JP3408306B2 - 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 bleaching composition, and more particularly, a powder or liquid bleaching containing a bleaching activator which reacts with hydrogen peroxide having a cation group to produce an organic peracid. Agent 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 drawbacks, have been remarkably popular recently because they do not have a 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),
Examples thereof include N-acylated products typified by tetraacetylethylenediamine and acid anhydrides typified by maleic anhydride. Further, an example of an organic peracid precursor having an anionic group is disclosed in JP-B-63-12520. However, among these bleach activators, O-acetyl compounds, N
-Acyl compounds and the like are effective for hydrophilic stains such as stain stains of stains for which a bleaching agent is used, but show little bleaching activity for oil stains. See also
The bleaching activator having an anionic group disclosed in Japanese Patent No. 520 is effective for oily stains, but has a low effect for hydrophilic stains.

As a bleach activator effective for oily and hydrophilic stains, it has been disclosed in JP-A-61-179300.
A bleaching activator having a cationic group in the molecule such as a quaternary ammonium compound is exemplified. However, this compound has a problem that the production rate of organic peracid is slow and the bleaching time becomes long under mild conditions such as washing conditions and bleaching conditions.

Further, these bleach activators are compounds which react with hydrogen peroxide to produce 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 maintain a dry state. 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 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.

[0006] Therefore, the problem to be solved by the present invention is to produce sufficient organic peracid in a short time under mild conditions such as washing or bleaching conditions, and to show an effect on both hydrophilic stains and oil stains. Another object of the present invention is to provide a bleach composition containing a bleach activator which can be used not only as a powder bleach but also as a liquid bleach.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the use of a quaternary ammonium salt having a very selected specific structure as a bleach activator The inventors have found that the above can be achieved and completed the present invention. That is, the present invention is as follows.
It is intended to provide a bleaching composition comprising the component (a) and the component (b). Component (a): Hydrogen peroxide, or peroxide that generates hydrogen peroxide in aqueous solution (b) Component: compound represented by general formula (I)

[0008]

[Chemical 3]

[Wherein A is represented by the following formulas (A-1) to (A-4)
A group having a Taft σ ^* value of 1.0 or more, which is selected from the following groups. R ¹ COO- (A-1) (In the formula, R ¹ is a linear or branched alkyl group having 6 to 22 carbon atoms.
Represents a group or an alkenyl group, or is an alkyl group having 6 to 22 carbon atoms.
Aryl which may be substituted with a kill group or an alkenyl group
Indicates a group. ^{) R 1 OCO- (A-2} ) ( wherein, R ¹ is the the same meaning as defined) R ¹ CONR ⁷ -. In (A-3) (wherein, R ¹ has the same meaning as described above, R ⁷ is Indicates a hydrogen atom
Or a linear or branched alkyl group having 1 to 22 carbon atoms or
Represents a alkenyl group or is an alkyl group having 1 to 22 carbon atoms
The aryl group which may be substituted is shown. ) R ¹ NR ⁷ CO- (A-4) (In the formula, R ¹ and R ⁷ have the above-mentioned meanings.) R ² represents a group represented by —CH ₂ — . R ³ : Indicates an alkylene group having 1 to ³ carbon atoms. R ⁴ , R ⁵ , and R ^{6 are the} same or different and each represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. Y ⁻ : Indicates an inorganic or organic anion group. ]

The present invention will be described in detail below.

<Component (a)> As the component (a) in the composition of the present invention, hydrogen peroxide or a peroxide capable of generating hydrogen peroxide in an aqueous solution is used.
Here, examples of peroxides that generate hydrogen peroxide in an aqueous solution include sodium percarbonate and sodium perborate.

<Component (b)> The compound represented by the general formula (I) is used. Here, the A group in the compound represented by the general formula (I) is a tuft σ ^*
Indicates a group selected such that its value is 1.0 or more. Preferably, the tuft σ ^* value is 1-4. When the tuft σ ^* value is less than this range, sufficient organic peracid is not produced under mild conditions such as washing conditions, and the bleaching performance deteriorates. On the other hand, if it exceeds this range, the stability of the organic peracid is poor and decomposition occurs in a short time.

In this case, the tuft σ ^* value of the A group is "Langu's Handbook of Chemistry (Lange '
Handbook of Chemistry), 13th Edition, Section (Secti
on) 3, P3-135, and the numerical values shown in Table 3-12. When the tuft σ ^* value of a certain group B is to be obtained, it is obtained by the following formula. Tuft σ ^* = (pKa ⁰ −pKa) / ρ [wherein pKa ⁰ : acid dissociation constant of acetic acid pKa: acid dissociation constant of compound represented by B—CH ₂ COOH. Here, B represents a group for which the tuft σ ^* value is to be obtained. ρ: Reaction parameter, which is the Lange's Handbook of Chemis
try) ”13th edition, Section 3, P3-140,
0.67 is adopted from the values shown in Table 3-14. ]

Examples of the quaternary ammonium salt represented by the general formula (I) having an A group having a tuft σ ^* value of 1.0 or more are as follows.

[0015]

[Chemical 4]

[Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and Y ⁻ : have the above meanings. q: Indicates 1 . ]

[0017]

[Chemical 5]

[In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , q, and Y ^{− are as} defined above. ]

[0019]

[Chemical 6]

[Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , q,
Y ^-: The meanings of the. ]

[0021]

[Chemical 7]

[Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , q,
Y ^-: The meanings of the. ]

Among the quaternary ammonium salts, the following compounds can be exemplified as preferable ones.

[0024]

[Chemical 8]

The bleaching composition of the present invention may be used in either powder form or liquid form. Each will be described below.

<Powder bleach composition> In the powder bleach composition of the present invention, the component (a) is
A peroxide that generates hydrogen peroxide in an aqueous solution is used, and examples thereof include sodium percarbonate or sodium perborate. The weight ratio of component (a) and component (b) is (a) /
(b) = 100/1 to 1/5 is preferable, and 50 is more preferable.
It is / 1-1 / 1.

Further, it is preferable to add a chelating agent as the component (c). Examples of such chelating agents include (1) phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, and phytic acid or their alkali metal salts or alkanolamine salts (2) ethane-1,1 -Diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-diphosphonic acid Carboxy-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 -Phosphoric acid such as tricarboxylic acid and α-methylphosphonosuccinic acid, or their alkali metal salts or alkanolamines Salts (4) Amino acids such as aspartic acid, glutamic acid, glycine or their alkali metal salts or alkanolamine salts (5) Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyl Iminodiacetic 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, carboxymethylsuccinic acid and carboxymethyltartaric acid, or 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.

Of these, preferred chelating agents are the above.
It is at least one selected from the group consisting of (2), (5), (6) and (7). The amount of such a chelating agent added to the composition is 0.0005 to 5% by weight, preferably 0.01 to 1% by weight.

Further, a surfactant may be added to the powder bleaching composition of the present invention. As the surfactant, (a) a surfactant having at least one straight-chain or branched-chain C8-24 alkyl group or alkenyl group (b) an aryl group substituted with a C8-24 alkyl group A surfactant having at least one is preferably used.

Examples of these surfactants include 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 alkyl phenyl ethers, higher fatty acid alkanolamides, or alkylene oxide adducts thereof, Examples thereof include sugar fatty acid esters, amine oxides, alkyl glycosides, sulfobetaines, and carbobetaines. In this case, the compounding amount of the surfactant is 0 to 20% by weight in the composition. Further, an alkaline agent such as sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide may be added to the powder bleaching composition of the present invention.

Further, the powder bleaching composition of the present invention may contain a substance known as a discoloration preventing agent. Examples of 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, and acrylonitrile and a fourth compound.
A copolymer of acrylonitrile having a primary ammonium group and one or more 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 improve the bleaching effect on white fiber, Tinopal C is used as a fluorescent whitening agent.
Optical brighteners such as BS [Ciba-Geigy], Tinopal SWN [Ciba-Geigy] and color index optical brighteners 28, 40, 61, 71 May be added to the composition in an amount of 0 to 5% by weight.

In the powder bleach composition of the present invention,
Various amounts of trace additives such as colorants such as dyes and pigments, fragrances, silicones, bactericides, ultraviolet absorbers and inorganic electrolytes can be added in appropriate amounts (about 0 to about 2% by weight each). Further, in the composition of the present invention, in order to improve the bleaching performance, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be added as necessary. The powder bleaching composition of the present invention can be obtained by powder-mixing the above-mentioned components with a super mixer or the like.

<Liquid bleach composition> In the liquid bleach composition of the present invention, the component (a) is
Hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution (sodium percarbonate, sodium perborate, etc.) is used. In this case, the compounding amount of component (a) is 0.5 in the composition.
-20% by weight is preferable, and 1-10% by weight is more preferable. In the liquid bleach composition of the present invention, the above (b)
Components are used, and the mixing ratio of the components (a) and (b) is preferably (a) / (b) = 100/1 to 1/1, and more preferably 50/1 to It is 1/1.

In the liquid bleach composition of the present invention,
It is preferable to add a chelating agent as the component (c) and an anionic surfactant and / or a nonionic surfactant as the component (d). In this case, as the chelating agent, those of the kind and the compounding amount described in the above section <Powder bleaching composition> are adopted.

The surfactant as the component (d) includes, for example, 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 addition thereof At least one selected from the group consisting of a product, sucrose fatty acid esters, amine oxides, and alkyl glycosides is used. Among these surfactants, they are selected from the group consisting of anionic surfactants represented by the following general formula (II) or (III) and nonionic surfactants represented by the general formula (IV) or (V). At least one is preferable.

[0037]

[Chemical 9]

[In the formula, R ^{8 is a} linear or branched carbon number of 6 to
22 represents an alkyl group or an alkenyl group. M: Indicates an inorganic or organic cation group. ] _{^{R 8 -O- (BO) p -Z}} (III) wherein, R ^8: The meanings of the. B: Shows an alkylene group having 2 to 3 carbon atoms. p: Indicates a number from 0 to 20. Z: represents a group represented by —SO ₃ M or —CH ₂ COOM. Where M
Indicates the above meaning. ] R ⁸ -O- (BO) in _p -H (IV) [wherein, R ^8, B, p: The meanings of the. R ⁹ COO- (BO) _p -H (V) [In the formula, R ^{9 represents a} linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, or alkyl having 6 to 22 carbon atoms] Represents an aryl group which may be substituted with a group or an alkenyl group. B, p: Indicates the above meaning. ]

The component (d) is in a weight ratio with the component (b).
(d) / (b) is 50/1 to 1/5, preferably 20/1 to 1 /
It is used in a ratio such that it becomes 1. In this case, sulfobetaine and / or carbobetaine, which is an amphoteric surfactant, is used as a surfactant other than the component (d) in an amount of 0 to 10% by weight in the composition.
It can be blended.

If desired, a dispersant and a hydrotrope agent may be added to the liquid bleaching composition of the present invention. Examples of these include toluene sulfonate, xylene sulfonate, ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin and the like. These hydrotropes can be incorporated in the bleaching composition 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, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, which are known as stabilizers of hydrogen peroxide, and DL-α-tocopherol, gallic acid derivatives, butylated hydroxy Anisole (BHA), 2,6-di-tert
-Butyl-4-methylphenol (BHT) and the like can be added. The amount of these stabilizers added to the liquid bleaching composition is about 0 to 5% by weight, preferably 0.01 to 3%.
It is preferable to contain it by weight%.

In the liquid bleach composition of the present invention, a thickener may be added 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 typically include polyacrylates,
Examples thereof include acrylic acid-maleic acid copolymers, carboxymethylcellulose derivatives, synthetic polymers such as methylcellulose and hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum and kerzan, and water-swelling clay minerals such as montmorillonite and bee gum. Further, as described in JP-A-1-319600,
By combining an amphoteric surfactant and an anionic surfactant, it is possible to impart viscoelastic rheological properties.

Further, in the liquid bleaching composition of the present invention, the discoloration preventing agent, the fluorescent whitening agent, the coloring agent, the fragrance, the silicones, the bactericidal agent, the ultraviolet absorbing agent described in the above section <Powder bleaching composition>. An appropriate amount of inorganic electrolyte (each of which is about 0 to about 2% by weight) can be added. Also, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be added as necessary.

The liquid bleaching composition of the present invention can be obtained by dissolving or solubilizing the above-mentioned components in tap water or ion-exchanged water. The liquid bleach composition thus obtained has a high transparency and a wavelength of 420 nm at an optical path length of 1 cm.
Has a light transmittance of 80% or more.

However, hydrogen peroxide [component (a)]
In general, since the stability to light is poor, an opaque agent may be added in the present invention. The opacifying agent is not particularly limited, but a partial ester of a polyhydric alcohol (for example, glycerin, polyglycerin, sorbitol, pentaerythritol, glucose, fructose, maltose, sucrose, etc.) and a fatty acid having 12 to 24 carbon atoms, and / or A polymer emulsion (for example, a polymer emulsion obtained by polymerizing or copolymerizing a monomer selected from the group consisting of vinyl acetate, styrene, vinyl chloride, allyl chloride, ethylene, propylene and acrylonitrile) is preferable. The amount of such opacifying agent added is 0 to 10% by weight in the composition. Liquid bleach composition of the present invention
The pH is preferably adjusted to be neutral or weakly acidic to acidic (pH 6 or less, preferably 3.5 or less).

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, sufficient organic peracid can be produced in a short time under mild conditions such as washing or bleaching conditions, and it is effective against both hydrophilic stains and oil stains. It is possible to provide a bleaching agent composition containing a bleaching activator which can also be used for a liquid bleaching agent. In the case of a liquid bleach composition, excellent storage stability is also obtained.

[0047]

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.

Synthesis Example 1 Synthesis of compound (b-1)

[0049]

[Chemical 10]

267.4 g (3.0 mol) of dimethylaminoethanol and 54 methyl glycolate were placed in a 1 liter four-necked flask equipped with a dehydration tube, a thermometer and a mechanical stirrer.
g (0.6 mol) and 0.5 g of sodium methylate were charged, and the temperature was raised to 90 ° C. After reacting for about 2 hours, sodium methylate and an equivalent amount of sulfuric acid were added, and excess dimethylaminoethanol and methanol produced by the reaction were distilled off by an evaporator. By distilling this product, 56 g of dimethylaminoethanol glycolate was obtained (yield: 63.3%). Next, 50 g (0.34 mol) of glycolic acid dimethylaminoethanol ester and 67.9 g of lauric acid.
(0.34 mol) and 0.1 g of sulfuric acid were charged into a 0.3 liter three-necked flask equipped with a thermometer, a mechanical stirrer, and a dehydration tube, and the temperature was raised to 150 ° C. The reaction was carried out for about 8 hours while distilling off the produced water of reaction. After neutralization with sulfuric acid and an equivalent amount of sodium hydroxide, a reaction product, 100 g of isopropanol, was charged into a 0.5 liter autoclave. 17.2 g of methyl chloride was added and reacted at 90 ° C. for about 3 hours. 132 g of compound (b-1) was obtained by distilling off isopropanol under reduced pressure with an evaporator. Yield 72
%, Purity 70.5%. The tuft σ ^* value of C ₁₁ H ₂₃ COO- group is 2.
Was 10.

Synthesis Example 2 Synthesis of compound (b-2)

[0052]

[Chemical 11]

Cooling pipe, introduction pipe, mechanical stirrer,
A 2 liter, 5-necked flask equipped with a pH meter and a dropping funnel was charged with 75.1 g (1.0 mol) of glycine, 40 g (1.0 mol) of sodium hydroxide and 500 g of ion-exchanged water, and 218.8 g of lauric chloride was added from the dropping funnel with stirring. 1.0 mol) was added dropwise. A 10% aqueous sodium hydroxide solution was added from an introduction tube while controlling the pH in the reaction system to 10 to 10.5. After dripping the acid chloride and aging for 1 hour, the pH in the system was lowered to 3 with a 35% HCl aqueous solution, and white crystals were precipitated. The crystals were collected by filtration and washed with ion-exchanged water several times to give lauroylglycine at 216.2
g was obtained (yield 84%). Then lauroyl glycine 87.5g
(0.34 mol), dimethylaminoethanol 60.6 g (0.68
Mol) and 0.1 g of sulfuric acid were charged into a 0.3-liter three-necked flask equipped with a dehydration tube, a thermometer, and a mechanical stirrer, and the temperature was raised to 150 ° C. The produced water of reaction was distilled off from the dehydration tube and reacted for about 8 hours. Then, it was neutralized with sulfuric acid and an equivalent amount of sodium hydroxide, and excess dimethylaminoethanol was distilled off under reduced pressure with an evaporator. Next, put the reaction product, isopropanol in a 0.5 liter autoclave.
I charged 100g. Add 17.2 g of methyl chloride, and add 9
The reaction was carried out at 0 ° C for about 3 hours. Compound (b-2) was obtained by distilling isopropanol under reduced pressure with an evaporator.
120 g was obtained. Yield 80%, Purity 74.4%. In addition, C ₁₁ H ₂₃ CONH-
The base tuft σ ^* value was 1.50.

Synthesis Example 3 Synthesis of compound (b-3)

[0055]

[Chemical 12]

A 1 liter three-necked flask equipped with a cooling tube, a thermometer and a mechanical stirrer was charged with 150 g (1.14 mol) of dimethyl malonate, 35.9 g (0.23 mol) of decylamine and 0.1 g of sodium methylate and heated to 90 ° C. did. After reacting for 2 hours, the mixture was neutralized with sodium methylate and an equivalent amount of sulfuric acid, and excess dimethyl malonate was distilled off under reduced pressure. Malonic acid monoamide ester obtained by distillation 46.3
g (0.18 mol) and dimethylaminoethanol 80.2 g (0.9
Mol) and sodium methylate 0.1 g 0.3 liter with a cooling tube, thermometer and mechanical stirrer attached 3
It was charged in a single-necked flask and heated to 90 ° C. After reacting for 2 hours, the mixture was neutralized with sodium methylate and an equivalent amount of sulfuric acid, and excess dimethylaminoethanol was distilled off under reduced pressure with an evaporator. Then, a reaction product, 100 g of isopropanol, was charged into a 0.5 liter autoclave. Methyl chloride 1
0.0 g was added and reacted at 90 ° C. for about 3 hours. 41 g of compound (b-3) was obtained by distilling off isopropanol under reduced pressure with an evaporator. Yield 43%, Purity 89.0%.
The tuft σ ^* value of the C ₁₀ H ₂₁ NHCO- group was 1.48.

Synthesis Example 4 Synthesis of compound (b- 4 )

[0058]

[Chemical 13]

The compound (b- 4 ) was synthesized by the method described in JP-A-61-179330. The tuft σ ^* value of the C ₁₀ H ₂₁ − group was −0.19.

Synthesis Example 5 Synthesis of compound (b- 5 )

[0061]

[Chemical 14]

Sodium laurate 50 g (0.23 mol), sodium bromobutyrate 43.4 g (0.23 mol) and octanol 500
1 g of liter was placed in a 4-necked flask and reacted at 100 ° C. for 3 hours. The reaction was cooled and placed in a 5 liter separatory funnel, 2 liters of water was added, and the pH was adjusted to 2.0 with 35% HCl aqueous solution.
Lowered. This liquid was extracted several times with hexane, and the hexane layer was distilled off under reduced pressure to obtain 76 g of a white solid. By distilling this, 52 g of lauroyloxybutyric acid was obtained. Dehydration esterification of this ester with dimethylaminoethanol,
Subsequently performed quaternized by dimethyl sulfate, compound (b-
5 ) was synthesized .

Examples 1 to 6 and Comparative Examples 1 to 4 [powder bleach composition] (a) Sodium percarbonate or sodium perborate as a component, (b)
Compounds (b-1) to (b- 3 ) as components, and formula as component (c)

[0064]

[Chemical 15]

A powder bleaching agent having the composition shown in Table 1 was prepared using the chelating agent (c-1) represented by and sodium carbonate as the alkaline agent. TAED as a bleach activator
(Tetraacetylethylenediamine), Compound (b-
4 ), a powder bleaching agent for comparison was prepared using the compound (b- 5 ). The bleaching performance and the peracid generation rate of the obtained powder bleaching agent were measured by the following methods, and the results are shown in Table 1.

<Method of measuring bleaching performance> 40 ml of the bleaching agent composition was added to a 2 liter aqueous solution containing 0.133% commercially available detergent solution (pH = 10.2), and 5 pieces of black tea-contaminated cloths prepared as described below were used 15 times each. Let it soak for a minute. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. Bleaching rate of tea-contaminated cloth

[0067]

[Equation 1]

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 80g of Nitto black tea (yellow package) is boiled in 3 liters of ion-exchanged water for about 15 minutes, and then rubbed with de-squeezed cotton, soaking the cotton cloth # 2003 in this liquid for about 15 minutes. Boiled. 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 became colorless, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used in the experiment.

<Measurement Method of Peracid Generation Rate> 5 g of the bleaching agent composition was placed in a 1 liter beaker, 1 liter of deionized water was added, and the mixture was dissolved for 10 minutes or 30 minutes while stirring with a magnetic stirrer. After that, 10 ml of 10% sulfuric acid aqueous solution and 10 ml of 10% KI aqueous solution were added, and effective oxygen was measured with 0.1 N hypo. The peracid production rate was calculated by the following formula.

[0070]

[Equation 2]

[0071]

[Table 1]

Examples 7 to 12 and Comparative Examples 5 to 7 [Liquid bleach composition] Hydrogen peroxide as component (a) and compound (b) as component (b).
-1) to (b- 3 ), the formula as the component (c)

[0073]

[Chemical 16]

The chelating agent (c-2) represented by the formula (d) and the surfactants (d-1) to (d) represented by the following formulas as the component (d):
-4) C ₁₂ H ₂₅ -O (C ₂ H ₄ O) ₁₀ -H (d-1) C ₁₈ H ₃₇ -O (C ₂ H ₄ O) ₂₀ -H (d-2)

[0075]

[Chemical 17]

C ₁₂ H ₂₅ —O (C ₂ H ₄ O) ₁₀ —SO ₃ Na (d-4) was used and dissolved in ion-exchanged water to obtain a liquid having the composition shown in Tables 2 and 3. Bleach was prepared. Further, a comparative liquid bleaching agent was prepared using TAED, compound (b- 4 ) and compound (b- 5 ) as the bleaching activator. The bleaching performance of the obtained liquid bleach before storage and after storage under the conditions shown in Tables 2 and 3 was measured by the above method, and the storage stability was measured by the following method. The results are shown in Tables 2 and 3.
Shown in.

The light transmittance of the product of the present invention was 1% and the transmittance of light having a wavelength of 420 nm was 80% in all cases without the opacifying agent.
It was above (measuring equipment: Hitachi Ltd. F-4010 spectrofluorimeter).

<Evaluation Method of Storage Stability> The amount of the bleach activator which produces an organic peracid in a sample after storage under the conditions shown in Tables 2 and 3 was measured, and effective bleach activation was performed by the following formula. The agent residual rate was calculated.

[0079]

[Equation 3]

[0080]

[Table 2]

[0081]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C11D 7:32) (56) Reference JP-A-5-255697 (JP, A) JP-A-6-136391 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 3/395 C11D 7/00 D06L 3/02 JICST file (JOIS) Patent file (PATOLIS) REGISTRY (STN) CAPLUS (STN)

Claims (7)

(57) [Claims] 1. A bleaching composition comprising the following component (a) and component (b). Component (a): Hydrogen peroxide or peroxide that generates hydrogen peroxide in an aqueous solution (b) Component: Compound represented by the general formula (I) [Wherein A: selected from groups represented by the following formulas (A-1) to (A-4):
Taft (Taft) sigma ^* value indicates 1.0 or more groups. R ¹ COO- (A-1) (In the formula, R ¹ is a linear or branched alkyl group having 6 to 22 carbon atoms.
Represents a group or an alkenyl group, or is an alkyl group having 6 to 22 carbon atoms.
Aryl which may be substituted with a kill group or an alkenyl group
Indicates a group. ^{) R 1 OCO- (A-2} ) ( wherein, R ¹ is the the same meaning as defined) R ¹ CONR ⁷ -. In (A-3) (wherein, R ¹ has the same meaning as described above, R ⁷ is Indicates a hydrogen atom
Or a linear or branched alkyl group having 1 to 22 carbon atoms or
Represents a alkenyl group or is an alkyl group having 1 to 22 carbon atoms
The aryl group which may be substituted is shown. ) R ¹ NR ⁷ CO- (A-4) (In the formula, R ¹ and R ⁷ have the above-mentioned meanings.) R ² represents a group represented by —CH ₂ — . R ³ : Indicates an alkylene group having 1 to ³ carbon atoms. R ⁴ , R ⁵ , and R ^{6 are the} same or different and each represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. Y ⁻ : Indicates an inorganic or organic anion group. ] Wherein further (c) bleach composition according to claim 1, further comprising a chelating agent as a component. 3. The bleaching composition is a powder, or
2 bleach composition. 4. The bleaching composition is liquid, or
2 bleach composition. 5. The bleaching composition according to claim 4, which further contains an anionic surfactant and / or a nonionic surfactant as the component (d). 6. An anionic surfactant is a compound represented by the general formula (II) or a compound represented by the general formula (III),
The bleaching composition according to claim 5 , wherein the nonionic surfactant is a compound represented by the general formula (IV) or a compound represented by the general formula (V), or a mixture thereof. [Chemical 2] [In the formula, R ^{8 represents a} linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms. M: Indicates an inorganic or organic cation group. ] _{^{R 8 -O- (BO) p -Z}} (III) wherein, R ^8: The meanings of the. B: Shows an alkylene group having 2 to 3 carbon atoms. p: Indicates a number from 0 to 20. Z: represents a group represented by —SO ₃ M or —CH ₂ COOM. Where M
Indicates the above meaning. ] R ⁸ -O- (BO) in _p -H (IV) [wherein, R ^8, B, p: The meanings of the. R ⁹ COO- (BO) _p -H (V) [In the formula, R ^{9 represents a} linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, or alkyl having 6 to 22 carbon atoms] Represents an aryl group which may be substituted with a group or an alkenyl group. B, p: Indicates the above meaning. ] 7. The bleaching composition according to claim 4 , which has a transmittance of light having a wavelength of 420 nm of 80% or more in an optical path length of 1 cm.