JP2758547B2 - Bleach detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bleaching detergent composition.

[0002]

2. Description of the Prior Art Conventionally, chlorine bleaching agents and oxygen bleaching agents have been used for bleaching fibers. Chlorine bleach is not suitable as a detergent composition because it has limitations on the fibers that can be used, cannot be used for colors and patterns, and has a unique odor.

[0003] Further, as an oxygen bleach, it is dissolved in water,
Sodium percarbonate and sodium perborate, which release hydrogen peroxide, are well known, but have the drawback that their bleaching power is weaker than that of chlorine bleach. In order to enhance the bleaching power of oxygen-based bleaching agents, a bleaching activator has been used in combination with sodium percarbonate and sodium perborate to increase the bleaching power. A bleach activator refers to an organic peracid precursor that reacts with hydrogen peroxide to produce an organic peracid with higher bleaching power. However, the bleaching activator becomes unstable during long-term storage when sodium percarbonate and sodium perborate coexist in a detergent system. Also,
It is well known that zeolites in detergent powders also act to accelerate decomposition. For this reason, the bleach activator must be protected from the surrounding environment by means such as granulation or surface coating. However, no protective measures should impair the dispersibility in the wash water. Many studies have hitherto been made to satisfy such conditions. For example,
57-126899, JP-A-2-29719, JP-A-61
JP-A-111400 and JP-A-57-192498 disclose methods for obtaining stable bleach activator granules. The granulated bleaching activator as described above has good storage stability when used alone, and dissolves relatively quickly under warm water conditions such as in Europe and the United States. However, under the washing conditions of weak stirring in cold water, as is often the case in Japan, the dissolution rate is low and the function of the bleach activator cannot be fully exploited.
When the bleach activator granules are blended with sodium percarbonate and sodium perborate, the storage stability is not sufficient due to the reaction between sodium percarbonate and sodium perborate and the bleach activator.

Accordingly, the present invention has a high dissolution rate under low-temperature, weakly agitated washing conditions, and has a high storage stability even when the bleaching activator granules and sodium percarbonate or sodium perborate are blended. An object is to obtain an excellent bleaching detergent composition.

[0005]

As a result of various studies, the present inventors have found that a bleaching activator, a water-soluble organic binder, an anionic surfactant and a carboxylic acid having 6 or less carbon atoms or a salt thereof are contained in a specific ratio. And the amount of a carboxylic acid having 6 or less carbon atoms and / or a salt thereof in the granulated product, and a carboxylic acid having 6 or less carbon atoms to be added to the composition. The inventors have found that the above problem can be solved by setting the amount of the salt and / or the salt thereof to a specific ratio, and have completed the present invention.

That is, the present invention relates to a bleaching activator granule containing 1 to 30% by weight containing the following (i) to (iv): hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution. ~ 40% by weight
And 8 to 35% by weight of a surfactant, a carboxylic acid having 6 or less carbon atoms and / or a salt thereof in addition to the bleach activator granules, and having 6 or less carbon atoms in the bleaching detergent composition. The total amount of the carboxylic acid or salt thereof is 0.5 to 10% by weight, and (the carboxylic acid and / or salt thereof having 6 or less carbon atoms in the bleaching activator granule) / (other than 6 or less carbon atoms) A bleaching detergent composition characterized in that the weight ratio of carboxylic acid and / or salt thereof is 1/50 to 1/1. (i) 10 to 85% by weight of bleach activator (ii) 1 to 30% by weight of water-soluble organic binder (iii) 1 to 10% by weight of anionic surfactant (iv) 5 to 50% by weight of carboxylic acid having 6 or less carbon atoms %.

[0007] In the bleaching activator granules according to the present invention (i)
As the bleach activator as a component, for example, tetraacetylethylenediamine, glucose pentaacetate,
Tetraacetyl glycoluril and alkanoyloxybenzenesulfonate. The alkanoyl group of the alkanoyloxybenzenesulfonate has 2 to 2 carbon atoms.
22 are used. A series of bleach activators represented by the following general formula (I) are also desirable.

[0008]

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(M is preferably 1 to 12, particularly preferably 1 to 5, and n
Is preferably 1 to 10, particularly preferably 1 to 5. ). a, b is a
= 0, b = 0, or a = 1, b = 1.
R ₂ and R ₃ are C ₁ -C ₂ alkyl groups. The linking group is not particularly limited, but is, for example, an alkylene group, a cycloalkylene group, a phenylene group or an alkylenephenylene group, an oxyalkylene group (such as —CH ₂ CH ₂ O—) and the like. The leaving group is not particularly limited, for example,

[0010]

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[0011]

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In the general formula of the organic peracid precursor, X ^- is an inorganic or organic counter ion, but the leaving group is

[0013]

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[0014] The time of the X ^- does not exist. The above general formula (II
In (I), the linking group is-(CH ₂ ) _x- (x = 1 to 12), particularly-(C
H ₂ ) _x- (x = 1 to 5), wherein the leaving group is (a), (b),
(C), (d), (f), (g), (w), (f),
Represented by the structural formulas (Y), (T), and (R), wherein R ₅ is C ₁ -C ₂
Alkyl group, R _6, R ₇ is H or an alkyl group of C ₁ -C ₂ of, R ₈
Is preferably a C ₁ -C ₂ alkyl group, and R ₉ is a C ₁ -C ₃ alkylene group, and particularly preferably compounds represented by the structural formulas (Y) and (T).

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

[0016]

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Wherein R is an alkyl group having 1 to 3 carbon atoms,
X ^- is an organic or inorganic anion, and n is an integer of 1 to 16. Among these bleach activators, particularly desirable are those represented by the following formulas.

[0018]

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[Wherein R ₁ and m are the same as above, and q is 1 to
The integer of 10 and the leaving group are groups represented by the above (Y) and (T). In the present invention, in particular, hydrogen peroxide as represented by the formula (I) reacts to form

[0020]

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Those which produce an organic peracid having the following are preferred.

Component (i) is contained in the bleaching activator granule in an amount of 10 to
85% by weight, preferably 40 to 60% by weight. If the bleaching activator is less than 10% by weight, the bleaching performance is unfavorably low, and if it exceeds 85% by weight, a part of the bleaching activator remains in the granulation system without being granulated and a good granulated product is obtained. I can't.

(Ii) in the bleaching activator granules according to the present invention
Specific examples of the water-soluble organic binder as a component include polyethylene glycol, polypropylene glycol, and a nonionic surfactant. Polyethylene glycol has a molecular weight of 400 to 20,000, preferably 600 to 10,000
Those in the range are suitable. As the nonionic surfactant, polyoxyethylene (ethylene oxide addition mole number = 3)
300) alkyl (C ₈ ~ ₂₂₎ ether, polyoxyethylene (ethylene oxide addition mole number = 10 to 300) alkyl (C ₈ ~
₁₄ ) Phenol ethers, nonionic surfactants commercially available under the trade names Pluronic and Tetronic, fatty acid glycerides having 8 to 20 carbon atoms, and the like. These water-soluble organic binders preferably have a melting point of 20 to 80 ° C, and more preferably polyethylene glycol, polypropylene glycol, and a nonionic surfactant having a melting point of 20 to 80 ° C. They do not melt at temperatures below 20 ° C.
It has tackiness or film forming property at a temperature of ℃ or more. From the viewpoint of thermal decomposition of the bleaching activator, it is not preferable that the temperature during granulation exceed 80 ° C.
A substance having a melting point of 20 to 80 ° C. is preferred, and a substance having a melting point of 30 to 70 ° C. is more preferably used.

The water-soluble organic binder is incorporated in the bleaching activator granule in an amount of 1 to 30% by weight, preferably 2 to 20% by weight. If the amount of the water-soluble organic binder is less than 1% by weight, the granulating properties are insufficient, and if it exceeds 30% by weight, kneading in the granulator becomes severe, and good granulating properties cannot be obtained.

In the bleaching activator granules according to the present invention, (ii)
i) Specific examples of the component anionic surfactant include:
Alkyl benzene sulfonate having 8 to 22 carbon atoms, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-
Sulfo fatty acid salt or ester salt of α-sulfo fatty acid, alkane sulfonate, saturated or unsaturated fatty acid, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant alkyl or alkenyl phosphate Esters or salts thereof are exemplified.

Among them, an alkylbenzene sulfonate having a total of 10 to 16 carbon atoms, an alkyl ether sulfate having an alkyl group having 10 to 16 carbon atoms (ethylene oxide is preferable as the alkylene oxide, and the average number of moles added is about 1 to 5; And alkylsulfates having 10 to 16 carbon atoms in the alkyl group are preferred. The alkyl benzene sulfonate preferably has a linear alkyl group (LAS). As the salt, an alkali metal salt is desirable.

The anionic surfactant is contained in the bleaching activator granule in an amount of 1 to 10% by weight, preferably 5 to 10% by weight.
When the amount of the anionic surfactant is less than 1% by weight, the solubility decreases, and when it exceeds 10% by weight, the hygroscopicity increases, and the stability of the bleaching activator (i) decreases. When a surfactant other than the anionic surfactant is incorporated into the bleaching activator granules, the solubility may be reduced.

Specific examples of (iv) a carboxylic acid having 6 or less carbon atoms and / or a salt thereof which can be used in the bleaching activator granules according to the present invention include acrylic acid, succinic acid, fumaric acid and the like. Examples include acids, citric acid, maleic acid, alginic acid and / or their salts. Of these, citric acid, succinic acid and / or their salts are more preferred. In the present invention, the carboxylic acid having 6 or less carbon atoms is particularly preferably in the form of an acid. As the number of carbon atoms in the carboxylic acid increases, the effect tends to be lower for the added amount, and it also causes a decrease in solubility, which is not preferable.

The granulated bleach activator contains the above components (i) to
(iv) In addition to the anti-redeposition agent such as polyvinylpyrrolidone, a bleaching stabilizer such as sodium polyacrylate, and magnesium sulfate and silicic acid which are known as stabilizers for peroxides or peroxide adducts Magnesium salts such as magnesium can also be used. In addition, a known 4A-type zeolite or an antifoaming agent can be added as a cleaning component. Further, the particle size of the granulated bleach activator of the present invention is
It is preferably from 100 to 3000 μm. When the thickness is less than 100 μm, not only the present effect cannot be obtained but also the anti-caking property tends to decrease. On the other hand, if it is 3000 μm or more, the solubility decreases.

The method for granulating the granulated product according to the present invention is not particularly limited, and a conventional method can be used, but the obtained granulated product is granulated by a granulation method that easily disintegrates or dissolves in a solution. Granulate. As the granulation method, a fluidized granulation method, a tumbling granulation method, and a stirring tumbling granulation method are suitably used. Among these granulation methods, the stirring tumbling granulation method is particularly preferable from the viewpoints of spheroidization of the granules, control of the particle size of the granules, mechanical strength of the granules and the like.

The bleach activator granules of the present invention are used in combination with hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution. In this case, the mixing ratio of the hydrogen peroxide or peroxide (a) and the bleaching activator granule (b) is usually (a) /
(b) (molar ratio) = 99.9 / 0.1 to 20/80 is preferable, and 99/1 to 50/50 is more preferable. Sodium percarbonate as peroxide, sodium tripolyphosphate-hydrogen peroxide adduct, sodium pyrophosphate-hydrogen peroxide adduct, urea-hydrogen peroxide adduct, or _{4NaSO 4 · 2H 2 O 2 ·} NaCl, perborate Sodium monohydrate, sodium perborate tetrahydrate,
Examples thereof include sodium peroxide and calcium peroxide.
Of these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferred. Also,
These peroxides are further storage-stabilized by coating them with borates and / or silicates.

In the present invention, a carboxylic acid having 6 or less carbon atoms and / or a salt thereof as described above must be blended in addition to the bleaching activator granules. As the carboxylic acid or a salt thereof, those exemplified for the granulated product can be used. Further, the carboxylic acid having 6 or less carbon atoms and / or a salt thereof to be blended here does not necessarily have to be the same as that in the granulated product. The method of adding a carboxylic acid having 6 or less carbon atoms and / or a salt thereof in addition to the granulated material is not particularly limited. For example, the carboxylic acid is put into a slurry containing a surfactant and zeolite, and this is spray-dried. There is a method, and a carboxylic acid having 6 or less carbon atoms and / or a salt thereof may be added as it is, but it is preferable to add it after granulation.

The carboxylic acid having 6 or less carbon atoms and / or a salt thereof is used in the bleaching detergent composition as a whole (the carboxylic acid having 6 or less carbon atoms and / or a salt thereof in the bleaching activator granule).
And (the other carboxylic acid having 6 or less carbon atoms and / or a salt thereof) have a weight ratio of 1/50 to 1/1, more preferably 1/50.
It needs to be 10 to 1/2. If a carboxylic acid having 6 or less carbon atoms and / or a salt thereof is not blended in addition to the granulated product, the storage stability in a detergent is significantly reduced. If the bleaching-activated granules are incorporated in a large amount in the bleaching-activated granules, the decomposition of the bleaching activator is promoted even with the granules alone. The total amount of the carboxylic acid having 6 or less carbon atoms and / or a salt thereof, which is blended in the bleaching activator granules and in addition to the bleaching activator granules, is 0.1 to 0.1% in the entire bleaching detergent composition. Must be 10% by weight. If the total amount of the carboxylic acid having 6 or less carbon atoms and / or a salt thereof in the composition is 0.1% by weight or less, the effect of the present invention cannot be obtained, and if it exceeds 10% by weight, the decomposition of the bleaching activator is accelerated. You.

The bleaching detergent composition of the present invention contains 8-35% by weight of a surfactant in addition to the bleaching activator granules and peroxide.
Be blended. The surfactant may be one commonly used in detergents, and examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.

Specifically, examples of the anionic surfactant include an alkylbenzene sulfonate having 8 to 22 carbon atoms in the alkyl chain, an alkyl or alkenyl ether sulfate, an alkyl or alkenyl sulfate, an α-olefin sulfonate, and an α-olefin sulfonate. -Sulfo fatty acid salts or ester salts, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphoric acid Esters or salts thereof are exemplified. Of these, alkylbenzene sulfonates and alkyl sulfates are preferred. There is no problem even if the anionic surfactant used here is the same as the one added to the bleaching activator granules. The amount of the anionic surfactant in the entire composition is not particularly limited as long as the particles are separated.

Examples of the nonionic surfactant include a polyoxyalkylene alkyl (or alkenyl) ether having a hydrophobic group having a hydrocarbon group having 8 to 22 carbon atoms, a polyoxyethylene alkyl phenyl ether, a higher fatty acid alkanolamide or an alkylene thereof. Oxide adducts, sucrose fatty acid esters, alkyl glucosides, fatty acid glycerin monoesters, alkylamine oxides and the like can be mentioned. Particularly, the following nonionic surfactants are preferable. (1) A polyoxyethylene alkyl ether having an alkyl group having an average of 10 to 20 carbon atoms and having 1 to 30 mol of ethylene oxide added thereto. (2) Alkyl phenyl ether having an alkyl group having an average of 9 to 12 carbon atoms and having 1 to 25 mol of ethylene oxide added thereto. (3) An alkyl glycoside represented by the following general formula. R (OC ₂ H ₄ ) _x G _y (wherein, R is an alkyl group having 9 to 14 carbon atoms, X is a number of 0 to 2, G is a glucose, fructose, maltose or scroll residue, and y is 1 to 4 The number of surfactants other than anionic surfactants may be partially incorporated in the bleaching activator granules described above in a small amount.

In addition, the bleaching detergent composition of the present invention includes:
General components used in cleaning agents may be blended. Specifically, a detergent builder such as a crystalline aluminosilicate, for example, a zeolite 4A, an alkali agent such as sodium carbonate, potassium carbonate, and sodium sulfate, and an inorganic salt, an oil-absorbing carrier described in EP 477974A, protease, lipase, and cellulase Enzymes, anti-redeposition agents, fluorescent dyes and fragrances.
Further, a bleaching stabilizer, an anti-caking agent, a dye, a solubilizing agent, an enzyme activity improver, and the like can be added to the composition of the present invention as needed. Components other than the bleach activator may be obtained by spray-drying a slurry and mixing granulated ones.In particular, when a high-density detergent is to be produced, for example,
JP-A-61-69897, JP-A-61-69899, JP-A-61-69899
The methods described in 69900 and EP 513824A can be used. In addition, only the builder is a polymer such as polyethylene glycol or a high melting point nonionic surfactant,
Alternatively, granulation using soap or the like as a binder may be performed after blending.

[0038]

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

(1) Method for synthesizing bleach activator (a) 100 g (0.46 mol) of sodium p-phenolsulfonate which had been previously dehydrated was added to dimethylformaldehyde (DMF) 30
06.8 g, 4-chlorocaproic acid chloride 76.8 g (0.46 mol) was stirred at 50 ° C with a mechanical stirrer.
And the mixture is reacted for 3 hours after the completion of the dropwise addition. DMF
Is distilled off at 100 ° C. under reduced pressure (0.5-1 mmHg) and washed with acetone to obtain 153.5 g (purity: 80.8%) of an ester compound (b) represented by the following formula. 90% yield.

[0040]

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N, N-dimethylpropylenediamine 50 g
(0.49 mol) was mixed with 64.1 g (0.44 mol) of n-caprylic acid,
100 ° C to 160 ° C while removing water generated by flowing nitrogen
The reaction was performed by raising the temperature over 11 hours. 0.45mmHg, 120
By distilling at ~ 140 ° C, 95.8 g (purity: 95%) of a transparent liquid amine compound (C) represented by the following formula is obtained.
92.2% yield.

[0042]

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Amine compound (c) 50 g (purity 95%, 0.21 mol
l) and ester compound (b) 66.9 g (purity 80.8%, 0.2 mol)
Was suspended in 150 g of DMF, reacted at 120 ° C for 12 to 14 hours, filtered, and the solvent of the filtrate was distilled off at 0.5 to 1 mmHg at 100 ° C. After washing with acetone, the following formula was obtained as a white powder. 87.0 g (purity 90%) of an organic peracid precursor (a) represented by the following formula is obtained. 80% yield.

[0044]

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(2) Method for producing granulated bleach activator Glauber's salt having a particle size of 500 μm, bleach activator (a) obtained above
, Polyethylene glycol (average molecular weight: 6000), sodium alkyl sulfate (carbon number of alkyl group: 12) and carboxylic acid having a weight average particle diameter of 500 μm in a ratio shown in Tables 1 to 4 by a granulator [Fukae Kogyo Co., Ltd .; High speed mixer FS-SG-
10 mold], the jacket temperature was set to 70 ° C., and granulation was carried out for about 20 minutes. Cool the granulation, sieve and granulate
A 00 μm granulation was obtained.

(3) Production of Detergent (Nonion Base) Of the detergent components shown in Tables 1 and 2, it is desirable to dry-mix later (10% by weight of zeolite and enzyme, bleaching activator granules, Powder kneader excluding sodium percarbonate, etc.) is batch kneader (Bench Kneader PNV-1 manufactured by Irie Shokai)
, And gradually introduce the liquid non-nonionic surfactant,
Then, a polyethylene glycol melt was added to produce a powder detergent fabric having an average particle size of 350 to 450 μm.

(4) Manufacture of detergent (anion-based) Among the detergent components shown in Tables 3 and 4, components which are preferably dry-mixed later (10% by weight of zeolite and enzyme, bleach activator granules, A slurry having a composition excluding sodium percarbonate) and a water content of 50% is prepared, and the powder obtained by spray-drying the slurry is charged into a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and agitated and granulated. By this, the average particle size 350-450
Various high-density granular detergent compositions having a μm bulk density of 0.70 to 0.80 g / cm ³ were obtained.

[Storage stability] 10 g of each of the bleaching detergent compositions having the component compositions shown in Tables 1 to 4 were placed in a 50 ml plastic container at 40 g.
Store for 4 weeks at 80 ° C and 80% relative humidity. The residual amount of the activator of the sample before and after storage was determined by the following titration method, and the residual ratio of the activator was calculated by the following formula.

[0049]

(Equation 1)

<Titration Method> 1 liter of water at 20 ° C. was placed in a 1 liter beaker, and 10 g of each bleaching detergent composition was applied at 100 rpm using a 2 cm mechanical stirrer with stirring blades.
After stirring for 10 minutes, 5 ml of a 0.3% catalase solution is added and stirred for 1 minute. 10% potassium iodide solution 10
Add 10 ml of 20% sulfuric acid solution and titrate with 0.1 N sodium thiosulphate solution.

The storage stability (activator residual ratio) obtained for the formulation examples in Tables 1 to 4 is shown in each table. As shown in Tables 1 to 4, the bleaching detergent composition of the present invention exhibited better storage stability than the comparative product.

[0052]

[Table 1]

Note) * 1 The number in parentheses in the column of granulated material indicates the ratio in the granulated material (the same applies hereinafter). * 2 Toksil AL-1: manufactured by Tokuyama Soda Co., Ltd., oil absorption 255m
l / 100g, SiO ₂ content of 94 wt%

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ identification code FI C11D 1:22 7:26 7:38) (56) References JP-A-3-64400 (JP, A) JP-A-62- 240395 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C11D 7/26-7/54 D06L 3/02 C11D 3/395

Claims (7)

(57) [Claims] 1. A bleaching activator granule containing 1 to 30% by weight containing the following (i) to (iv), and 1 to 40% by weight of hydrogen peroxide or a peroxide capable of generating hydrogen peroxide in an aqueous solution. %, A surfactant of 8 to 35% by weight, and a carboxylic acid having 6 or less carbon atoms and / or a salt thereof in addition to the bleach activator granules. The total amount of the following carboxylic acids or salts thereof is 0.5 to 10% by weight, and (the carboxylic acids having 6 or less carbon atoms and / or salts thereof in the bleaching activator granules) /
A bleaching detergent composition characterized in that the weight ratio of the other carboxylic acid having 6 or less carbon atoms and / or a salt thereof is 1/50 to 1/1. (i) 10 to 85% by weight of bleach activator (ii) 1 to 30% by weight of water-soluble organic binder (iii) 1 to 10% by weight of anionic surfactant (iv) Carboxylic acid having 6 or less carbon atoms and / or Salt 5-50% by weight 2. The bleaching activator granules having a particle size of 100 to 3000.
The bleach activator composition according to claim 1, which has a particle size of 1 µm. 3. The bleaching detergent composition according to claim 1, wherein the component (iv) is a carboxylic acid having 6 or less carbon atoms. 4. The bleaching detergent composition according to claim 1, wherein the component (iv) is citric acid or succinic acid. (Ii) the water-soluble organic binder has a melting point of 20;
The bleaching detergent composition according to any one of claims 1 to 4, wherein the temperature is from 80 to 80 ° C. 6. The bleaching detergent composition according to claim 1, wherein (iii) the anionic surfactant is selected from an alkyl benzene sulfonate, an alkyl ether sulfate and an alkyl sulfate. Stuff. 7. A bleach activator reacts with hydrogen peroxide to form in the molecule: The bleaching detergent composition according to any one of claims 1 to 3, which is an organic peracid precursor that produces an organic peracid having the formula: