JPH1135978A - Detergent composition containing bleaching agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To substantially enhance cleaning and bleaching power by using a glycine-N-N'-diacetic acid derivative, a small amount of an anionic surfactant and an alkali agent with a system containing an oxygen type bleaching agent, a bleaching precursor and a nonionic surfactant. SOLUTION: A detergent composition containing a bleaching agent comprises 2-50 wt.% of a percarbonate or a perborate, 3-40 wt.% of a glycine-N,N'-diacetic acid derivative of formula I (wherein M is H, Na, K or NH4 and R is 1-18C alkyl group or an alkenyl group), 0.5-30 wt.% of a bleaching precursor of formula II (wherein R is a 5-23C alkyl group and L is a leaving group), 10-40 wt.% of a nonionic surfactant (A) having an HLB of 10.5-15.0 prepared by addition of an alkylene oxide on a 10-18C primary or secondary alcohol, 1/2-1/40, as a weight ratio of an anionic surfactant (B) to component A and 5-50 wt.% of an alkali agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bleach-containing detergent composition. More specifically, the present invention relates to a detergent composition having good bleaching power, containing an organic builder having a high hardness component blocking power.

[0002]

2. Description of the Related Art In daily life, various stains adhere to clothes and the like, but washing with a normal detergent alone does not provide sufficient detergency against so-called stains such as blood stains, food stains, and pigment stains of plants. I can not say. Since bleaching agents are very effective against these stains, attempts have been made to incorporate bleaching components into detergents. Bleaching components are roughly classified into oxygen-based and chlorine-based. Examples of the chlorine type include hypochlorous acid and dichlorocyanuric acid. This has problems in stability, smell and the like, is not suitable for detergent formulation, and has to be nervous to color and pattern due to its strong bleaching power.

[0003] For this reason, oxygen-based bleaching components such as percarbonate and perborate are used in powder detergents. Oxygen-based bleaching agents have little problem with colored or patterned products and have relatively good stability, but their bleaching power is not sufficient. Therefore, various bleach precursors for improving the bleaching power have been developed,
Concomitant use with oxygen-based bleach has been studied.

On the other hand, the main base of the detergent is a surfactant.
Surfactants emulsify, solubilize or disperse soil and serve an important role in removing soil from fibers. Surfactants incorporated in detergents can be broadly classified into those mainly containing anionic and those mainly containing nonionic. Nonionic surfactants have characteristics such as good hard water resistance, outstanding washing power of oily stains such as sebum stains, and very good biodegradability. Technical development of detergents mainly composed of nonionic surfactants has been actively conducted.

[0005]

However, in a bleaching system in which a detergent mainly composed of a nonionic surfactant and a bleaching precursor are used in combination, the bleaching precursor has a high affinity for the nonionic surfactant and a nonionic surfactant. Since the activator is strongly taken into micelles and hardly comes out of the micelles, there has been a problem that the amount of generated peracid is reduced and the bleaching power is greatly reduced.

[0006]

Means for Solving the Problems The present inventors have intensively studied a detergent mainly composed of a nonionic surfactant in order to solve the above problems. As a result, glycine-N- was added to the system containing bleach, bleach precursor and nonionic surfactant.
The present inventors have found that the combined use of an N'-diacetate derivative, a small amount of an anionic surfactant and an alkali agent can significantly improve the bleaching detergency, thereby completing the present invention.

That is, the present invention relates to (a) a percarbonate or perborate 2 to 50% by weight (b) a glycine-N-N'-diacetate derivative represented by the following general formula (1) 3 to 40% by weight %

[0008]

Embedded image

(Wherein M is selected from H, Na, K, and NH ₄ , and R is selected from an alkyl group or an alkenyl group having 1 to 18 carbon atoms.) (C) Formula (2) Bleaching precursor 0.5 to 30
weight%

[0010]

Embedded image

Wherein R is an alkyl group having 5 to 23 carbon atoms,
L is a leaving group. (D) Nonionic surfactant 10 to 40% by weight (e) Anionic surfactant (e) / (d) = 1/2 to 1/40
(Weight ratio) (f) A bleach-containing detergent composition containing 5 to 50% by weight of an alkaline agent.

In the present invention, a bleaching detergency is obtained by using a non-ionic surfactant having a low foaming as a main component instead of an anionic surfactant having a high foaming, and adding a specific proportion of the anionic surfactant to the non-ionic surfactant. Not only is improved, but also foaming during washing and cedar is suppressed. In particular, the bleaching detergency includes oxygen-based bleach (a), glycine-N-N'-
The combination of the diacetate derivative (b) and the bleach precursor (c) is greatly involved. In addition, as described above, in the case of a detergent mainly composed of a nonionic surfactant, when used in combination with a bleaching precursor, the bleaching precursor has a high affinity with the nonionic surfactant, and thus is strongly incorporated into micelles of the nonionic surfactant. However, the bleaching precursor is less likely to come out of the micelles and the amount of peracid is reduced, but as in the present invention, in a system in which an anionic surfactant is blended at a specific ratio with respect to a nonionic surfactant. Since the micelles become anionic, the anionic bleaching precursor also has an electrical repulsion, so it is easy to come out of the micelles, and the amount of peracid generated is reduced, and the bleaching detergency is improved. . Hereinafter, each component used in the present invention will be described.

[Component (a)] The available oxygen concentration in a percarbonate generally used in the field of bleaching agents, for example, sodium percarbonate is 8 to 16% by weight, and the available oxygen concentration in a perborate, for example, sodium perborate is used. The effective oxygen concentration is 8 to 16% by weight, depending on the concentration of the water of crystallization. In the present invention, (a)
A component having an effective oxygen concentration in this range is used as a component. The effective oxygen concentration is measured by the following method.

Method for measuring effective oxygen concentration 500 ml of ion-exchanged water is placed in a 1000 ml tall beaker,
Add the desired percarbonate or perborate, stir for 10 minutes, allow to stand for 5 minutes, sample with a 20 ml hole pipette, and place in a 200 ml Erlenmeyer flask. And 20
20 ml of aqueous sulfuric acid solution are 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 O 2}} + 6H + → 2Mn 2 + + 5O 2 + 8H 2 O and a potassium permanganate titration, than the added amount of percarbonate or perborate, percarbonate or perborate in Obtain the effective oxygen concentration of

The percarbonate used in the present invention includes sodium percarbonate, and the perborate includes sodium perborate. Particularly, sodium percarbonate is more preferable in terms of bleaching performance. The component (a) is incorporated in the composition at 2 to 50% by weight, preferably 5 to 25% by weight.

[Component (b)] Glycine used in the present invention
The N—N′-diacetate derivative is represented by the general formula (1), wherein M in the formula (1) is selected from H 2, Na, K 2 and NH ₄ , and R 2 has 1 to 18 carbon atoms. Selected from the alkyl groups or alkenyl groups of When R is a methyl group, it has the most chelating ability and is suitable as the organic builder of the present invention. M is H,
Although Na and K are generally used, those that have been partially neutralized have the highest chelating power and a high effect of improving the bleaching / cleaning power. Those completely neutralized also show a sufficient effect of improving the bleaching detergency.

In the present invention, the component (b) glycine-N-
The N'-diacetate derivative is incorporated in the detergent composition in an amount of 3 to 40% by weight, preferably 5 to 20% by weight. If the amount of component (b) is out of this range, the detergency of the bleaching detergency is reduced. (b) The glycine-N-N'-diacetate derivative of the component is DE4319935A1, WO942942
1 and the like, and known compounds as builders. However, it is only known that it has a performance as a builder of a general detergent, and as in the present invention, a detergent containing an oxygen-based bleaching agent (a), a non-ionic For the system containing surfactant (d) as a main component and / or the combined system containing anionic surfactant having good detergency for mud and dirt in such an amount as to maintain the property of nonionic surfactant, (c) ) Component and (d) component,
It was not known at all how the glycine-N-N'-diacetate derivative as the component (b) contributes to the improvement of the bleaching detergency. In particular, it was not known at all that a combination of the compound of the general formula (3), particularly the compound of the general formula (4), among the bleaching precursors had a particularly excellent effect.

[Component (c)] The component (c) of the present invention is a bleaching precursor represented by the aforementioned general formula (2). In the general formula (2), R is an alkyl group having 5 to 23 carbon atoms, and L is a leaving group. The bleaching precursor (c) has the effect of further enhancing the effect of the bleaching agent (a). Since the bleaching precursor represented by the general formula (2) has an alkyl group (R), it has excellent bleaching detergency even for lipophilic stains. Among the bleaching precursors represented by the general formula (2), the following general formula (3)
The compound represented by has an excellent effect as a bleaching precursor.

[0019]

Embedded image

[Wherein, m is a number from 0 to 5, X and Y are the same or different and each represents hydrogen, -SO ₃ M, or -COOM. Where M 1 is a cation or H 2. R is the same as in the above formula (2). Among the compounds represented by the general formula (3), the compound represented by the following general formula (4) exhibits a more excellent bleaching activity effect.

[0021]

Embedded image

Wherein Z is -SO ₃ M or -COOM. R
, M are the same as in the above formula (3). Z can be either -SO ₃ M or -COOM, but -SO ₃ M has a somewhat better effect. In the general formulas (3) and (4), R is an alkyl group having 5 to 23 carbon atoms, preferably an alkyl group having 8 to 14 carbon atoms. In the case of an alkyl group having a large number of carbon atoms, the lipophilicity becomes too large, so that the effect on dirt having a large polarity is reduced. The effect on dirt is reduced.

The bleaching precursor of the component (c) is contained in the composition in an amount of 0.1%.
-25% by weight, preferably 1-10% by weight. Also, the bleaching precursor (c) was added in an amount of 0.1 to 100 parts by weight of the component (a).
It is desirable that the compounding amount be from 50 to 50 parts by weight, preferably from 1 to 25 parts by weight.

As the bleaching precursor, besides the component (c), tetraacetylethylenediamine, acetoxybenzenesulfonate, JP-A-59-22999, JP-A-63
JP-A-258447, JP-A-6-316700, an organic peracid precursor, or a metal catalyst in which a transition metal is stabilized with a sequestering agent can also be used.

[Component (d)] Examples of the nonionic surfactant of the component (d) include linear or branched primary or secondary alcohols having 10 to 18 carbon atoms and alkylene oxides such as ethylene oxide and propylene oxide. And the HLB value (calculated by the Griffin method) is 10.5-15.0, preferably 11.0-1.
It is preferable to set the value to 4.5. Polyoxyalkylene alkyl phenyl ether obtained by the same method, polyoxyalkylene sorbitan fatty acid ester,
Polyoxyalkylene glycol fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycol fatty acid esters, polyoxyalkylene higher fatty acid alkanolamides, and the above-mentioned HLB are also included therein. Biodegradability, safety,
In view of performance and the like, the former alkylene oxide adduct of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms is preferred. It is a nonionic surfactant that is liquid at room temperature. Therefore, an oil-absorbing carrier is added, and a nonionic surfactant is absorbed into the oil-absorbing carrier to improve the powder properties.

The nonionic surfactant (d) is incorporated in the detergent composition in an amount of 10 to 40% by weight, preferably 15 to 25% by weight. If the amount is more than this range, the powder properties of the detergent will be impaired. If the amount is too small, the cleaning performance is reduced.

[Component (e)] As the anionic surfactant of the component (e), a sulfuric ester salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, One or more selected from a sulfate salt of an ethoxylated alcohol, an alkylbenzene sulfonate having 8 to 18 carbon atoms in the alkyl group, a paraffin sulfonate, an α-olefin sulfonate and an α-sulfofatty acid alkyl ester salt. Two or more are preferred. (e) component is (d)
(E) / (d) = 1/2 to 1/30, preferably 1/3 to 1/15 (weight ratio) based on the components.

Although the nonionic surfactant alone has poor dyeing properties on the cotton of the fluorescent dye, this disadvantage can be improved by blending the above-mentioned amount of the anionic surfactant. A characteristic of nonionic surfactant-based detergents is that they have excellent detergency against sebum stains. As the anionic surfactant is added to the nonionic surfactant, the cleaning effect of sebum dirt gradually decreases, but the cleaning effect of inorganic particles such as clay by the anionic surfactant is improved. Is done. As a result, a system in which a nonionic surfactant and an anionic surfactant are blended at the above ratio maintains the cleaning effect particularly on sebum stains, and improves the cleaning effect on inorganic particle stains. Improves. If the amount of the anionic surfactant is more than 1/3 (weight ratio) relative to the amount of the nonionic surfactant, the cleaning effect on sebum stains is significantly reduced. When the nonionic surfactant and the anionic surfactant are blended in the above-mentioned specific blending ratio, the bleaching power is improved, as described above, because the nonionic surfactant molecules and the bleaching precursor in the nonionic surfactant micelles The affinity of the body molecules is due to the weakness of the anion-anion electrical repulsion caused by the entry of the anionic surfactant molecule, which makes it easier for the bleaching precursor molecule to exit the micelle.

In general, since the nonionic surfactant (d) is liquid, a higher fatty acid salt can be used for the purpose of improving powder properties, particularly, caking and bleeding of the liquid surfactant. In this case, the higher fatty acid salt is preferably a saturated fatty acid salt having 13 to 17 carbon atoms. When the number of carbon atoms is 18 or more, the solubility is reduced. When the number of carbon atoms is 12 or less, the solubility in water is increased, so that the effect of improving the powder properties is reduced. The higher fatty acid salt is incorporated in the detergent in an amount of 0 to 20% by weight. It is preferable to add 3 to 10% by weight. Since higher fatty acid salts having 13 to 17 carbon atoms have poor cleaning performance, the cleaning performance of the composition decreases when the amount of the higher fatty acid salt is increased.

[Component (f)] Examples of the alkali agent used in the present invention include inorganic alkali metal salts and polyphosphates. Specifically, the following (1) and (2) can be used. I can do it.

(1) Inorganic alkali metal salts sodium carbonate, potassium carbonate, sodium silicate [(Na ₂
O) _m (SiO ₂ ) _n , where m is 1 to 3 and n is 1 to 5], sodium bicarbonate, potassium bicarbonate, sodium sulfite, potassium sulfite, sodium sesquicarbonate, potassium sesquicarbonate, crystal And the like. Particularly, a crystalline silicate is preferred.

The crystalline silicate used in the present invention is preferably an alkali metal salt of silicic acid (SiO ₂ ). Among them, SiO ₂ / M ₂ O (where M represents an alkali metal) of an alkali metal silicate is preferred. Those having a ratio of 0.5 to 2.6 are preferably used. Crystalline silicate known conventionally SiO ₂ / M ₂ O is from 1.9 to 4.0
However, if this ratio exceeds 2.6, it may not be suitable for high-density detergent formulations.

The preferred crystalline silicate used in the present invention has the following composition. _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (5) ( wherein, M is Group Ia elements of the periodic table (particularly preferably K and / Or Na), and Me is an element of group IIa of the periodic table, II
One or a combination of two or more selected from group b elements, group IIIa elements, group IVa elements or group VIII elements (preferably M
g / Ca), y / x = 0.5-2.6, z / x = 0.01-
0.9, w = 0 to 20, and n / m = 0.5 to 2.0. The production method of the crystalline silicate represented by the general formula (5) can be referred to JP-A-7-89712.

Further, a crystalline silicate having the following composition can also be preferably used. M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (6) (wherein M represents an alkali metal (particularly preferably K and / or Na), x ′ = 1.5 to 2.6, y '= 0 to 20 (particularly preferably substantially 0). The crystalline silicate of the general formula (6) is disclosed in JP-A-60-227895 and Phys. Chem. Glasses. 7, 127-138 ( 1966), Z. Kristall
ogr., 129, 396-404 (1969). In addition, a powdery or granular product is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ).

In the present invention, the crystalline silicate represented by the general formula (5) and the crystalline silicate represented by the general formula (6) can be used alone or in combination of two or more. These crystalline silicates are preferably incorporated in the composition in an amount of 1 to 30% by weight, particularly preferably 3 to 15% by weight. Of the alkali agents to be incorporated in the composition, preferably 30 to 100% by weight, more preferably 70 to 100% by weight.
It preferably occupies ~ 100% by weight.

(2) Polyphosphate In the present invention, polyphosphates such as orthophosphate, metaphosphate, pyrophosphate, tripolyphosphate and hexametaphosphate can be used. As salts, H, N
a and K are common.

The alkaline agent as the component (f) is used in the composition in an amount of 5 to 50.
% By weight, preferably 10 to 40% by weight. By blending the alkaline agent in the detergent composition in this range, the bleaching power can be synergistically increased.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the above (a) to
In addition to the essential component (f), the following components can be blended.

[Aluminosilicate] The composition of the present invention preferably contains an aluminosilicate as an inorganic builder from the viewpoint of detergency. Both amorphous and crystalline aluminosilicates can be used. The crystalline aluminosilicate is generally referred to as zeolite, and has the following formula: a ′ (M ₂ O) · Al ₂ O ₃ · b ′ (SiO ₂ ) · w (H ₂ O) (A) [ In the formula, M represents an alkali metal atom, a ′, b ′, and w represent a molar ratio of each component, and are generally 0.7 ≦ a ′ ≦ 1.5, 0.8 ≦ b ′ <
6, w is any positive number. ], And
Above all, the following general formula (B): Na ₂ O.Al ₂ O ₃ .n (SiO ₂ ) .w (H ₂ O) (B) [where n is 1.8 to 3.0 and w is a number of 1 to 6 Represent. ]
Is preferably represented by As the crystalline aluminosilicate (zeolite), a synthetic zeolite having an average primary particle size of 0.1 to 10 μm typified by A-type, X-type and P-type zeolites is suitably used. The zeolite may be blended as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry.

As the amorphous aluminosilicate, those containing 30% by weight or more, preferably 40% by weight or more of silicon as SiO ₂ are good, and the pH of the 5% dispersion is 9 or more. The use thereof further improves the deterioration of the solubility of the detergent after storage at high humidity.

Examples of the amorphous aluminosilicate used in the present invention include those represented by the following general formula (C), which have high oil absorption and high cation exchange ability. a (M ₂ O) · Al ₂ O ₃ · b (SiO ₂ ) · c (H ₂ O) (C) [wherein M is an alkali metal atom, and a, b and c represent the number of moles of each component. , Generally 0.7 ≤ a ≤ 2.0, 0.8 ≤ b <
4, c is any positive number. ] In particular, the following general formula (D): Na ₂ O · Al ₂ O ₃ · b (SiO ₂ ) · c (H ₂ O) (D) [where b is 1.8 to 3.2 and c is a number of 1 to 6] Represents ]
Is preferably represented by

In the present invention, ion exchange capacity 100 CaCO ₃ mg /
It is preferable to use an amorphous aluminosilicate having an oil absorption capacity of 200 g / 100 g or more. Such an amorphous aluminosilicate can be produced with reference to JP-A-6-179899. The oil-absorbing ability contributes to the powder properties when a surfactant in liquid or paste form at normal temperature, particularly a nonionic surfactant is used. Amorphous aluminosilicate is preferred because it has an ion exchange water capacity and an action as an oil-absorbing carrier.

An amorphous aluminosilicate having an oil absorbing ability can be used when a nonionic surfactant having a melting point of 40 ° C. or less is blended as a surfactant in an amount of 5% by weight or more, especially 10% by weight. Problem can be suppressed, and it is effective for anti-caking. In that case, the amorphous aluminosilicate is preferably used in combination with the crystalline aluminosilicate.

In order to improve the hygroscopicity of the glycine-N-N'-diacetate derivative as the component (b), to suppress the generation of water-insoluble components, and to improve the caking property during storage of a detergent, zeolite or non-zeolite is used. It is effective to incorporate a crystalline aluminosilicate. In particular, the surface of the detergent particles containing the glycine-N-N'-diacetate derivative may be coated with these zeolites or amorphous aluminosilicate. Particularly, when the detergent particles are coated with an amorphous aluminosilicate having an oil absorbing ability, a favorable result can be obtained with a small amount. For use in these coatings, it is preferable that the aluminosilicate is incorporated in an amount of 5% by weight or more. Therefore, in order to satisfy the requirements of the solubility, caking property or water-insoluble content of the detergent, zeolite or amorphous aluminosilicate is preferably incorporated in the detergent in an amount of 5 to 40% by weight. Preferably 5
~ 30% by weight.

[Organic Builder] In the present invention, the following organic builders can be used in addition to inorganic builders such as aluminosilicate.

<Organic builders other than component (b)> 1) Phosphonic acid salts such as ethane-1,1-diphosphonic acid and ethane-1,1,2-triphosphone 2) Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, Polymer electrolytes such as carboxymethyl cellulose and polyaspartic acid 3) Organic acid salts such as diglycolic acid and oxydisuccinic acid 4) Copolymers having a molecular weight of several hundred to 100,000 and represented by the following formula (7) or / and ( 8) Polycarboxylates such as homopolymers represented by the formula

[0047]

Embedded image

Wherein Z is a monomer copolymerizable with (anhydrous) maleic acid or maleic acid salt of 1 to 8 olefins, acrylic acid, methacrylic acid, itaconic acid, methallylsulfonic acid, etc. salts of copolymers of acid or maleic acid salt, m is .M molecular weight of the copolymer have the values shown a several hundred-100000 is Na, K, is NH _3.)

[0049]

Embedded image

(Wherein P is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. M ′ is a value such that the molecular weight of the homopolymer is several hundred to 100,000. in a. salt homopolymers are Na, K, etc. NH _4.) among the above 1) to 4) is 4) are most preferred. 4) (7)
The compounding amount of the copolymer of the formula or / and the homopolymer of the formula (8) is 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the detergent composition. These acrylic acid among the polycarboxylate - salts of maleic acid copolymers and salts of polyacrylic acid (each, Na, K, NH ₄₎ has particularly excellent. The molecular weight is suitably from 1,000 to 80,000.

[Other components] The following components can be further blended as components other than those described above. Enzymes (enzymes that essentially perform an enzymatic action during the washing step) include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified according to the reactivity of the enzyme. Any of the embodiments can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases.

Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B. As commercial products, Savinase, Alcalase (Novo Industries), API 21 (Showa Denko KK), Maxacal (Gyst Procaides), Protease K-14 or K-16 described in JP-A-5-25492 There is. Specific examples of the esterase include gastric lipase, bankreatic lipase, plant lipases, and phospholipase.
Sesses, cholinesterases and phosphotase. As specific examples of the lipase, commercially available lipases such as lipolase (Novo Industries) and liposam (Showa Denko KK) can be used. As cellulase, commercially available cellzyme (Novo Industry),
The cellulase according to claim 4 of JP-A-63-264699,
KAC500, KAC500G (both Kao Corporation) can be used,
As the amylase, commercially available termamyl (Novo Industries) or the like can be used.

The enzyme is separately granulated as stable particles and dry-blended with detergent fabric (particles).

As an enzyme stabilizer, a reducing agent (sodium sulfite, sodium hydrogen sulfite), a calcium salt, a magnesium salt, a polyol, a boron compound and the like can be used. The reducing agent removes chlorine in tap water,
Stabilizes the enzyme. Sulfite also has an effect as an antioxidant.

Various bluing agents can be added as required. As the bluing agent, Japanese Patent Publication No. 49-8005,
JP-B-49-26286 or JP-B-53-458.
No. 08 substance.

Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, and magnesium oxide.

Examples of the antioxidant include tert-butylhydroxytoluene, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), and 2,2′-butylidenebis-
(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis- (4-hydroxyphenyl) cyclohexane and the like.

As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) A) a naphthothiazole derivative, a 4,4'-bis (triazol-2-yl) stilbene derivative or a bis (triazinylamino) stilbene disulfonic acid derivative in an amount of 0 to 2% by weight in the composition; For example, those commercially available under the trade names such as Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.) and Tinopearl CBS (manufactured by Ciba Geigy) can be used.

As the fragrance, a fragrance conventionally incorporated in detergents, for example, a fragrance described in JP-A-63-101496 can be used. Of course, the perfume components to be blended and, if necessary, the blending ratio and blending amount are taken into account so as not to be deteriorated by other detergent components.

The detergent composition of the present invention is a powdery or lumpy composition containing a bleaching component, but the production method is not particularly limited, and a conventionally known method can be used. A detergent having a bulk density of preferably 0.6 to 1.2 g / cm ³ is preferably used. Examples of the method for increasing the bulk density include a method of spraying a nonionic surfactant on spray-dried particles to increase the density, and a method of increasing the density while directly absorbing nonions into the powder component including the oil absorbing carrier. Japanese Patent Application Laid-Open Nos. 61-69897 and 61-6989.
No. 9, JP-A-61-69900, JP-A-2-222498
JP-A-2-222499, JP-A-3-33199, JP-A-5-86400, and JP-A-5-209200 can be referred to. When a crystalline aluminosilicate is blended as the aluminosilicate, a small amount thereof may be added during granulation or immediately before the completion of granulation, since it can be used as a surface modifier for the granulated product. When a crystalline silicate is blended, it is preferable to add the crystalline silicate at the time of increasing the bulk density or to add the crystalline silicate by dry blending. When the alkali metal carbonate is blended, it may be added to the slurry, during granulation or in the dry blend. (b) The glycine-N-N'-diacetate derivative of the component may be added before the spray drying step or after the step. The percarbonate or perborate of the component (a) and the bleaching precursor of the component (c) are preferably added and mixed in the last step.

[0061]

According to the present invention, the bleaching / cleaning effect of a detergent composition mainly composed of a nonionic surfactant using an oxygen bleaching agent and a bleaching precursor is remarkably improved.

[0062]

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.

Example 1 <Preparation of granular detergent composition> The product 1 of the present invention shown in Table 1 was prepared by the following method.

MGDA (methyl glycine-N-N'-diacetate sodium salt) 1.0 kg, LAS 0.2 kg, FA 0.3 kg, crystalline aluminosilicate 1.0 kg, sodium polyacrylate
0.3 kg, sodium carbonate 1.0 kg, fluorescent dye (4,4'-bis- (2-sulfostyryl) -biphenyl salt) 0.05 kg and water slurry of 60% solids are prepared from sodium sulfate used for balance and sprayed. dry. The obtained particles are put into a high speed mixer (Fukae Kogyo Co., Ltd.). Further, 1.5 kg of a porous silica compound, 1.0 kg of a crystalline aluminosilicate, and 1.0 kg of a silicate (5) were added, and while these were mixed, 1.5 kg of AE-1 heated to 70 ° C, PEG 0.1 kg, and granulation is performed, and then PC (2Na ₂ CO ₃ .3H ₂ O
₂ ) 0.5 kg, bleach precursor particles (granules of AV-1) 0.46
kg and 0.1 kg of enzyme, respectively, and mixed with a V blender to obtain a high-density granular bleaching detergent composition (average particle size of 480).
μm, bulk density 810 g / l).

The bleach precursor particles (granules of AV-1) were prepared by the following method. A mixture of 2.7 kg of sodium dodecanoyloxybenzenesulfonate (bleaching precursor), 0.6 kg of polyethylene glycol (molecular weight 6000) and 1.7 kg of sodium lauryl sulfate [Fukae Kogyo Co., Ltd .: High-speed mixer] FS-GC-10 type), mixing and heating at a jacket temperature of 80 ° C, a spindle rotation speed of 200 rpm, and a crushing blade rotation speed of 1500 rpm.
When the temperature reached ℃, the mixture was extracted and extruded through an 800 μm pore size screen by an extrusion granulator (manufactured by Fuji Paudal Co., Ltd.) to consolidate. After cooling the obtained extrudate, it was crushed by a sizing machine. The obtained crushed product was classified, and the one having a weight average particle size of 880 μm was used as particles (granulated material) of the bleaching precursor. The PC used was manufactured by Nippon Peroxide Company. The granules of AV-2 were prepared in the same manner as for AV-1, except that sodium decanoyloxybenzenecarboxylate was used as a bleaching precursor.

With respect to the other products of the present invention and comparative products shown in Tables 1 to 6, high-density granular bleaching detergent compositions were prepared in accordance with the above-mentioned schemes, in respective mixing ratios. The obtained detergent compositions were subjected to a bleaching power test and a detergency test by the following methods. The results are shown in Tables 1 to 6.

[Bleaching Test] <Preparation of Stained Cloth > Preparation of Stained Black Cloth 10 tea bags (Lipton) in 1 liter of water (20
b) Add 50 g of sugar to g) and boil for 10 minutes. Thereafter, the tea bag is taken out and the total volume is reduced to 1 liter. After cooling, put it in a vat and put a 10 x 55 cm desizing cloth on both sides
Soak for 10 seconds each, pass through a roller and air dry to obtain a tea-stained cloth.

Preparation of Red Wine Contaminated Cloth Put red wine in the vat as it is, and place an 8 × 50 cm cloth on the front and back.
Soak for 10 seconds each, pass through a roller and air dry to obtain a red wine stained cloth.

<Cleaning Conditions and Evaluation Method> Five 1 × 10 cm artificially-stained cloths prepared as described above were placed in 1 liter of the aqueous detergent solution for evaluation, and washed with a tergotometer at 100 rpm.

Washing condition Temperature: 20 ° C Detergent concentration: 0.067% Washing time: 10 minutes Water quality: tap water The reflectance of the washed contaminated cloth was measured by NDF-30 manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured using 0A. The reflectance measurement wavelength is 4 for black tea stained cloth.
The thickness was 60 μm, and the size of the red wine-contaminated cloth was 520 μm. The bleaching rate is
Based on the reflectance of the stained cloth washed in Test No. 22, the improvement in the bleaching effect was evaluated based on the difference (Δ bleaching rate).

[Detergency test] <Preparation of artificially stained cloth> An artificially stained cloth having the following composition was attached to the cloth to prepare an artificially stained cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The process of adhering the artificially contaminated liquid to the cloth to produce the artificially contaminated cloth is based on the cell capacity of the gravure roll.
The drying was performed at 8 cm ³ / cm ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten).

(Composition of artificial contaminated liquid) Lauric acid 0.44% by weight Myristic acid 3.09% by weight Pentadecanoic acid 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Oleic acid 7.75% by weight 13.06% by weight N-hexadecyl palmitate 2.18% by weight Squalene 6.53% by weight Egg white lecithin liquid crystal 1.94% by weight Kanuma red clay 8.11% by weight Carbon black 0.01% by weight Tap water balance.

(Cleaning Conditions and Evaluation Method) Five 1 cm × 10 cm artificially-stained cloths prepared as described above were placed in 1 liter of an aqueous cleaning agent solution for evaluation, and washed at 100 rpm with a tergotometer. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Washing agent concentration 0.067% Water hardness 5 ° DH Water temperature 20 ° C Rinse with tap water 5 minutes Washing power is the self-recording color at 550 nm of the original cloth before and after cleaning. The cleaning rate (%) was determined by the following equation, and the average of the measured values of the five sheets was shown as the cleaning power.

[0074]

(Equation 1)

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

[Table 6]

(Note) PC: sodium percarbonate 2Na ₂ CO ₃ .3H ₂ O ₂ .PB: sodium perborate NaBO ₃ .1H ₂ O MGDA: methyl glycine di-N, N'-acetate sodium salt Crystal Silicate (5): M ₂ O · 1.8 SiO ₂ · 0.02 M′O (where M: Na, K, K / Na = 0.03, M ′ = Ca, Mg, Mg / Ca =
0.01), ion exchange capacity 224CaCO ₃ mg / g, average particle size 30
μm ・ Crystalline silicate (6): M ₂ O ・ 2SiO ₂ , ion exchange capacity 22
4CaCO ₃ mg / g, average particle size 30 μm, trade name SKS (manufactured by Hoechst-Tokuyama Corporation) AE-1: polyoxyethylene dodecyl ether (HL
B 13.1) AE-2: Polyoxyethylene dodecyl ether (HL
B 12.0) AE-3: Polyoxyethylene dodecyl ether (HL
B 16.5) LAS: linear alkyl (C ₁₂ ) benzenesulfonic acid sodium salt FA: palmitic acid sodium salt (however, the product of the present invention)
Sodium laurate was used in 29) ・ Zeolite: crystalline aluminosilicate, M ₂ O ・ Al ₂ O
₃・ 2SiO ₂・ 2H ₂ O, average particle size 2μm, ion exchange capacity 2
90 CaCO ₃ mg / g ・ Porous silica compound: amorphous aluminosilicate, thixolex (manufactured by Kofuran Chemical Co.) ・ Polyacrylic acid sodium salt (PA): average molecular weight 80
00 • PEG: polyethylene glycol with an average molecular weight of 7000 • Enzyme: Sabinase 12.0T type W (Novo Nordisk), Lipolase 100T (Novo Nordisk), KAC5
00G (Kao Corporation) and Termamyl 60T (Novo Nordisk) mixed in a ratio of 2: 1: 1: 1 ・ Common component: 1.0% enzyme, 0.5% fluorescent component and sodium sulfate, The volume was adjusted to 100%.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/34 C11D 3/34 3/37 3/37 3/39 3/39 3/395 3/395

Claims (5)

[Claims] (A) Percarbonate or perborate: 2 to 50% by weight (b) Glycine-N-N'-diacetate derivative represented by the following general formula (1): 3 to 40% by weight 1) (Wherein, M is selected from H, Na, K, and NH ₄ , and R is selected from an alkyl group or an alkenyl group having 1 to 18 carbon atoms.) (C) Bleaching represented by the following general formula (2) Precursor 0.5-30
% By weight (In the formula, R is an alkyl group having 5 to 23 carbon atoms, and L is a leaving group.) (D) Nonionic surfactant 10 to 40% by weight (e) Anionic surfactant (e) / (d) ) = 1/2 to 1/40
(Weight ratio) (f) A bleach-containing detergent composition containing 5 to 50% by weight of an alkali agent. 2. The weight ratio of the component (d) to the component (e) is (e) /
2. The detergent composition according to claim 1, wherein (d) = 1/3 to 1/15. 3. The detergent composition according to claim 1, wherein the bleaching precursor is a compound represented by the following general formula (3). Embedded image [Wherein, m is a number from 0 to 5, X and Y are the same or different,
Hydrogen, -SO ₃ M, and -COOM are shown, respectively. Where M 1 is a cation or H 2. R is the same as in the above formula (2). ] 4. The detergent composition according to claim 1, comprising 5 to 30% by weight of an aluminosilicate. 5. The detergent composition according to claim 1, which contains a polycarboxylate having an average molecular weight of 1,000 to 100,000.