JP2635288B2 - Bleach composition and bleach detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to powder or granular bleach compositions and bleach detergent compositions. More specifically, the present invention relates to a powdery or granular bleaching agent composition and a bleaching detergent composition which are excellent in bleaching performance and prevent color and pattern from being faded.

[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 smell. Oxygen bleaches without these drawbacks have recently become very popular. As the oxygen bleaching agent, sodium percarbonate and sodium perborate are particularly used as bleaching bases in terms of bleaching performance and stability.

However, the oxygen bleaching agent has a lower bleaching power than the chlorine bleaching agent, and various bleaching activators are used in combination. Representative bleach activators include tetraacetylethylenediamine, acetoxybenzenesulfonate,
Tetraacetylglycolyluril, glucose pentaacetate and the like have been used.

JP-A-59-22999 discloses a peroxygen bleaching compound and a compound of the general formula

[0005]

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Wherein R is an alkyl group having about 5 to about 18 carbon atoms, and the longest linear alkyl chain extending from the carbonyl carbon and containing the carbonyl carbon has about 6 to about 10 carbon atoms. And L is a leaving group, the conjugate acid of which has a pKa in the range of about 6 to about 13), the hydrogen peroxide produced by the peroxygen bleaching compound versus the bleaching activity. Bleach compositions are disclosed wherein the molar ratio of the agent is greater than about 1.5.
The publication states that this bleaching composition provides a very effective and efficient surface bleaching of fabrics, whereby stains and / or stains are removed from the fabrics.

[0007] However, the above-mentioned composition is excellent in bleaching performance, but when the composition is in the form of powder or granules,
If the bleaching treatment is performed in a state in which the composition is in direct contact with clothing such as a colored pattern until the composition is dissolved, that is, if the concentration of the bleaching activator is locally high, the clothing of the colored pattern is used. Has been found to be partially bleached and the mottled colored portions.

Accordingly, an object of the present invention is to provide a powdery or granular bleaching composition or a bleaching detergent composition which is excellent in bleaching performance and capable of suppressing the fading of the color of patterned textiles. It is to provide.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, as a hydrogen peroxide emitting body that generates hydrogen peroxide in an aqueous solution, sodium percarbonate and a bleaching activator concentration were used. It has been found that a powdery or granular bleaching agent composition or a bleaching detergent composition obtained by blending a bleaching activator having a specific relationship with an organic peracid generation rate can solve the above-mentioned problems. The invention has been completed.

That is, the present invention provides the following components (a) to (c)
It is intended to provide a powder or granular bleach composition containing the components. (a) Component: sodium percarbonate 0.1 to 99% by weight (b) Component: Bleaching activator 0.1 to 95% by weight satisfying the following conditions (i) and (ii) [Condition (i)] Water temperature 25 ° C, In a reaction system of 1 liter of water using a 1 liter beaker having an inner diameter of 120 mm, 0.003% by weight of (b)
After reacting the component and sodium percarbonate three times in weight ratio with respect to the component (b) in a cylindrical magnetic stirrer piece having a diameter of 10 mm and a long diameter of 30 mm under stirring at a rotation speed of 100 rpm for 20 minutes. Organic peracid generation rate [(molar concentration of organic peracid measured by iodine titration method) × 100 / (molar concentration of component (b) initially added)] is 20% or more. [Condition (ii)] In a reaction system of 1 liter of water using a 1 liter beaker having a water temperature of 25 ° C. and an inner diameter of 120 mm, 0.03% by weight of the component (b) and the weight ratio with respect to the component (b). A three-fold amount of sodium percarbonate was reacted with a cylindrical magnetic stirrer piece having a diameter of 10 mm and a long diameter of 30 mm for 20 minutes under stirring at a rotation speed of 100 rpm for 20 minutes to produce an organic peracid [(measured by an iodometric method. (Molar concentration of organic peracid) × 100 / (molar concentration of component (b) initially added)] is 40% or less. (c) Ingredient: less than 10% by weight of surfactant.

Further, the present invention provides a powdery or granular bleaching detergent composition containing the following components (a) to (c). (a) Component: sodium percarbonate 0.1 to 60% by weight (b) Component: Bleaching activator 0.1 to 50% by weight that satisfies the above conditions (i) and (ii) Component (c): Surfactant 10 to 60% by weight (provided that the proportion of the nonionic surfactant in the component (c) is 50% by weight or less in all the surfactants).

Hereinafter, the present invention will be described in detail.

[I] Bleach composition <Component (a)> In the present invention, the component (a) is sodium percarbonate generally known as a peroxide that releases hydrogen peroxide in an aqueous solution. is there.

In general, hydrogen peroxide reacts with a bleach activator to produce an organic peracid. As a hydrogen peroxide emitter,
Sodium percarbonate, sodium peroxide adduct tripolyphosphate, sodium peroxide adduct pyrophosphate, urea-hydrogen peroxide adduct, or _{4Na 2 SO 4 · 2H 2 O} 2 ·
NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide and the like are known.As the component (a) of the present invention, sodium percarbonate is (b) Necessary in combination with the components, for example, in a combination system with sodium perborate, excellent bleaching power cannot be obtained.

The sodium percarbonate which is the component (a) of the present invention preferably satisfies the following condition (iii). [Condition (iii)] 1000 ml of ion exchanged water at 20 ° C is 120 mm in inner diameter
Into a cylindrical beaker, and stirring at 100 rpm with a cylindrical magnetic stirrer piece with a diameter of 10 mm and a length of 30 mm, the average particle diameter is 200-710 μm, and 350 μm.
After the addition of 1 g of sodium percarbonate in which particles having an average particle size of m ± 150 μm occupy 80% by weight or more, immediately after the addition of sodium percarbonate when the conductivity of the solution was measured, the maximum value of the conductivity was 80%. % Is the dissolution time, and the dissolution time is 15 to 100 seconds.

Conventionally, sodium percarbonate has been found to have the advantage of being more excellent in solubility in cold water than sodium perborate. However, in the present invention, sodium percarbonate has a relatively high solubility in view of the dispersibility of the component (b). Those having a low dissolution rate are preferred. However, if the dissolution rate under the condition (iii) exceeds 100 seconds, excellent bleaching power cannot be obtained.

The sodium percarbonate having a dissolution rate as defined in the above condition (iii) can be coated with, for example, sodium percarbonate with a polymer or an inorganic salt, or granulated with a small particle size to increase the density. It can be easily obtained by such a method.

The component (a) having a particle size of 200 to 710 μm has a particle size of 70% by weight or more, preferably 90% by weight or more of the total sodium percarbonate particles. It is preferable in terms of improving stability and bleaching power.

As the component (a) used in the present invention, a granulated product of the component (a) containing a conventionally known stabilizer, dissolution accelerator, and in some cases a chelating agent is used. Is also possible.

<Component (b)> A bleach activator satisfying the above conditions (i) and (ii) is used in the powder or granular bleach composition of the present invention.

Examples of the bleach activator satisfying the above conditions include the following general formula (I)

[0022]

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Wherein R is an alkyl group having 11 to 17 carbon atoms in the longest linear carbon chain and having 11 to 23 carbon atoms, and L is a leaving group. And more preferably a compound represented by the following general formula (I-1).

[0024]

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[Wherein, R is as defined above.

X, Y: same or different, H, -SO ₃ M or
-COOM (where M is a cation or H that confers water solubility on the bleach activator) m: a number from 0-5. Here, examples of the M group include alkali metal salts (such as lithium, sodium and potassium salts), ammonium salts and organic amine salts (such as mono-, di- or triethanolamine, morpholine, ethylamine, butylamine, diethylenetriamine, and polyethyleneimine). Is mentioned.

More preferably, a compound represented by the following formula (I-2) is exemplified.

[0028]

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[In the formula, R ¹ represents a straight-chain alkyl group having 11 to 15 carbon atoms, M ¹ represents Na or K. Here, examples of the compound represented by the formula (I-1) or (I-2) are as follows.

[0030]

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The compound groups (I) and (I-
1) to (I-7) satisfy the above conditions (i) and (ii).

In general, the available oxygen concentration in sodium percarbonate used in the field of bleach is 12 to 13% by weight, and the available oxygen concentration is 12 to 13% by weight even in the conditions (i) and (ii).
Use those. The available oxygen concentration in sodium percarbonate is measured by the following method. The effective oxygen concentration in the conditions (i) and (ii) is the concentration of oxygen atoms derived from hydrogen peroxide released when the component (a) is dissolved in ion-exchanged water, expressed as a percentage by weight. .

・ Measurement method of effective oxygen concentration Put 500 ml of ion-exchanged water into a 500 cc tall beaker,
After adding the desired sodium percarbonate and stirring for 10 minutes,
After allowing to stand for 5 minutes, sample with a 20 ml whole pipette and place in a 200 ml Erlenmeyer flask. Then, 20 ml of a 20% sulfuric acid aqueous solution is added. The solution was titrated with a 1 / 10N aqueous potassium permanganate solution, and the time when the color became light red was determined as the end point. This reaction is represented as follows: 2MnO ₄ ^- + 5H ₂ and ^{_{O 2 + 6H + → 2Mn 2}} + + 5O 2 + 8H 2 O potassium permanganate titration, than the added amount of sodium percarbonate, determine the effective oxygen concentration in the sodium percarbonate.

Under the above conditions, the bleaching activator has a
The reason why the organic peracid generation rate of the 003% by weight aqueous solution is 20% or more is that if it is less than this, the bleaching performance is not sufficient at a normal washing concentration.

The reason why the organic peracid generation rate of the component (b) of the present invention in a 0.03% by weight aqueous solution thereof is 40% or less is that the component (b) exceeding this value can be used even at a high concentration. This is because local acid bleaching tends to occur due to generation of peracid, which causes uneven bleaching. For example, linear sodium hexanoyloxybenzenesulfonate and linear sodium octanoyloxybenzenesulfonate disclosed in JP-A-59-22999 have an organic peracid generation rate of 0.03% by weight of an aqueous solution thereof. The value exceeds 40%, and the fading of the color of the color or patterned textile product cannot be sufficiently suppressed.

In order to satisfy the above conditions (i) and (ii), it is considered that a compound having a high affinity between alkyl groups and generating a diacyl peroxide is preferable. ) To 11 to 11 carbon atoms such as (I-7)
Those having an active species containing a linear alkyl group at 15 are preferred and effective.

<Component (c)> The component (c) of the bleaching composition of the present invention.
The components are surfactants, various anionic surfactants,
Nonionic surfactants, cationic surfactants, and amphoteric surfactants can be blended.

(1) A linear or branched alkylbenzene sulfonate having an alkyl group having an average of 10 to 18 carbon atoms.

(2) having a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and having an average
0.5 to 8 moles of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.
Alkyl or alkenyl ether sulfates added in a ratio of 1 or in a ratio of ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1.

(3) An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms.

(4) An olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(5) Alkanesulfonates having an average of 10 to 20 carbon atoms in one molecule.

(6) A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule.

(7) having an alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, and having an average of 0.5 to 8 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 in one molecule. 9.9 / 0.1 or ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9
/ Alkyl or alkenyl ether carboxylate added at a ratio of /0.1.

(8) α-Sulfo fatty acid salts or esters represented by the following general formula:

[0046]

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Wherein Y represents an alkyl group having 1 to 3 carbon atoms or a counter ion. Z: indicates a counter ion. R ^10: an alkyl group or alkenyl group having 10 to 20 carbon atoms. Here, examples of the counter ion of the anionic surfactant include alkali metal ions such as sodium and potassium.

(9) A polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms and having 1 to 30 mol of ethylene oxide added thereto.

(10) Polyoxyethylene alkyl phenyl ether having an alkyl group having an average of 6 to 12 carbon atoms and having 1 to 25 mol of ethylene oxide added thereto.

(11) Polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average of 10 to 20 carbon atoms and having 1 to 20 mol of propylene oxide added thereto.

(12) Polyoxybutylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms and having 1 to 20 mol of butylene oxide added thereto.

(13) A nonionic activator having an alkyl group or alkenyl group having an average of 10 to 20 carbon atoms and having a total of 1 to 30 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added thereto (ethylene The ratio of oxide to propylene oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1).

(14) A higher fatty acid alkanolamide represented by the following general formula or an alkylene oxide adduct thereof.

[0054]

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[Wherein, R ¹¹ represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. R ^{12 represents} H or a CH ₃ group. n: Indicates the number of 1 to 3. m: represents a number from 0 to 3. (15) A sucrose fatty acid ester comprising a fatty acid having an average carbon number of 10 to 20 and sucrose.

(16) Fatty acid glycerin monoester consisting of a fatty acid having an average of 10 to 20 carbon atoms and glycerin.

(17) An alkylamine oxide represented by the following general formula.

[0058]

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[Wherein, R ¹³ represents an alkyl or alkenyl group having 10 to 20 carbon atoms. R ¹⁴ and R ¹⁵ each represent an alkyl group having 1 to 3 carbon atoms. (18) "Pluronic" obtained by condensation of ethylene oxide
Non-ionic surfactant under the trade name.

(19) A cationic surfactant represented by the following general formula.

[0061]

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[Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ : at least one of them represents an alkyl or alkenyl group having 8 to 24 carbon atoms, and the other represents an alkyl group having 1 to 5 carbon atoms. Show. X ^{1 represents a} halogen ion or metsulfate. ]

[0063]

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[Wherein, R ¹⁶ , R ¹⁷ , R ¹⁸ and X ^{1 have} the same meanings as above. ]

[0065]

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[Wherein, R ¹⁶ , R ¹⁷ , X ^{1 have} the same meaning as described above. R ²⁰ represents an alkylene group having 2 to 3 carbon atoms. p: Indicates the number of 1 to 20. (20) Sulfobetaine or carbobetaine represented by the following general formula:

[0067]

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Wherein R ²¹ represents an alkyl group having 8 to 22 carbon atoms. R ²² and R ²³ each represent an alkyl group having 1 to 3 carbon atoms. R ²⁴ represents an alkyl group having 1 to 5 carbon atoms which may contain a hydroxy group. D: represents an -NHCO- group or a -CONH- group. E: represents an alkylene group having 1 to 5 carbon atoms. a, b: 0 or 1, and when a = 0, b = 0 and a
When = 1, b = 1. Y ^-: -SO ₃ ^- or -COO ^- shows the. In the above formula (20), R ²¹ is an alkyl group having 8 to 22 carbon atoms, particularly preferably an alkyl group having 12 to 18 carbon atoms.
R ²² and R ²³ are an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. R ²⁴ is preferably a propylene group or a hydroxypropylene group in the case of sulfobetaine, and is preferably an alkylene group having 1 to 5 carbon atoms in the case of carbobetaine. In the case of carbobetaine, the D group is a -NHCO- group,
Compounds in which the E group is a propylene group (a = b = 1) are particularly preferred.

<Bleach composition> In the powder or granular bleach composition of the present invention, the component (a) is contained in the composition in an amount of 0.1 to 99% by weight, preferably 10 to 95% by weight, more preferably 30 to 90% by weight.
% By weight. Further, the component (b) is 0.1 to
95% by weight, preferably 0.3-70% by weight, more preferably
0.5 to 50% by weight is blended.

In the bleaching composition of the present invention, the molar ratio of (hydrogen peroxide) / (component (b)) formed by the component (a) is preferably from 2.5 to 50, more preferably from 2.5 to 20. From the viewpoint of bleaching performance and economy, the molar ratio is preferably within the above range.

In the bleaching composition of the present invention, (c)
The components are present in the composition in less than 10% by weight.

The bleaching composition of the present invention comprises the component (a)
In addition to the component (b) and the component (c), for example, the following components usually added to a bleaching composition, a bleaching detergent composition or a detergent composition can be added.

[1] Divalent metal ion scavenger One or more builder components of the following various alkali metal salts and alkanolamine salts can be contained in an amount of 1 to 50% by weight.

(1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate.

(2) ethane-1-1.1-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
-Salts of phosphonic acids such as 2-dicarboxy-1 -2-diphosphonic acid and methanehydroxyphosphonic acid.

(3) Salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

(4) Salts of amino acids such as aspartic acid, glutamic acid and glycine.

(5) nitrilotriacetate, iminodiacetic acid,
Aminopolyacetates such as ethylenediaminetetraacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate, triethylenetetramine hexaacetate, and diencholate.

(6) Polymer electrolytes such as polyacrylic acid, polyfumaric acid, polymaleic acid, poly-α-hydroxyacrylic acid, polyacetal carboxylic acid and salts thereof.

(7) Diglycolic acid, oxydisuccinic acid,
Organic acid salts such as carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid. Alkali metal salts are preferred as salts.

(8) Aluminosilicates represented by zeolite A.

It is preferable that the above-mentioned surfactant and / or builder be incorporated in the composition in a total amount of 1 to 60% by weight.

[2] Alkaline agent or inorganic electrolyte
~ 50% by weight silicates, carbonates, sulfates. Alkali metals are preferred as salts.

[3] 1 to 10% by weight of a re-contamination inhibitor Polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose.

[4] 1 to 10% by weight of enzyme Protease, lipase, amylase, cellulase.

[5] 1-10% by weight of a fluorescent dye, 4,4'-bis- (2-sulfostyryl) -biphenyl salt,
4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (stilphenyl) naphthothiazole derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (tri Azinylamino) stilbene disulfonic acid derivatives.

[6] 0.1 to 10% by weight of a peroxide stabilizing agent Magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium hydroxide and sodium silicate Silicates.

[7] 0.1 to 5% by weight of fragrance and pigment.

Next, the bleaching detergent composition of the present invention will be described.

[II] Bleaching detergent composition <Component (a)> In the powder or granular bleaching detergent composition of the present invention, as the component (a), the bleaching agent composition described in the above [I] is used. Is used. In this case, it is also possible to use a granulated component (a) containing a conventionally known stabilizer, dissolution accelerator, and optionally a chelating agent.

<Component (b) and Component (c)> In the powder or granular bleaching detergent composition of the present invention, the component (b)
As (c), those described in the above-mentioned bleach composition [I] are used.

Used in the bleaching detergent composition of the present invention
Examples of the surfactant (c) include the following, but are not limited thereto.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate,
α-olefin sulfonate, alkane sulfonate,
Saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphates or salts thereof, and the like. Anionic surfactants suitable for use in the present invention include
Alkylbenzene sulfonate of 10-18, or carbon number
It is an alkyl sulfate of 10-18. The counter ion is preferably a sodium, potassium or ammonium salt, and particularly preferably a potassium or sodium salt. As the nonionic surfactant, for example, polyoxyalkylene alkyl or alkenyl ether having a total of 10 to 18 carbon atoms,
Examples include polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide, or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoside, fatty acid glycerin monoester, and alkylamine oxide. In the present invention, in particular, the total carbon number is 12 to
A polyoxyalkylene alkyl or alkenyl ether having an ethylene oxide addition mole number of 16 and 5 to 15 is effective for oil stains and is preferred.

In addition, betaine-type amphoteric surfactants, sulfonic acid-type amphoteric surfactants, phosphate-based surfactants,
You may mix | blend a cationic surfactant etc.

<Bleaching detergent composition> In the bleaching detergent composition of the present invention, the component (a) is 0.1 to 60% by weight of the composition,
Preferably, the content is 1 to 40% by weight. (a) If the compounding amount of the component is less than 0.1% by weight, it is difficult to generate organic peracid, while if it exceeds 60% by weight, the bleaching effect does not change and the degree of freedom of mixing is limited. You. In the bleaching detergent composition of the present invention, the component (b) is contained in the composition in an amount of 0.1 to 50.
%, 0.5 to 30% by weight.

The mixing ratio of the component (a) and the component (b) at the time of mixing is as follows:
The molar ratio of hydrogen peroxide generated from the hydrogen peroxide emitter [component (a)], which is an essential component, to the organic peracid precursor [component (b)] is (a) / (b) = 3/1 to 1 / (b). It is preferably 30/1, more preferably 5/1 to 20/1. If the molar ratio is less than 3/1, the performance of the organic peracid precursor will not be sufficiently exhibited, and even if it is more than 30/1, it will not only be effectively saturated but also reduce the flexibility of mixing. This is undesirable.

The total amount of the surfactant (c) in the bleaching detergent composition of the present invention is 5 to 60% by weight in the composition, preferably
5 to 40% by weight. In the composition of the present invention, a surfactant as a detergent and a penetrant is essential, and unless it is incorporated in the composition in an amount of 6% by weight or more, it cannot function as a cleaning base.

When a large amount of the nonionic surfactant that can be blended in the present invention is blended, the organic peracid precursor having the above characteristics is solubilized in a nonionic solution, and the organic peracid precursor is dissolved. It is considered that since the reaction site is blocked, hydrogen peroxide and the organic peracid precursor hardly react with each other, and the bleaching performance is significantly reduced. Therefore, the amount of nonionic surfactant in the total surfactant [component (c)] is 50% by weight.
Or less, preferably 35% by weight or less.

The residue of the bleaching detergent composition of the present invention includes a chelating agent, an alkali agent, a dispersant and the like. For example, alkali agents such as silicates, carbonates and sesquicarbonates, extenders such as sodium sulfate, zeolite (aluminosilicate), orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetic acid Examples include divalent metal ion scavengers such as salts, citrates, and isocitrates. Further, usually, the following small amount added components are blended. For example, recontamination inhibitors such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, and polyacrylate, enzymes such as protease, esterase, lipase, and cellulase, caking inhibitors, peroxide stabilizers, antioxidants, and fluorescence Dyes, bluing agents, light-activated bleaching agents, fragrances and the like, and more specifically, those described in (I) Bleaching agent composition.

[0100]

The bleaching composition or bleaching detergent composition provided by the present invention not only exhibits excellent bleaching effect,
Even when used at a high concentration, the color of the textile product of the color / pattern does not fade.

[0101]

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

Synthesis Examples <Synthesis of Compounds (I-3) to (I-5) and Comparative Compound> (1) Synthesis of Compound (I-3) Sodium p-phenolsulfonate previously dehydrated
100 g (0.46 mol) of dimethylformamide (DMF) 300 g
Lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer, and the reaction was carried out for 3 hours after completion of the addition. DMF was removed under reduced pressure (0.5 to 1 mmh).
g), distilled off at 100 ° C., washed with acetone, and recrystallized in a water / acetone (= 1/1 mol) solvent. 85% yield. (2) Synthesis of Compound (I-4) In the synthesis of Compound (I-3), myristic acid chloride is used for alkyl instead of lauric acid chloride. 75% yield. (3) Synthesis of Compound (I-5) In the synthesis of the above (I-3), a dehydrate of sodium p-phenolcarboxylate is used in place of sodium p-phenolsulfonate. 65% yield. (4) Synthesis method of sodium hexanoyloxybenzenesulfonate In the synthesis of the above (I-3), sodium hexanoyloxybenzenesulfonate was prepared in the same manner except that hexanoic acid chloride was used as the alkyl source instead of lauric acid chloride. I got 87% yield. (5) Method of synthesizing sodium octanoyloxybenzenesulfonate In the synthesis of the above (I-3), sodium octanoyloxybenzenesulfonate was prepared in the same manner except that octanoic acid chloride was used as the alkyl source instead of lauric acid chloride. I got 87% yield.

Test Example <Measurement of Organic Peracid Production Rate of Bleaching Activator> The bleaching activator was previously dissolved in ion-exchanged water while heating to make the total volume 100 ml. The amount of bleach activator added at this time is 0.03
g (a) or 0.3 g (a). These bleach activator solutions (a) or (b) and sodium percarbonate 0.09 g
100 ml of a solution of (I) or 0.9 g (II) dissolved at 25 ° C
800 ml in a cylindrical 1 liter beaker with an inner diameter of 120 mm
Aqueous sodium percarbonate solution (I) was filled with a bleach activator aqueous solution (a) and sodium percarbonate aqueous solution (II) was filled with a bleach activator aqueous solution (a) while filled with ion-exchanged water (25 ° C.).
And keep it at 25 ° C, diameter 10mm, length 30
mm at 100 rpm with a cylindrical magnetic stirrer piece
Stir for 20 minutes. And 10 ml of 0.3% catalase aqueous solution
The mixture was further stirred for 2 minutes, and the concentration of the organic peracid was measured by an iodine titration method. Table 1 shows the results.

[0104]

[Table 1]

Example 1 8 cm × 32 cm from underwear (made of cotton) which was repeatedly worn and turned yellow
Ten cm samples were prepared. Then, the samples were cut in half to produce 10 sets of half-split samples.

Commercial heavy detergent (surfactant concentration 40% by weight)
0.0833% by weight of sodium percarbonate (particle size 300-71
0 μm occupies 80% by weight or more, the dissolution rate under the above condition (iii) is 30 seconds) is 0.0083% by weight, and the linear sodium hexanoyloxybenzenesulfonate is 0.0042% by weight.
% By weight of sodium poly-α-hydroxyacrylate (PHAS) was added to ion-exchanged water so as to be 0.0042% by weight (comparative product). Using one of the above half-split samples with this detergent solution, the plate was washed with a tergotometer at 100 rpm at 20 ° C. for 10 minutes, and then washed with water and dried.

Next, the same commercially available heavy-duty detergent was added in an amount of 0.0833% by weight, 0.0083% by weight of sodium percarbonate, and 0.0042% by weight of the bleaching activator (I-3) shown in Table 1 (the present invention). ) And the other half of the half-split sample was washed similarly.

The cleaned samples are compared on the left and right side by side on a white mount, and the degree of cleaning of 10 pairs of samples is visually judged (three judges). The judgment was made according to the following criteria.・ Scoring criteria The degree of dirt washed with the product of the present invention is clearly superior to the degree of dirt washed with the comparative product… +2 Somewhat less… +1 Little difference… 0 Little worse… − 1 In case of inferiority ... Score as -2. Aggregate the results of the three students
(Scheffe) paired comparison method (method according to JIS K 3371)
Then, a significant difference test was performed. The results are shown in Tables 2 and 3.

[0109]

[Table 2]

[0110]

[Table 3]

The results in the table show that the product of the present invention is superior to the comparative product in bleaching detergency (5% significance level). Further, a bleaching activator (I
Bleach activator (I-4), (I-5) instead of -3)
Was used to conduct a comparative experiment with linear sodium hexanoyloxybenzenesulfonate. The results for (I-4) are shown in Tables 4 and 5, and the results for (I-5) are shown in Tables 6 and 5.
FIG.

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

[Table 6]

[0115]

[Table 7]

The results in the table show that the product of the present invention has a significant difference and is superior in bleaching detergency as compared with the comparative product.

Example 2 A decolorization test shown below was performed. Naphthol dye on petri dish (dipping agent: Naphthol AS, developer: Fast Red GB
Prepare a cotton cloth (10cm x 10cm) dyed with ase). Place 0.1 g of the powder bleach composition shown in Table 8 on the cloth and further
5 ml of tap water at 20 ° C. is added over the powder. After 30 minutes, the cloth was washed and dried, and the degree of decolorization was evaluated by the following four-step evaluation. Table 8 shows the results. Not bleached at all ◎ ◎ A little faint, but not at all annoying ・ ・ ・ ○ Partially bleached ・ ・ ・ △ Decolorization spreads over the whole cloth… ×

[0118]

[Table 8]

Example 3 A bleaching detergent composition having the composition shown in Table 9 was prepared, and its bleaching test and performance confirmation for yellowing underwear were performed. Decolorization test A decolorization test was performed by the following method. Naphthol dye (Naphthol AS, developer F)
A cotton cloth (10 cm × 10 cm) dyed with astRed G Base) is prepared, 0.2 g of the bleaching detergent composition shown in Table 5 is placed on the cloth, and 5 ml of tap water at 20 ° C. is further added from above the powder. After a minute, the cloth was washed and dried, and the degree of decolorization was evaluated in the following four steps. Table 9 shows the results. Not decolorized at all ◎◎ It is a little thin but not bothersome ◎ ○ Partially decolorized ・ ・ ・ △ The cloth is decolorized entirely ・ ・ ・ × In addition, sodium percarbonate is sodium metaborate tetrahydrate Stable in detergent (2.5%) coated with salt was used.

[0120]

[Table 9]

Performance against Yellowing Underwear Repeatedly wearing yellowing underwear (made of cotton) is 8 cm × 8
Samples of 10 cm were prepared. Then, the samples were cut in half to make 10 sets of half-broken samples. Inventive product No. 1 of the bleaching detergent composition shown in Table 11 was added to water so as to have a concentration of 0.0833% by weight, and the above half-split sample was used at 100 rpm with a tergotometer at 25 ° C. for 15 minutes. After washing, it was washed with water and dried. The washed samples are compared on the left and right sides on a white mount, and the degree of washing of the 10 samples is visually judged (three judges). The judgment was made according to the following criteria. -Scoring standard The degree of stain removal washed with the product of the present invention is clearly inferior to the degree of stain removal washed with the comparative product. -2 Slightly inferior ...- 1 There is almost no difference ... 0 Slightly superior ... 1 Clearly Excel ... Score as 2 Aggregate the results of the three students
(Scheffe) pairwise comparison method was used to perform a significant difference test (JIS K
See Reference Example of 3371 Evaluation Method). The results are shown in Tables 10 and 11.

[0122]

[Table 10]

[0123]

[Table 11]

As a result of an f-test from the analysis of variance table, it can be seen that the product of the present invention is superior to the comparative product in bleaching detergency (significant level 5%). In addition, even when the products (2) and (3) of the present invention are used in the same manner as described above, the product of the present invention has a significant difference as compared with the comparative product, and has a superior bleaching detergency. confirmed.

Example 4 <Preparation of Curry-Contaminated Cloth> House food industry was added to 1 liter of water.
Add 200g of curry roux made by Co., Ltd. and boil for 25 minutes.
Then, stir well to bring the total volume to 1 liter. Temperature 45
℃, put it in a vat, put a 10 × 55cm desizing cloth
It is immersed every second, passed through a roller and air dried to obtain a curry-contaminated cloth.

<Cleaning / Bleaching of Curry-Contaminated Cloth> The curry-contaminated cloth obtained above is washed with a bleaching detergent composition having the composition shown in Table 12. The cleaning conditions for the curry-contaminated cloth at this time are as follows. Temperature; 20 ° C Bath ratio; 1/60 Detergent concentration: 0.08333% (using tap water) Targotometer 10 minutes <Measurement of washing bleaching rate> Self-recording color meter (Shimadzu Co., Ltd.) Was determined by the following formula, and the washing bleaching ratio was determined by the following formula to evaluate the bleaching performance.

[0127]

(Equation 1)

The cleaning bleaching ratio was determined from the above formula, and the cleaning power was evaluated in comparison with a reference blended product containing no organic peracid precursor. The comparison criteria are as follows. …: Bleaching rate of more than 5% is higher than that of the reference composition. ○: Bleaching rate of 3 to 5% is better than that of the reference composition. Δ: Bleaching rate of not more than 3% but higher than that of the reference composition. ×: Same as the reference compound or inferior in bleaching rate. The same sodium percarbonate as in Example 3 was used.

[0129]

[Table 12]

Note) Those marked with * are the products of the present invention, and No. 7 is the standard blended product. 1) Oil-absorbing carrier: Toksil AL-1 (amorphous silica manufactured by Tokuyama Soda Co., Ltd.) Example 5 A cleaning evaluation experiment of a contaminated cloth was performed with the composition shown in Table 13.
Note that the hydrogen peroxide emitters shown in Table 13 were those shown in Table 14.

Preparation of Soiled Cloth 0.03 g of bilirubin (reagent manufactured by Merck) was dissolved in 100 cc of chloroform, and 0.06 cc of the solution was placed on an 8 cm × 8 cm cotton cloth.
Was dripped so as to be uniform, and after drying, the reflectance was measured at 420 nm, followed by washing by the following washing method. After washing
The reflectance was measured to determine the cleaning rate. The cleaning rate was determined by the following equation.

[0132]

(Equation 1)

Washing method Put 500 cc of ion-exchanged water into a 1 liter beaker,
Was stirred at 100 rpm for 1 minute, then 5 contaminated cloths were put in, and immersed for 30 minutes. In addition,
The concentration of the bleaching detergent composition was 5 g / 5 liter.

[0134]

[Table 13]

Note) Nonionic surfactant: polyoxyethylene (average number of moles of ethylene oxide added = 7) alkyl (C ₁₂ -C ₁₄ ) ether The dissolution rate of the hydrogen peroxide releasing substance was also examined. The results are shown in Table 14.

Method for Measuring Dissolution Rate of Hydrogen Peroxide Emitting Body The measurement of the dissolution rate of the hydrogen peroxide emitting body was carried out in accordance with the above condition (iii). In other words, 1000 ml of ion exchange water at 20 ° C
Place in a 120 mm cylindrical beaker and stir at 100 rpm with a cylindrical magnetic stirrer piece 10 mm in diameter and 30 mm in length. There, a hydrogen peroxide emitter (see Table 14) whose average particle diameter is in the numerical value shown in Table 14 and whose particles having an average particle diameter of 350 µm ± 150 µm account for 80% by weight or more. 1) was added. The change in conductivity of the solution at that time was measured using a conductivity meter “CM-60S” manufactured by Toa Denpa Kogyo Co., Ltd. and a conductivity cell “CG-511B” manufactured by Toa Denpa Kogyo. The time that the conductivity had until immediately after the addition of sodium percarbonate to reach 80% of the maximum value was taken as the dissolution time.

[0137]

[Table 14]

In Table 14, Sample No. β is the sodium percarbonate used in Example 3. From the results in Table 14, the condition (ii
It can be seen that when sodium percarbonate satisfying i) is used, an excellent bleaching effect can be obtained although the dissolution rate is lower than that of sodium perborate.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // (C11D 7/60 7:18 7:34 7:26) (72) Inventor Satoshi Suzuki Tochigi 3-4-15 Utsunomiya City Tomatsuri (56) References JP-A-4-332796 (JP, A) JP-A-3-115496 (JP, A) JP-A-2-77500 (JP, A)

Claims (10)

(57) [Claims] A powdery or granular bleaching composition comprising the following components (a) to (c): (a) Component: sodium percarbonate 0.1-99% by weight (b) Component: Bleaching activator 0.1-95% by weight satisfying the following conditions (i) and (ii) [Condition (i)] Water temperature 25 ° C, In a reaction system of 1 liter of water using a 1 liter beaker having an inner diameter of 120 mm, 0.003% by weight of the component (b) and sodium percarbonate in a weight ratio of 3 times the amount of the component (b) were added. Organic peracid generation rate after reacting with a cylindrical magnetic stirrer piece having a diameter of 10 mm and a major axis of 30 mm at a rotation speed of 100 rpm for 20 minutes [(molar concentration of organic peracid measured by iodine titration method) × 100 / (Molar concentration of component (b) initially added)] is 20% or more. [Condition (ii)] 0.03% by weight in a reaction system of 1 liter of water using a 1 liter beaker having a water temperature of 25 ° C. and an inner diameter of 120 mm.
Concentration of the component (b) and sodium percarbonate in a weight ratio 3 times the weight of the component (b) were stirred with a cylindrical magnetic stirrer piece having a diameter of 10 mm and a long diameter of 30 mm at a rotation speed of 100 rpm.
The organic peracid production rate after the reaction for 20 minutes [(molar concentration of organic peracid measured by iodometric titration) × 100 / (molar concentration of component (b) initially added)] is 40% or less. thing. (c) Ingredient: less than 10% by weight of surfactant 2. The powder or granular bleach composition according to claim 1, wherein the component (b) is a compound represented by the following general formula (I). Embedded image [Wherein, R represents an alkyl group having 11 to 17 carbon atoms in the longest linear carbon chain and having 11 to 23 carbon atoms in total, and L represents a leaving group. ] 3. The powder or granular bleach composition according to claim 2, wherein the component (b) is a compound represented by the following general formula (I-1). Embedded image [Wherein, R represents the above-mentioned meaning. X, Y: same or different, H, —SO ₃ M or —COOM (where M is a cation or a cation that imparts water solubility to the bleach activator)
M: 0 to 5; ] 4. The powder or granular bleach composition according to claim 3, wherein the component (b) is a compound represented by the following general formula (I-2). Embedded image [Wherein, R ¹ represents a straight-chain alkyl group having 11 to 15 carbon atoms M ¹ : Na or K. ] 5. The bleaching composition according to claim 1, wherein the component (a) is sodium percarbonate satisfying the following condition (iii). [Condition (iii)] 1000 ml of ion exchanged water at 20 ° C is 120 mm in inner diameter
Into a cylindrical beaker, and stirring at 100 rpm with a cylindrical magnetic stirrer piece with a diameter of 10 mm and a length of 30 mm, the average particle diameter is 200-710 μm, and 350 μm.
After the addition of 1 g of sodium percarbonate in which particles having an average particle size of m ± 150 μm occupy 80% by weight or more, immediately after the addition of sodium percarbonate when the conductivity of the solution was measured, the maximum value of the conductivity was 80%. % Is the dissolution time, and the dissolution time is 15 to 100 seconds. 6. A powdery or granular bleaching detergent composition comprising the following components (a) to (c): (a) Ingredient: sodium percarbonate 0.1 to 60% by weight (b) Ingredient: Bleaching activator 0.1 to 50% by weight satisfying the following conditions (i) and (ii) [Condition (i)] Water temperature 25 ° C, In a reaction system of 1 liter of water using a 1 liter beaker having an inner diameter of 120 mm, 0.003% by weight of (b)
After reacting the component and sodium percarbonate three times in weight ratio with respect to the component (b) in a cylindrical magnetic stirrer piece having a diameter of 10 mm and a long diameter of 30 mm under stirring at a rotation speed of 100 rpm for 20 minutes. Organic peracid generation rate [(molar concentration of organic peracid measured by iodine titration method) × 100 / (molar concentration of component (b) initially added)] is 20% or more. [Condition (ii)] In a reaction system of 1 liter of water using a 1 liter beaker having a water temperature of 25 ° C. and an inner diameter of 120 mm, 0.03% by weight of the component (b) and the weight ratio with respect to the component (b). A three-fold amount of sodium percarbonate was reacted with a cylindrical magnetic stirrer piece having a diameter of 10 mm and a long diameter of 30 mm for 20 minutes under stirring at a rotation speed of 100 rpm for 20 minutes to produce an organic peracid [(measured by an iodometric method. (Molar concentration of organic peracid) × 100 / (molar concentration of component (b) initially added)] is 40% or less. Component (c): surfactant 10 to 60% by weight (provided that the proportion of nonionic surfactant in component (c) is 50% by weight or less in all surfactants) 7. The powder or granular bleaching detergent composition according to claim 6, wherein the component (b) is a compound represented by the following general formula (I). Embedded image [Wherein, R represents an alkyl group having 11 to 17 carbon atoms in the longest linear carbon chain and having 11 to 23 carbon atoms in total, and L represents a leaving group. ] 8. The powder or granular bleaching detergent composition according to claim 7, wherein the component (b) is a compound represented by the following general formula (I-1). Embedded image [Wherein, R represents the above-mentioned meaning. X, Y: same or different, H, —SO ₃ M or —COOM (where M is a cation or a cation that imparts water solubility to the bleach activator)
M: 0 to 5; ] 9. The powder or granular bleaching detergent composition according to claim 8, wherein the component (b) is a compound represented by the following general formula (I-2). Embedded image [Wherein, R ¹ represents a straight-chain alkyl group having 11 to 15 carbon atoms M ¹ : Na or K. ] 10. The bleaching composition according to claim 6, wherein the component (a) is sodium percarbonate satisfying the following condition (iii). [Condition (iii)] 1000 ml of ion exchanged water at 20 ° C is 120 mm in inner diameter
Into a cylindrical beaker, and stirring at 100 rpm with a cylindrical magnetic stirrer piece with a diameter of 10 mm and a length of 30 mm, the average particle diameter is 200-710 μm, and 350 μm.
After the addition of 1 g of sodium percarbonate in which particles having an average particle size of m ± 150 μm occupy 80% by weight or more, immediately after the addition of sodium percarbonate when the conductivity of the solution was measured, the maximum value of the conductivity was 80%. % Is the dissolution time, and the dissolution time is 15 to 100 seconds.