JPH05171192A - Bleaching agent and bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a specific peroxide, a specified bleaching activator and a specific surfactant in a specified proportion and capable of exhibiting excellent bleaching power for stains or foulings containing a metal and useful for clothes, etc. CONSTITUTION:The objective composition containing (A) 1-90wt.% hydrogen peroxide or a peroxide such as sodium carbonate.hydrogen peroxide adduct capable of generating the hydrogen peroxide in an aqueous solution, (B) 0.1-50wt.% bleaching activator, reactive with the hydrogen peroxide and producing an organic peracid and (C) 0.5-60wt.% dianionic type surfactant such as a malonic acid type surfactant expressed by the formula [R is 6-30C alkyl or alkenyl; X is H, 6-30C alkyl, alkenyl, hydroxyl Group, etc.; M1 and M2 are H, alkaline (earth) metal, transition metal of the third period, ammonia, etc.; (n1) and (n2) are the number of charges in cations of M1 and M2] and having 2 anionic polar groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an excellent bleaching (cleaning) power,
In particular, the present invention relates to a bleaching agent and a bleaching detergent composition which exhibit excellent bleaching (cleaning) power against stains and stains containing metals.

[0002]

2. Description of the Related Art Chlorine bleaching agents are limited in the fibers that can be used, cannot be used in colors and patterns, and have a unique odor. Oxygen-based bleaching agents, which do not have the above-mentioned drawbacks, have recently become extremely popular. As the oxygen-based bleaching agent, sodium percarbonate and sodium perborate are particularly used in view of bleaching performance and stability.

The oxygen-based bleaching agent has a weaker bleaching power than the chlorine-based bleaching agent, and various bleaching activators are used together. This bleach activator is represented by nitriles such as acetonitrile and glucose pentaacetate (GPAC).
O-acetylated product, tetraacetylethylenediamine (T
Examples thereof include N-acylated compounds represented by AED) and acid anhydrides represented by maleic anhydride. Further, as a result of the research conducted by the present inventors, JP-A-63-233969, JP-A-63-
315666, JP 64-68347, JP 1-19
No. 4 by reacting with hydrogen peroxide as exemplified in No. 0654
It has been found that compounds which produce organic peracids having a quaternary ammonium group are very good as bleach activators.

However, the organic peracid produced from the bleach activator as described above is rapidly decomposed in the presence of heavy metals, and therefore various chelating agents are added to stabilize the organic peracid. For example, JP-A-53-31871 and JP-A-54-
74287, Japanese Patent Laid-Open No. 55-142100, Japanese Patent Publication No. 56-21
799, Japanese Patent Publication No. 58-51998, Japanese Patent Publication No. 59-2359
No. 6, etc. include aminopolycarboxylic acid salts, triazole compounds, imidazole compounds, amino acid salts, di (tri) peptides, (hydroxyethyl) iminodiacetic acid salts,
Chelating agents such as hydroxyethyl ethylene diamino triacetate have been disclosed. Further, JP-A-52-103386 discloses a bleaching stabilizer composed of sodium poly-α-hydroxyacrylate (PHAS) having very excellent performance. However, while the above stabilizers are effective against metals in solution, they are not effective against metals present in clothing as part of stains and stains. Therefore, the organic peracid is decomposed by the metal on the clothes, and the excellent performance cannot be obtained.

[0005]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have improved the bleaching (cleaning) power by using a chelating agent having a hydrophobic group in the molecular structure in combination. The inventors have found that a bleaching agent and a bleaching detergent composition can be obtained, and completed the present invention.

That is, the present invention relates to (a) hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution 1 to 90% by weight (b) bleaching which reacts with hydrogen peroxide to produce an organic peracid Activator 0.1 to 50% by weight (c) A bleaching agent and a bleaching detergent composition containing 0.5 to 60% by weight of a dianion type surfactant having two anionic polar groups are provided.

As the peroxide which generates hydrogen peroxide in the aqueous solution which is the component (a) of the present invention, sodium carbonate / hydrogen peroxide adduct, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / Hydrogen peroxide adduct,
Examples thereof include urea / hydrogen peroxide adduct, 4Na ₂ SO ₄ 2H ₂ O ₂ .NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide and the like. Of these, sodium carbonate / hydrogen peroxide adduct is particularly preferable. The component (a) is contained in the composition in an amount of 1 to 90% by weight, but in a bleaching system, it is 50 to 90% by weight, particularly 50 to 80% by weight, and in a bleaching detergent system, 3 to 30% by weight, particularly 10 to 20% by weight is preferable.

The bleaching activator (b) which reacts with hydrogen peroxide to produce an organic peracid used in the present invention includes glucose pentaacetate (GPAC), tetraacetylethylenediamine (TAED) and nonanoyloxybenzene. Typical examples are sodium sulfonate (NOBS) and the like. As the bleach activator, those that generate an organic peracid having a quaternary ammonium group are particularly preferable, and examples thereof include those having the following structures.

[0009]

[Chemical 12]

A, b is a = 0, b = 0, or a =
1, b = 1. R ₂ and R ₃ are alkyl groups having 1 to 2 carbon atoms. The linking group is not particularly limited, for example, a linear or branched alkylene group, a cycloalkylene group,
Examples thereof include a phenylene group, an alkylenephenylene group, an oxyalkylene group (-CH ₂ CH ₂ O-) and the like. Further, the leaving group is not particularly limited, for example,

[0011]

[Chemical 13]

[0012]

[Chemical 14]

In the above general formula (I), the linking group is -C _p H
_2p- (p is 1 to 12, particularly preferably 1 to 5) and the leaving group is (a), (b), (c), (d), (f), (to), (wa), (F),
(Yo), (ta), represented by the structural formula of (re), R ₅ is a C ₁ -C ₂ alkyl group, R ₆ , R ₇ is H or a C ₁ -C ₂ alkyl group, R ₈ is C ₁
To C ₂ alkyl group and R ₉ is a C _{1 to} C ₃ alkylene group are desirable, and compounds represented by the structural formulas (yo) and (ta) are particularly desirable.

Further, a nitrile compound represented by the following general formula (II) is also useful.

[0015]

[Chemical 15]

Among these bleach activators, those particularly desirable are those represented by the following formulas.

[0017]

[Chemical 16]

[Wherein R ₁ and m are the same as defined above, and p is 1 to
The integer of 10 and the leaving group are groups represented by the above (yo) and (ta). In the present invention, the peroxide (a) and the bleaching activator (b) are (a) / (b) in a weight ratio of 100/1 to 1/20, preferably 50/1 to 1/1. Used in.

Further, the dianionic surfactant having two anionic polar groups (c) of the component (c) of the present invention is 0.5 to 60% by weight, preferably 1 to 20% by weight, particularly preferably in the composition. Is blended in an amount of 1 to 10% by weight. 2 anionic polar groups
It is preferable to use a dicarboxylic acid-type surfactant as the dianion-type surfactant to have, and those having a suitable structure as the dicarboxylic acid-type surfactant are shown below.

[0020]

[Chemical 17]

(Wherein R represents a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms. X represents H or a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms. , A hydroxyl group, or an ethylene oxide group having an addition mole number of 1 to 10 moles, and M ₁ and M ₂ represent H, an alkali metal, an alkaline earth metal, a third period transition metal, ammonia, amines or alkanolamines. (Here, M ₁ and M ₂ may be the same or a combination of different cations. N ₁ and n ₂ are equal to the number of charges in the cations of M ₁ and M ₂ , respectively.)

[0022]

[Chemical 18]

(In the formula, R and M ₁ , M ₂ , n ₁ and n ₂ are the same as above.)

[0024]

[Chemical 19]

(Wherein R and M ₁ , M ₂ , n ₁ , n ₂ are the same as above, and m represents an integer value from 2 to 4), malonic acid, succinic acid , Glutaric acid, adipic acid, and pimelic acid type surfactants. The basic skeleton of this compound group can be constructed by various existing methods such as an ionic addition reaction of a corresponding divalent organic acid ester and an alkyl halide under basic conditions.

In addition,

[0027]

[Chemical 20]

(In the formula, R ₁ represents H or a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, and R, M ₁ , M ₂ , n ₁ and n ₂ are the same as above. It is.)

[0029]

[Chemical 21]

Examples thereof include aspartic acid type, malic acid ether type, malic acid ester, tartaric acid ether type, and tartaric acid ester type surfactants. Compound
The basic skeleton of (4) and (6) can be constructed by addition reaction of the corresponding amine or alcohol to maleic anhydride. Further, the compound (8) can be constructed by O-etherification of tartaric acid, and the compounds (7) and (9) can be constructed by an acylation reaction of maleic anhydride or tartaric acid.

In addition,

[0032]

[Chemical formula 22]

(In the formula, R ₁ represents H or a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms. R, M ₁ ,
M ₂ , n ₁ and n ₂ are the same as above. ) A citric acid monoester-type or citric acid monoamide-type surfactant represented by Compounds (10) and (11) are obtained by the esterification reaction of citric acid and the corresponding alcohol,
Often given as a mixture. Also, (12), (13)
Is often provided as a mixture by treating the citric acid anhydride formed after stirring the citric acid in acetic anhydride with the corresponding amine.

In addition,

[0035]

[Chemical formula 23]

An iminodiacetic acid type surfactant represented by the formula (wherein R, M ₁ , M ₂ , n ₁ and n ₂ are the same as above) can be mentioned. This compound (14) is synthesized by nucleophilic substitution reaction with the corresponding amine and 2 equivalents of ethyl halide acetate under basic conditions.

In addition,

[0038]

[Chemical formula 24]

(In the formula, R ₂ represents a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms, and R ₃ and R ₄ are H or linear or branched chain having 1 to 30 carbon atoms. An alkyl group or an alkenyl group, wherein R, M ₁ , M ₂ , n ₁ and n ₂ are the same as the above), and an ethylenediamine diester type or ethylenediamine diamide type surfactant represented by The present compounds (15) and (16) are provided by treating ethylenediaminetetraacetic acid obtained by treating ethylenediaminetetraacetic acid in a mixed solvent of acetic anhydride and pyridine with a corresponding alcohol and amine.

In addition,

[0041]

[Chemical 25]

(Wherein R, R ₁ , M ₁ , M ₂ , n ₁ , n ₂ are the same as above), an α-sulfosodium benzene or sulfosuccinic acid monoester type surfactant is used. Can be mentioned. Compounds (17) to (20) are provided by adding a corresponding alcohol or amine to maleic anhydride to form maleic acid monoester and maleic acid monoamide, and then sulfonation with Na ₂ SO ₃ . .. At this time, compounds (13) and (15), (14) and (16) are provided as a mixture thereof.

Further, a specifically preferred dianion type surfactant is a malonate having an alkyl chain length of C _{8 to} C ₁₈ , more preferably C ₁₄ malonic acid · 2Na salt and C ₁₄ malonic acid · 2 mono. Ethanolamine salt, C ₁₄ malonic acid / Zn
Salt, C ₁₂ malonate · 2Na salt, C ₁₂ malonic acid 2 monoethanolamine salt, C ₁₆ malonic acid 2 monoethanolamine salt, C ₁₀ malonic acid 2 monoethanolamine salt; alkyl chain length C ₈ -C A glutarate having ₁₈ , more preferably a C ₁₄ glutaric acid / 2Na salt, a C ₁₄ glutaric acid / 2 monoethanolamine salt, a C ₁₂ glutaric acid / 2Na salt, a C ₁₂ glutaric acid / 2 monoethanolamine salt; an alkyl chain Length C ₈ ~
Single-chain alkyl aspartate having C ₁₈ , more preferably C ₁₄ aspartic acid · 2Na salt, C ₁₄ aspartic acid · 2 monoethanolamine salt, C ₁₂ aspartic acid ·
2Na salt, C ₁₂ aspartic acid / 2 monoethanolamine salt; O-alkyl malate and malate ester salt having an alkyl chain length of C _{8 to} C ₁₈ , and more preferably C ₁₄ -O.
- alkyl malate · 2Na salt, C ₁₂ -O - alkyl malate · 2Na salt, C ₁₃ malic acid ester 2 monoethanolamine salt, C ₁₁ malic acid ester 2 monoethanolamine salts, C ₉ malic acid ester 2 monoethanolamine salt; citric acid monoester salt having alkyl chain length C _{8 to} C ₁₈ , more preferably C ₁₄ citric acid monoester. 2
Monoethanolamine salt, C ₁₆ citric acid monoester
2 monoethanolamine salt, C ₁₂ citric acid monoester, 2 monoethanolamine acid; citric acid monoamide salt having one or two alkyl chain lengths C _{4 to} C ₁₈ , more preferably N, N-diC ₈ Citric acid monoamide 2Na salt, N, N-
Di-C ₈ citric acid monoamide-2 monoethanolamine salt;
Iminodiacetic acid-type surfactants having an alkyl chain length C ₈ -C _18, more preferably C ₁₄ iminodiacetic acid · 2Na salt, C ₁₂ iminodiacetic acid · 2Na salt; alkyl chain length C ₄ -C ₁₈ a 2 inborn to ethylenediamine diester salt and ethylenediamine amide salt, more preferably, di-C ₁₂ diamine diester · 2Na salt, di C ₁₀ diamine diester · 2Na salt, di C ₈ ethylenediamine diester · 2Na
Salt, di-C ₁₂ ethylenediamine diamide 2Na salt, di-C ₁₀
Ethylenediamine amide · 2Na salt, di C ₈ ethylenediamine amide · 2Na salt; single-chain sulfosuccinic acid monoester salts having an alkyl chain length C ₈ -C _18, more preferably,
C ₁₆ sulfosuccinic acid monoester-2Na salt, C ₁₆ sulfosuccinic acid monoester-2 monoethanolamine salt, C
₁₄ Sulfosuccinic acid monoester-2Na salt, C ₁₄ Sulfosuccinic acid monoester-2 monoethanolamine salt, C
₁₂ Sulfosuccinic acid monoester, 2Na salt, C ₁₂ Sulfosuccinic acid monoester, 2 monoethanolamine salt, C
₁₆ sulfosuccinic acid monoamide, 2Na salt, C ₁₆ sulfosuccinic acid monoamide, 2 monoethanolamine salt, C ₁₄ sulfosuccinic acid monoamide, 2Na salt, C ₁₄ sulfosuccinic acid monoamide, 2 monoethanolamine salt, C ₁₂ sulfosuccinic acid monoamide, 2Na salt, Examples thereof include C ₁₂ sulfosuccinic acid monoamide and 2 monoethanolamine salts.

The bleaching agent and the bleaching detergent composition of the present invention further have the following general formula

[0045]

[Chemical formula 26]

(Wherein R ′ is H or OH, and R ″ is H or COOH).
It is preferable to add from 00 to 200,000, preferably from 200,000 to 100,000 of a water-soluble polymer. Further, the compounding amount in the composition is preferably 0.3 to 5% by weight. Specific examples of such water-soluble polymer include polyacrylic acid, poly-α-hydroxyacrylic acid, polymaleic acid, maleic anhydride-ethylene copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-butylene. Copolymers, maleic anhydride-styrene copolymers, maleic anhydride-methyl vinyl ether copolymers, maleic anhydride-acrylic acid copolymers, hydrolysates of these copolymers, acrylic acid-acrylamide copolymers and These salts (sodium salt, potassium salt, ammonium salt, etc.) and the like can be mentioned.

The bleaching agent and bleaching detergent composition of the present invention are
In addition to the above-mentioned components, known components usually added to a bleaching agent or a bleaching detergent composition can be added. For example, as a builder, sulfate, carbonate, bicarbonate, silicate,
In addition to water-soluble inorganic builders such as phosphates and water-insoluble inorganic builders such as zeolites, organic builders such as ethylenediaminetetraacetate, nitrilotriacetic acid salts, tartrate salts, and citrate salts can be used. Also known magnesium sulfate as a stabilizer of peroxide or hydrogen peroxide adduct,
Magnesium salts such as magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium hydroxide and silicates such as sodium silicate can be used. Further, if necessary, anti-redeposition agents such as carboxymethyl cellulose, polyvinyl pyrrolidone, and polyethylene glycol, alkyl sulfates,
Anionic surfactants other than the present invention such as alkane sulfonates, alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates and higher fatty acid soaps, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, higher grades Add nonionic surfactants such as fatty acid mono- or diethanolamide and amine oxide, amphoteric surfactants such as betaine, enzymes such as protease, lipase, amylase and cellulase, optical brighteners, dyes, pigments and fragrances. be able to.

[0048]

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

Example 1 Various bleaching compositions shown in Table 1 were prepared using a bleaching activator and a chelating agent represented by the following formulas, and the bleaching effect of each was investigated.

[0050]

[Chemical formula 26]

Measurement of bleaching effect Sodium percarbonate is dissolved in 300 ml of water at 20 ° C. so that the effective oxygen becomes 0.05%, and the bleaching activator is adjusted so as to be 1/16 equivalent of hydrogen peroxide in this solution. It was added in proportions shown in table 1, respectively, and adding a chelating agent 2% by weight, with a tea-stained cloth ^* and curry-stained cloth ^** each five were prepared in the following way
After immersion bleaching for 30 minutes, washing with water and drying, the bleaching rate was calculated by the following formula.

[0052]

[Equation 1]

The reflectance is NDR-1001D manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at P using a 460 nm filter.

* Black tea-contaminated cloth: 80 g of commercially available black tea leaves (Nitto black tea, yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes, then rubbed with desalted cotton, and this solution was woven with a cotton cloth. # 2003 Soak the cloth and boil for about 15 minutes. Remove from heat as it is, let stand for about 2 hours and let it air dry,
Rinse with water until the washing liquid does not become colored, dehydrate, press,
A test piece of 8 cm × 8 cm was used for the experiment. The results of the bleaching test are shown in Table 1. ** Curry-contaminated cloth: Warm commercial retort pack curry (Otsuka Foods, Boncurry Gold Medium Spicy), remove the ingredients with a 1000μ sieve, and sprinkle the curry roux with a cotton cloth # 200.
3 A piece of cloth, which was naturally dried and applied, was used as a test piece of 8 cm x 8 cm. The results of the bleaching test are shown in Table 1.

[0055]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location (C11D 7/54 7:18 7:32)

Claims (13)

[Claims] 1. A bleaching activator which produces (a) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution, 1 to 90% by weight (b) which reacts with hydrogen peroxide to produce an organic peracid. 0.1 to 50% by weight (c) A bleaching agent and a bleaching detergent composition containing 0.5 to 60% by weight of a dianionic surfactant having two anionic polar groups. 2. The bleaching agent and bleaching detergent composition according to claim 1, wherein the bleaching activator (b) is a bleaching activator which produces an organic peracid having a quaternary ammonium group. 3. The dianion type surfactant (c) has the following general formula (1): (In the formula, R represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms. X represents H or a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms, a hydroxyl group, Or an ethylene oxide group having an addition mole number of 1 to 10 moles, and M ₁ and M ₂ represent H ₂ , an alkali metal, an alkaline earth metal, a third period transition metal, ammonia, amines or alkanolamines. M _1, .n ₁ M ₂ is that it may be a combination of different cations may be the same,
n ₂ is equal to the number of charges in M ₁ and M ₂ cations, respectively. ) A malonic acid type surfactant represented by
Alternatively, the bleaching agent and the bleaching detergent composition described in 2. 4. The dianion type surfactant (c) has the following general formula (2): (In the formula, R and M ₁ , M ₂ , n ₁ and n ₂ are the same as above.)
The succinic acid type surfactant represented by
The bleaching agent and bleaching detergent composition described. 5. The dianion type surfactant (c) has the following general formula (3): (In the formula, R and M ₁ , M ₂ , n ₁ , n ₂ are the same as above, and m represents an integer value of 2 to 4.) A glutaric acid type, adipic acid type or The bleaching agent and bleaching detergent composition according to claim 1 or 2, which is a pimelic acid type surfactant. 6. The dianionic surfactant (c) is represented by the following general formula (4) or (5): (In the formula, R ₁ represents H or a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, and R, M ₁ , M ₂ ,
n ₁ and n ₂ are the same as above. The bleaching agent and the bleaching detergent composition according to claim 1 or 2, which is an aspartic acid type surfactant represented by the formula (1). 7. The dianion type surfactant (c) is represented by the following general formula (6) or (7): A malic acid ether type or malic acid ester type surfactant represented by the formula (wherein R, M ₁ , M ₂ , n ₁ and n ₂ are the same as above). Bleaching agent and bleaching detergent composition. 8. A dianion type surfactant (c) is represented by the following general formula (8) or (9): (In the formula, R ₁ represents H or a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, and X represents H or 1 carbon atom.
~ 30 carboxyalkyl groups. R, M ₁ , M ₂ , n ₁ , n
₂ is the same as above. ) A bleaching agent and a bleaching detergent composition according to claim 1 or 2, which is a tartrate ether type or tartrate ester type surfactant represented by 9. The dianion type surfactant (c) has the following general formulas (10) to (13): (In the formula, R ₁ represents H or a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms. R, M ₁ , M ₂ , n ₁ , n ₂
Is the same as above. The bleaching agent and the bleaching detergent composition according to claim 1 or 2, which is a citric acid monoester type or citric acid monoamide type surfactant represented by the formula (1). 10. The dianion type surfactant (c) has the following general formula (14): A bleaching agent and a bleaching detergent according to claim 1 or 2, which is an iminodiacetic acid type surfactant represented by the formula (wherein R, M ₁ , M ₂ , n ₁ and n ₂ are the same as above). Composition. 11. The dianionic surfactant (c) is represented by the following general formula (15) or (16): (In the formula, R ₂ represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms, R ₃ and R ₄ are H or 1 to 1 carbon atoms.
30 linear or branched alkyl or alkenyl groups are shown. R, M ₁ , M ₂ , n ₁ and n ₂ are the same as above. The bleaching agent and the bleaching detergent composition according to claim 1 or 2, which is an ethylenediamine diester type or ethylenediamine diamide type surfactant represented by the formula (1). 12. The dianion-type surfactant (c) has the following general formulas (17) to (20): (In the formula, R, R ₁ , M ₁ , M ₂ , n ₁ and n ₂ are the same as above.) A sulfosuccinic acid monoester type or sulfosuccinic acid monoamide type surfactant. Alternatively, the bleaching agent and the bleaching detergent composition described in 2. 13. The following general formula: Wherein R ′ is H or OH and R ″ is H or COOH. A water-soluble polymer having a molecular weight of 1,000 to 200,000 and having a repeating unit represented by the formula A bleaching agent and a bleaching detergent composition according to any one of 1 to 12.