JPH0841493A - Bleaching cleaner composition - Google Patents

Abstract

PURPOSE:To obtain a composition showing highly bleaching and cleaning power on lipophilic stain such as sebum, oils, etc., not decoloring dye of fiber, containing a peroxy acid bleaching agent precursor mixture having high lipophilic nature and an inorganic peroxide, etc. CONSTITUTION:This bleaching cleaner composition comprises (A) 1-95wt.% of an inorganic peroxide capable of producing hydrogen peroxide in an aqueous solution, (B) 0.1-30wt.% of a precursor which is a peroxy acid bleaching agent precursor of formula I [R is a (substituent group or connecting group-containing) 5-22C alkyl, alkenyl or (substituted) aryl; L is an eliminable group], has <HLB 23 and produces >=0.1mM formed amount of a diacyloyl of formula II at 20 deg.C after 10 minutes in formation of an aqueous solution containing 10mM of the precursor and 50 mM of hydrogen peroxide, (C) 0.1-100ppm of one or more metal cations selected from Mn, Cu and Fe and (D) 0.1-50wt.% of one or more surfactants selected from an anionic, a nonionic, a cationic and an ampholytic surfactants.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching detergent composition containing a highly lipophilic peroxo acid bleaching precursor and an inorganic peroxide, and particularly has a high bleaching detergency for lipophilic stains. And a bleaching detergent composition which does not cause decolorization of the dye.

[0002]

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 cannot be used in colors and patterns. Oxygen-based bleaching agents, which do not have these drawbacks, have recently become remarkably popular due to their non-existence and unique odor. Among the oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid bleaching agent.

However, these oxygen-based bleaching agents have a weaker bleaching power than chlorine-based bleaching agents, and various peroxo acid bleaching agent precursors are used together. Examples of these peroxo acid bleaching precursors include O-acetylated compounds represented by glucose pentaacetate, N-acylated compounds represented by tetraacetylethylenediamine, and acid anhydrides represented by maleic anhydride. These peroxo acid bleach precursors enhance bleaching power by producing peracetic acid in the wash bath. However, since peracetic acid is hydrophilic, it has a high bleaching power for hydrophilic stains such as black tea and wine, but has a drawback that it is less effective for lipophilic stains such as sebum stains and oil stains.

As a precursor of a peroxo acid bleaching agent, which has improved this drawback, the present inventors have disclosed in JP-A-63-233969, JP-A-63-31566, JP-A-64-68347, and JP-A-1. As disclosed in JP-A-190654, it was found that a compound that reacts with hydrogen peroxide to generate an organic peracid having a quaternary ammonium group is excellent as a precursor of a peroxo acid bleaching agent. An example of a peroxo acid bleaching agent precursor having an anionic group having a lipophilic group introduced into the molecule is disclosed in Japanese Patent Publication No. 63-12520. However, although the peroxo acid bleach precursors described in these publications have an effect on lipophilic stains, they are not satisfactory. In addition, since it has a property as a surfactant itself, when peracid is generated in a high-concentration aqueous solution, diacryloyl peroxide is by-produced. It has been found from studies by the present inventors that this diacylloyl peroxide has a function of decolorizing the dye of the fiber. Therefore, when the above-mentioned peroxo acid bleaching agent precursor is used for bleaching or washing, there is a problem that if there is an undissolved portion, that portion is discolored.

The problem to be solved by the present invention is as follows.
It is an object of the present invention to provide a bleaching detergent composition containing a peroxo acid bleaching precursor which has a high bleaching power for lipophilic stains and does not decolor the dye of the fiber.

[0006]

Means for Solving the Problems The present inventors have conducted extensive studies in order to solve the above problems, and a bleaching detergent composition containing a specific peroxo acid bleaching precursor and an inorganic peroxide, It has been found that the above object can be achieved by blending a specific metal cation in an amount within a specific range, and the present invention has been completed.

That is, the present invention comprises: (a) 1 to 95% by weight of an inorganic peroxide capable of generating hydrogen peroxide in an aqueous solution (b) a peroxo acid bleach precursor represented by the general formula (1): There

[0008]

[Chemical 4]

[In the formula, R may have a substituent such as —OH, —SO ₃ M, and —COOM, and also —CONH—, —NHCO—, —COO—, and —OC.
O-, -O- such as an alkyl group or an alkenyl group having 5 to 22 carbon atoms which may include a linking group, or an aryl group which may be substituted with an alkyl group or alkenyl group having 1 to 18 carbon atoms. Where L represents a leaving group. ] The fatty acid sodium salt RCOONa corresponding to the organic peracid generated from the peroxo acid bleach precursor represented by the general formula (1)
Davies' method of JT Davies, Proc. In
tern. Cong. Surface Active Substances, 2nd (Londo
n), Vol.1, p426 (1957)] has an HLB of 23 or less, and further the peroxo acid bleach precursor is 10 m
The following general formula (2) after 10 minutes at 20 ° C when an aqueous solution containing M and hydrogen peroxide at a concentration of 50 mM is prepared

[0010]

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0.1 to 30% by weight of a precursor of peroxo acid bleaching agent having a production amount of diacyloyl peroxide of 1 mM or more (c) 0.1 to at least one metal cation selected from Mn, Cu and Fe. 100 ppm (d) A bleaching detergent composition containing 0.1 to 50% by weight of at least one surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. It is provided. Hereinafter, the present invention will be described in detail.

The inorganic peroxide capable of generating hydrogen peroxide in the aqueous solution which is the component (a) of the present invention is a bleaching compound,
Specific examples thereof include granular or powdery percarbonate, perborate, perphosphate, persilicate, and the like, and percarbonate, especially sodium percarbonate, is particularly effective. (A) in the composition of the present invention
The blending amount of the components is 1 to 95% by weight, preferably 5 to 90% by weight, more preferably 5 to 85% by weight. If the blending amount is less than 1% by weight, sufficient bleaching performance cannot be obtained,
The bleaching performance does not improve so much even if it is blended more than 95% by weight.

The peroxo acid bleach precursor is bleached with an organic peracid formed by reacting with hydrogen peroxide under mild conditions in a washing bath, and the bleaching power is affected by the structure of this organic peracid. . Peroxo acid bleach precursors such as tetraacetylethylenediamine and glucose pentaacetate produce peracetic acid. Since this peracetic acid is hydrophilic, it is less effective against lipophilic stains. Therefore, it is effective to introduce an alkyl group having affinity for lipophilic stain into the peroxo acid bleach precursor.

The present inventors have proceeded with the investigation on the peroxo acid bleach precursor represented by the general formula (1), and in particular, the fatty acid sodium salt RCOONa corresponding to the organic peracid generated from the peroxo acid bleach precursor. Davis (Davies)
His method [JT Davies, Proc. Intern. Cong. Surface Ac
Correlation between HLB calculated by tive Substances, 2nd (London), Vol. 1, p426 (1957)] and the amount of diacyloyl peroxide produced from the peroxo acid bleach precursor, and the bleaching power of lipophilic stains. As a result, when HLB was 23 or less, and when an aqueous solution containing the peroxo acid bleach precursor precursor at a concentration of 10 mM (mmol) and hydrogen peroxide at a concentration of 50 mM (mmol) was prepared, 10 minutes after the preparation, General formula (2) at (20 ℃)

[0015]

[Chemical 6]

It has been found that the peroxo acid bleach precursor, which produces 1 mM or more of diacylloyl peroxide, has an extremely excellent bleaching power. When the HLB is more than 23 or the production amount of diacylloyl peroxide is less than 1 mM, the affinity for lipophilic stain is lowered and the bleaching effect of lipophilic stain becomes insufficient.

The compound represented by the general formula (3) is preferable as an example of such a precursor of peroxo acid bleaching agent.

[0018]

[Chemical 7]

[In the formula, R ₁ may be substituted with -SO ₃ M, -OH, -COOM, and also -COO- group, -OCO- group, -NHCO-
Group, a -CONH- group, a linear or branched alkyl group or alkenyl group having 7 to 22 carbon atoms which may be linked with an -O- group, or an aryl group which may be substituted with an alkyl group , X represents -SO ₃ M or -COOM. Here, M represents an inorganic or organic cation. ] More specific examples include the compounds shown in Tables 1 and 2.

[0020]

[Table 1]

[0021]

[Table 2]

* Production amount of corresponding diacylloyl peroxide after 10 minutes at 20 ° C. in an aqueous solution having a concentration of peroxoic acid bleaching agent precursor of 10 mM and hydrogen peroxide of 50 mM. These compounds can be converted by known methods such as chlorination of corresponding fatty acid. It can be synthesized by reacting with a chlorinating agent such as thionyl to synthesize an acid chloride and then reacting with sodium p-phenolsulfonate or sodium p-hydroxybenzoate.

The component (b) is 0.1 to 30% by weight in the composition,
The amount is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight.

However, these peroxo acid bleach precursors have a property as a surfactant because the HLB of the corresponding carboxylic acid is low, and therefore they have a high concentration of peroxo acid bleach precursor and a high concentration of peroxy acid bleach precursor. In an aqueous solution containing hydrogen oxide, diacyloyl peroxide is easily generated as shown in the following reaction formula.

RCO-L + H ₂ O ₂ → RCOOH RCOOH + RCO-L → RCOOOCOR Then, the present inventors have studied a peroxo acid bleach precursor which is highly effective for lipophilic stains, and as a result, Bleaching agent precursor, when the peroxo acid bleaching agent precursor 10mM, when preparing an aqueous solution containing a concentration of hydrogen peroxide 50mM, immediately after preparation, after the reaction for 10 minutes at 20 ℃, the formation of diacylloyl peroxide It was found that the amount was 1 mM or more.

From this, it was found that it is desirable to use a peroxo acid bleach precursor in which the production amount of diacyloyl peroxide is 1 mM or more. However, such a peroxo acid bleach precursor is used as an inorganic peroxide, For example, it has been found that when placed on a dyed cloth with sodium percarbonate, tap water is added and left for about 30 minutes to cause decolorization of the dye. This means that when the peroxo acid bleach precursor is used for actual bleaching, the presence of the undissolved residue causes decolorization of the dye, and it is necessary to solve this problem.

As a result of further investigations to solve this problem, the inventors of the present invention have found that, as the component (c), at least one metal cation selected from Mn, Cu and Fe is mixed in a specific range ratio. It is possible to provide a bleaching detergent composition which not only has high bleaching performance for hydrophilic stains but also has an extremely excellent bleaching effect for lipophilic stains and further does not cause decolorization of dyes. did.

It has been reported that these metal cations decompose diacylloyl peroxide in the following reaction to generate a more reactive acyloxy radical near room temperature [Chemistry of Organic Peroxides] Yoshiro et al., Nankodo Co., Ltd.
].

[0029]

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This acyloxy radical has an extremely high bleaching power for lipophilic stains. Moreover, since the diacylloyl peroxide, which is the cause of decolorization, is decomposed, the decolorization prevention property is also enhanced. As Mn, Cu and Fe ions, Mn (II), Mn (I
At least one metal cation selected from II), Mn (IV), Fe (II) and Cu (I) is preferable.

In the present invention, the content of the metal cation as the component (c) is 0.1 to 100 ppm, preferably 1 to 100 ppm, more preferably 5 to 50 ppm. (c) The amount of ingredient is 0.
If it is less than 1 ppm, the bleaching performance will be poor, and if it exceeds 100 ppm, the fiber will be damaged.

The metal cation as the component (c) is incorporated into the composition in the form of, for example, a hydrochloride salt, a sulfate salt, a phosphate salt, a fatty acid salt or an oxide. Further, as disclosed in JP-A-2-261547 and JP-A-4-270798, a nitrogen-containing macrocyclic organic compound may be added as a ligand-complex. In either case, it is necessary to add a salt or the like so that the amount of the metal cation is within the above range.

In the present invention, as component (d), at least one surface active agent selected from anionic surface active agents, nonionic surface active agents, cationic surface active agents and amphoteric surface active agents is used in the composition. ~ 50% by weight, preferably 0.5 ~
50% by weight, and more preferably 1 to 50% by weight. Examples of these surfactants are alkylbenzene sulphonates, alkyl or alkenyl ether sulphates, alkyl or alkenyl sulphates, olefin sulphonates, alkane sulphonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acids. Anionic surfactants such as acid salts, α-sulfo fatty acid salts, or α-sulfo fatty acid esters, polyoxyethylene or polyoxypropylene or copolymers thereof, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl Ethers, higher fatty acid alkanolamides,
Or its alkylene oxide adducts, nonionic surfactants such as sucrose fatty acid esters and alkyl glucosides, amphoteric surfactants such as amine oxides, sulfobetaines and carbobetaines, or cationic surfactants such as quaternary ammonium salts. Examples thereof include ionic surfactants.

Of these, alkylbenzene sulfonates having 10 to 20 carbon atoms, alkyl or alkenyl sulphates having 10 to 20 carbon atoms, alkyl or alkenyl ether sulfates having 10 to 20 carbon atoms, and 10 to 20 carbon atoms, Particularly preferred are polyoxyethylene alkyl or alkenyl ethers having 4 to 30 moles of oxyethylene added, and sulfobetaine or carbobetaine having an alkyl group having 8 to 20 carbon atoms.

Further, in the present invention, a sequestering agent can be blended if desired. As the sequestering agent, 1) a phosphoric acid compound such as phytic acid or an alkali metal salt, an alkaline earth metal salt, an ammonium salt or an alkanolamine salt 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) Acrylic acid, maleic acid , Itaconic acid, anicotic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid, citraconic acid, or other polymers or copolymers of two or more kinds, and having an average molecular weight of 500 to 100,000 and part or all of these carboxyl groups. Polycarboxylic acids which may be alkali metal salt, alkaline earth metal salt, ammonium salt, alkanolamine salt 4) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid , Phosphonocarboxylic acids such as α-methylphosphonosuccinic acid or their alkalis Group salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 5) Aspartic acid, glutamic acid, glycine and other amino acids or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 6) Nitrilotriacetic acid , Iminodiacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine 6-acetic acid and diencoric acid or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid , Organic acids such as 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 8) Zeolite A Alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts of aluminosilicate represented by

Of these, at least one selected from 2), 3), 6) and 8) is particularly preferable. The amount of such a sequestering agent is preferably 0.0005 to 25% by weight, more preferably 0.1 to 20% by weight, based on the bleaching detergent composition.

Further, in the present invention, in addition to the above-mentioned components, known components which are usually added may be added. For example, as an optical brightener to increase the bleaching effect on bleached fibers, alkaline agents such as sodium carbonate, Chinopearl CBS
(Manufactured by Ciba Geigy), Chino Pearl SWN (manufactured by Ciba Geigy), and color index optical brightener 28, 4
If necessary, a fluorescent whitening agent such as 0, 61, 71, etc., and conventionally known enzymes (cellulase, amylase, protease, lipase) for improving the bleaching performance can be added.

Further, in the present invention, various trace additives such as colorants such as dyes and pigments, fragrances, silicones, bactericides, ultraviolet absorbers and the like can be added in appropriate amounts.

The method for producing the composition of the present invention comprises the steps of (b) component and (c)
The powder obtained by mixing the components uniformly in advance is used as component (a) and component (d).
It is characterized by being mixed with an ingredient and an optional ingredient. Specifically, for example, bleaching components (component (a) such as sodium percarbonate), powders containing components (b) and (c), enzymes, fluorescent dyes, and bases that are unstable in alkaline solutions, etc. To
A method of dry blending with particles of a cleaning component that has been separately granulated is preferable, and a method of granulating the cleaning component is described, for example, in JP-A-5-209200, JP-A-61-69897, and JP-A-61-89797.
The methods described in JP-A-61-69899 and JP-A-61-69900, that is, a method in which a detergent component is slurried, spray-dried, and then granulated with a high-speed mixer or the like can be used.

[0040]

According to the present invention, it is possible to provide a bleaching detergent composition which has an extremely excellent bleaching power for lipophilic stains and does not cause decolorization of dyes.

[0041]

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

Examples 1 to 18 and Comparative Examples 1 to 12 Sodium percarbonate as the component (a) and the following as the component (b)
(b) -1 to (b) -4, Fe (PO) ₄ as the component (c), (C ₇ H
₁₅ COO) ₂ Fe, CuSO ₄ , MnCl ₂ , Mn ₂ (SO ₄ ) ₃ , MnO ₂ (d) as components (d) -1 to (d) -5 below, and ethane-1- as a sequestering agent. Hydroxy-1,1-diphosphonic acid sodium salt [(e) -1], ethylenediaminetetraacetic acid [
(e) -2] and acrylic acid-maleic acid copolymer (BAS
Sokalan CP-5) [(e) -3] manufactured by Company F was used, and sodium carbonate, zeolite, and other components were further added as an alkaline agent, and Table 3 (Examples 1 to 9) and Table 5 were used.
Bleaching detergent compositions having the compositions shown in (Examples 10 to 18) were prepared, and the bleaching performance was measured by the following method. The results are shown in Tables 3 and 5.

As a comparative example, the following is given as the component (b).
The results when (b ')-1 and (b')-2 were used are shown in Tables 4 and 6.

[0044]

[Chemical 9]

[0045]

[Chemical 10]

Measurement of Bleaching Performance Examples 1-9 and Comparative Examples 1-6 10 g of the bleaching detergent composition shown in Tables 3-4 was added to a 2 liter aqueous solution containing 25 g of a commercial detergent and prepared as follows. Each of the hydrophilic soiled black tea soiled cloth and the lipophilic soiled curry soiled cloth was immersed for 5 minutes in 15 minutes. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula.

[0047]

[Equation 1]

The reflectance is NDR-1 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with a 460 nm filter at 01DP.

(Preparation 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, then rubbed with de-squeezed cotton and soaked in cotton rag # 2003. , Boiled for 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 became colorless, dehydrated, pressed, and then used as a test piece of 10 × 10 cm for an experiment. (Preparation of Curry Contaminated Cloth) “Bon curry” manufactured by Otsuka Foods Co., Ltd. was heated at 80 ° C./30 minutes, filtered through a colander to remove the solid content, and a cotton gold cloth # 2003 was dipped in the solution and heated for 15 minutes. After leaving it as it was for about 2 hours, the cloth was taken out from the liquid and the excess liquid was removed to naturally dry it. After pressing, it was used in an experiment as a 10 cm × 10 cm test piece.

◎ Decoloring Test A garment dyed with a commercially available dye was cut into 10 × 10 cm pieces, and 5 g of the bleaching detergent composition was placed on the cloth. From above, 5 ml of tap water was poured and left for about 30 minutes. Then, it was rinsed with tap water and dried, and then evaluated as follows. ◎… No bleaching at all ◯… Slightly discolored but not at all Δ… Some bleaching has occurred ×… Discoloration has occurred on the entire cloth

[0051]

[Table 3]

[0052]

[Table 4]

Examples 10-18 and Comparative Examples 6-12 For the compositions of Tables 5-6, 25 g of each composition was added.
It was dissolved in 30 liters of tap water, and 20 pieces of the above black tea-contaminated cloth or curry-contaminated cloth were washed with a washing machine for 10 minutes, then rinsed with tap water and dried, and the bleaching rate was calculated by the same method as above. Further, a decolorization test was conducted in the same manner as above.

[0054]

[Table 5]

[0055]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C11D 3:34)

Claims (5)

[Claims] 1. (a) 1 to 95% by weight of an inorganic peroxide capable of generating hydrogen peroxide in an aqueous solution (b) a peroxo acid bleach precursor represented by the general formula (1): Chemical 1] [In the formula, R is an alkyl group or an alkenyl group having 5 to 22 carbon atoms, which may have a substituent, and may contain a linking group, or an alkyl group or alkenyl group having 1 to 18 carbon atoms. L represents an optionally substituted aryl group, L
Represents a leaving group. ] The fatty acid sodium salt RCOONa corresponding to the organic peracid generated from the peroxo acid bleach precursor represented by the general formula (1)
Davies' method of JT Davies, Proc. In
tern. Cong. Surface Active Substances, 2nd (Londo
n), Vol.1, p426 (1957)] has an HLB of 23 or less, and further the peroxo acid bleach precursor is 10 m
When an aqueous solution containing M and hydrogen peroxide at a concentration of 50 mM was prepared at 20 ° C. for 10 minutes, the following general formula (2): 0.1 to 30% by weight of a peroxo acid bleach precursor having a production amount of diacyloyl peroxide of 1 mM or more (c) 0.1 to 100 ppm (d) of at least one metal cation selected from Mn, Cu and Fe. ) A bleaching detergent composition containing 0.1 to 50% by weight of at least one surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. 2. The bleaching detergent composition according to claim 1, wherein the component (b) is a peroxo acid bleaching precursor represented by the following general formula (3). [Chemical 3] (In the formula, R ₁ may be substituted with -SO ₃ M, -OH, -COOM, and also -COO- group, -OCO- group, -NHCO- group, -CONH- group,
A linear or branched C7-C22 alkyl or alkenyl group that may be linked by an -O- group, or an aryl group that may be substituted by an alkyl group, and X is -S;
Indicates O ₃ M or -COOM. Here, M represents an inorganic or organic cation. ] 3. The bleaching detergent composition according to claim 2, wherein in the peroxo acid bleach precursor of the general formula (3), R ₁ is an alkyl group or an alkenyl group having 10 to 18 carbon atoms. 4. The metal cation of the component (c) is Mn (I
The bleaching detergent composition according to any one of claims 1 to 3, which is at least one selected from I), Mn (III), Mn (IV), Fe (II) and Cu (I). 5. The bleaching detergent composition according to claim 1, further comprising a sequestering agent.