^{5 represents a} linear or branched alkylene group having 1 to 18 carbon atoms. J: indicates H, alkali metal (Na, K, etc.), alkaline earth metal or NH ₄ ⁺ . Examples of preferable compounds as the bleach activator represented by the general formula (II) include the following.

[0013]

[Chemical 4]

[Component (c)] As the component (c) used in the bleaching composition of the present invention, a compound represented by the above general formula (I) is used. In the general formula (I), the M group represents H 2 or a cation group, and examples of the cation group include NH ₄ ⁺ , alkali metal (Na, K, etc.) ions and the like. Examples of the compound represented by the general formula (I) are as follows.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[Component (d)] As the component (d), a nonionic surfactant other than the surfactant represented by the general formula (I), an anionic surfactant, a cationic surfactant is used. At least 1 selected from the group consisting of agents and amphoteric surfactants
Certain surfactants are used. Examples of these are alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α- Sulfo fatty acid salts or α-sulfo fatty acid esters, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, amine oxides, Examples include quaternary ammonium salts, alkyl glycosides, sulfobetaines, carbobetaines and the like.

Of these, selected from the group consisting of the surfactant represented by the general formula (III), the surfactant represented by the general formula (IV) and the surfactant represented by the general formula (V). At least one is preferred. R ¹⁰ O(QO) _m H (III) [In the formula, R ¹⁰ is a linear or branched alkyl group or alkenyl having 10 to 24 carbon atoms, which may have an amide group, an ester group, or an ether group. Represents a group or has 8 carbon atoms
An aryl group substituted with an alkyl group of -24 is shown. Q: Shows an optionally branched alkylene group having 2 to 3 carbon atoms. m: Indicates a number of 2 to 30. ]

[0019]

[Chemical 7]

[Wherein R ¹¹ represents a linear or branched alkyl or alkenyl group having 10 to 24 carbon atoms, which may have an amide group, an ester group or an ether group, or has a carbon number of 8
An aryl group substituted with an alkyl group of -24 is shown. R ¹² , R ¹³ : represents an alkyl group having 1 to 5 carbon atoms or -(Q
O) a group represented by _a H. Here, Q has the above-mentioned meaning, and a shows the number of 0-30. R ¹⁴ : Shows a linear or branched alkylene group having 1 to 10 carbon atoms, which may have an —OH group. E: indicates —SO ₃ ⁻ , −OSO ₃ ⁻ , −OPO ₃ ⁻ or −COO ⁻ . ]

[0021]

[Chemical 8]

[Wherein R ¹¹ , R ¹² , and R ¹³ are as defined above. R ¹⁵ represents a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may have an amide group, an ester group or an ether group, or -(QO) _a
A group represented by H is shown. Here, Q and a have the above-mentioned meanings. X ⁻ : Indicates an anionic group. Specific examples of these surfactants 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 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

[0024]

[Chemical 9]

[0025]

[Chemical 10]

The surfactants exemplified here may be used alone, or may be used as a mixture of two or more kinds.

[Liquid bleach composition] In the composition of the present invention, the content of the component (a) in the composition is 0.3 to 30% by weight, preferably 0.5 to 20% by weight, and the content of the component (b) is 0.1. ~20% by weight, preferably 0.1-10% by weight, more preferably 0.5
˜5% by weight, the content of the component (c) is 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, and the content of the component (d) is 0.1 to 30% by weight, Preferably
The amount is 0.5 to 20% by weight, more preferably 0.5 to 15% by weight. In this case, the weight ratio of the component (b) and the component (d) is [(b) component]/[(d) component]=1/50 to 5/1, preferably 1/20 to 2/1. It is mixed in proportion. 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, the storage stability of hydrogen peroxide itself becomes unstable, which is dangerous. If the content of the 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. If the content of the component (c) is less than 0.01% by weight, the storage stability of the component (b) tends to be poor. On the other hand, if it exceeds 10% by weight, there is a problem of recontamination of the fiber. The amount of component (d) is 0.1
When it is outside the range of up to 30% by weight, sufficient bleaching performance tends not to be obtained. When the weight ratio of the (b) component to the (d) component [(b) component]/[(d) component] is less than 1/50, sufficient bleaching performance cannot be obtained and recontamination may occur. On the other hand, when it exceeds 5/1, the storage stability of the component (b) tends to be poor.

The liquid bleaching composition of the present invention may contain known components which are usually added in addition to the above essential 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. Further, the liquid bleaching composition of the present invention can be used by mixing it with a conventionally known laundry detergent.

The liquid bleaching composition of the present invention is basically a solution or dispersion of the above components (a) to (d) in water. It is possible to add a hydrotrope agent for the purpose of improving the above or preventing liquid separation at high temperature. As such a hydrotrope, in general, toluene sulfonate,
Examples thereof include short-chain alkylbenzene sulfonates represented by xylene sulfonate, alcohols represented by ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin and the like, and polyhydric alcohols.

Further, in the present invention, a chelating agent may be added, if desired. As the chelating 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 , Oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, and other organic acids, or their alkali metal salts or alkanolamine salts (7) Alkali metal salts or alkanolamine salts of aluminosilicate represented by zeolite A (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),
At least one selected from (7) is preferable. The amount of such chelating agent is 0.0005 relative to the liquid bleach composition.
-5% by weight, preferably 0.01-1% by weight.

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 amino acids and amino acid salts such as phenylalanine, histidine, lysine, tyrosine and 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 monomers copolymerizable therewith is used. 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 increase 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], color index fluorescent whitening agents 28, 40, 61,
A fluorescent whitening agent 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. It is also possible to give viscoelastic rheological properties by combining an amphoteric surfactant and an anionic surfactant, as described in JP-A-1-319600.

Further, in the present invention, various trace additives such as colorants such as dyes and pigments, fragrances, silicones, germicides, ultraviolet absorbers, inorganic electrolytes, etc. are added in appropriate amounts (0 to 0 each).
(About 2% by weight). In addition, as the dye, an acidic dye having hydrogen peroxide resistance in an acidic solution is particularly preferable. Further, in the present invention, in order to improve the bleaching performance, conventionally known enzymes (cellulase, amylase,
Proteases, lipases, etc.) can be added as required.

The liquid bleach composition of the present invention has a pH of 6 or less,
It is desirable to set it to 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 them or adjust them 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 their alkali metal salts and their alkaline earth metal salts (for example, NaCl, Na ₂ SO ₄ , H ₃ PO _4, etc.) in an amount of 0 to 5% by weight.

[0037]

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.

[0038]

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

Examples 1 to 6 and Comparative Examples 1 to 5 Compounds (b-1) to (b-3) as components (b) and surfactants (c-1) to (c- as components (c)). 4), a surfactant (d-1) to (d-3) as a component (d), and a compound (e-1) as a chelating agent, and a liquid bleaching agent having a composition shown in Table 1 and Table 2. Was prepared, and the bleaching performance, storage stability and discoloration preventive property of each were measured by the following methods. The results are shown in Tables 1 and 2. The blending composition shown in Table 1 and Table 2 is 0.5
The pH was adjusted to 2 with an aqueous solution of N-sulfuric acid.

[0040]

[Chemical 11]

(1) Storage stability evaluation method After storing the liquid bleaching composition under the conditions shown in Tables 1 and 2, the amount of the bleaching activator which produces an organic peracid in the sample composition was determined. After measurement, the effective bleach activator residual rate was calculated by the following formula.

[0042]

[Equation 1]

(2) Method for measuring bleaching performance To a 2 liter aqueous solution containing 0.133% commercial detergent solution (pH=10.2), 40 ml of the bleaching agent composition shown in Tables 1 and 2 was added,
Each of the black tea-contaminated cloths prepared as described below was immersed in 5 pieces for 15 minutes. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. The bleaching properties of the bleaching agent composition before storage and after storage under the conditions shown in Tables 1 and 2 were measured. Bleaching rate of tea-contaminated cloth

[0044]

[Equation 2]

The reflectance is NDR-101D manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at P using a 460 nm filter.

Preparation Method of Black Tea-Contaminated Cloth 80 g of Nitto black tea (yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes, rubbed with de-squeezed bleached cotton, and then soaked in a cotton cloth #2003. Boiled for about 15 minutes. It was removed from the heat as it was, allowed to stand for about 2 hours, then naturally dried, washed with water until the washing liquid was not colored, dehydrated, pressed, and made into a test piece of 10 cm×10 cm, which was subjected to an experiment.

(3) Decolorization test Nattofur dye (under-pickling agent; Naphthol AS,
A cotton cloth (10cm×10c) dyed with a color developer; Fast Red GBase)
m) is prepared. 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), and the solution was soaked 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 ・・・ ○ ・Partly bleaching ・・・ △ ・Decolorization spreads over the entire cloth ・・・×

[0048]

[Table 1]

[0049]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takaomi Himo 1450 Nishihama, Wakayama City, Wakayama Kao Mizuken Dormitory 1234

Claims (4)

[Claims] 1. The following component (a) is 0.3 to 30% by weight, component (b) is 0.1 to 20% by weight, component (c) is 0.01 to 10% by weight, and
0.1 to 30% by weight of component (d) is contained, and the weight ratio of component (b) to component (d) is [(b) component]/[(d) component]=1/50 to 5/
1. A liquid bleaching composition which is 1. Component (a): Hydrogen peroxide (b) Component: Bleach activator that reacts with hydrogen peroxide to produce organic peracid (c) Component: Surfactant represented by general formula (I) R ¹ O (AO) _n R ² (I) [In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or phenyl substituted with the alkyl group or the alkenyl group. Indicates a group. R ² : represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or represents a group represented by —R ³ —COOM. Here, R ³ is a linear or branched carbon number 1 to
10 is an alkylene group, and M is H or a cation group. A: Shows an optionally branched alkylene group having 2 to 3 carbon atoms. n: 1 to 50 is shown, and n A's may be the same or different. Component (d): a group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant (provided that the surfactant represented by the general formula (I) is At least one surfactant selected from 2. In the general formula (I), R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ² is a linear or branched alkyl group having 1 to 10 carbon atoms. A liquid bleach composition according to claim 1. 3. In the general formula (I), R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ² is —CH ₂
The liquid bleaching composition according to claim 1, which is a group represented by COOM (where M has the above-mentioned meaning). 4. The liquid bleach composition according to claim 1, wherein the component (b) is a bleach activator represented by the general formula (II). [Chemical 1] [Wherein R ⁴ is a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may have an amide group, an ester group, an ether group or a quaternary ammonium group, or Or, it represents an aryl group which may be substituted with an alkyl group or an alkenyl group having 1 to 20 carbon atoms. G: Indicates a leaving group containing an anionic group. p: 0 or 1 is shown. ]