JP3365867B2 - Granular bleach composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to peroxo having high lipophilicity.
(Peroxo) relates to a bleaching composition containing an acid bleaching precursor and an inorganic peroxide, and in particular, has a high bleaching power for lipophilic stains, and provides a bleaching composition having excellent storage stability. To do.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents, but chlorine-based bleaching agents are limited in the fibers that can be used, and cannot be used in colors and patterns. Oxygen-based bleaching agents, which do not have these drawbacks, have recently become extremely popular due to their non-existence and unique odor. Among the oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid bleaching agent.

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

As a precursor of a peroxo acid bleaching agent, which has improved this drawback, the inventors of the present invention have disclosed JP-A-63-233969, JP-A-63-31566, JP-A-64-68347 and JP-A-1. As disclosed in JP-A-190654, it was found that a compound which reacts with hydrogen peroxide to form an organic peracid having a quaternary ammonium group is excellent as a peroxo acid bleaching precursor. An example of a peroxo acid bleaching agent precursor in which a lipophilic group is introduced into the molecule is disclosed in JP-B-63-12520. These peroxoacid bleach precursors have an effect on lipophilic stains but are unsatisfactory.

In order to enhance the bleaching power of lipophilic stains, it is effective to introduce a long chain alkyl group or alkenyl group into the peroxo acid bleach precursor. However, such a peroxo acid bleach precursor, if not protected by granulation, surface coating, or the like, has a problem in that it gradually decomposes due to interaction with other components.

[0006] Therefore, the problem to be solved by the present invention is
It is an object of the present invention to provide a bleaching agent composition which can efficiently produce an organic peracid having a high bleaching power on lipophilic stains even in an aqueous solution and is excellent in long-term storage stability.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have produced a specific peroxo acid bleaching agent precursor and sodium percarbonate in an average particle size within a specific range. The inventors have found that the objects can be achieved by granulating and blending them so that the average particle diameters of both particles are in a ratio within a specific range, and the present invention has been completed.

[0008] Thus, the present invention contains the following components (a) and component (b), the average particle size B of the average particle diameter A and component (b) of component (a) satisfies the following formula (I) , The weight ratio of component (a) and component (b) is
[(A) component] / [component (b)] = 1 / 10-1 / 3 a is this <br/> the particulate bleach composition characterized. | A-B | / A ≦ 0.2 (I) [component (a)] was granulated formula (II) peroxyacids bleach precursor represented by the presence of a water-soluble organic binder, the average particle diameter of 350 1
Granules of 000 μm 0.1 to 50% by weight

[0009]

[Chemical 2]

[Wherein R: -SO ₃ M, a substituent selected from -OH, -COOM or a linking group selected from -COO-, -OCO-, -NHCO-, -CONH- 5 to 5 carbon atoms in a straight or branched chain which may be
22 is an alkyl group or an alkenyl group, or is an aryl group which may be substituted with a linear or branched alkyl group having 5 to 22 carbon atoms. Here, M represents an inorganic or organic cation. X: indicates -SO ₃ M or -COOM. Here, M has the above-mentioned meaning. [Component (b)] Granules obtained by granulating sodium percarbonate having an effective oxygen content of 9% or more in the presence of a water-soluble organic binder to have an average particle size of 350 to 1000 µm 1 to 95 % by weight or less, The invention will be described in detail.

[Component (a)] In the present invention, the compound represented by the above general formula (II) is used as a peroxo acid bleach precursor. Specifically, the following compounds are exemplified.

[0012]

[Chemical 3]

The peroxo acid bleach precursor (II) is gradually decomposed by the interaction with the bleach component or the detergent component. In order to prevent this, the peroxo acid bleaching agent precursor of the present invention is granulated in the presence of a water-soluble organic binder to give a granulated product having an average particle size of 350 to 1000 μm, which is used as the component (a). . If the average particle size of component (a) is less than 350 μm,
The storage stability of the powder bleaching composition decreases, while when the average particle size of the component (a) exceeds 1000 μm, the solubility of the powder bleaching composition in water decreases, resulting in a bleaching power. Is reduced.

In this case, the average particle size A of the component (a) is
It is important that the following expression (I) is satisfied in relation to the average particle size B of the component (b) described below. When | AB | /A≦0.2 (I) | AB | / A> 0.2 , the storage stability of the powder bleaching composition decreases.

In the present invention, as the component (a), the peroxo acid bleach precursor (II) is granulated in the presence of a water-soluble organic binder, and then the average particle size is 350 to 1000 μm using a sieve or a sizing machine.
The average particle size of the granules of the component (a) and the component (b) of the present invention is measured using a sieve.

In this case, examples of the water-soluble organic binder used in the present invention include polyethylene glycol, polypropylene glycol, nonionic surfactants and the like. Polyethylene glycol has a molecular weight of 400
.About.20000, preferably in the range of 600 to 10,000. As the nonionic surfactant, polyoxyethylene (ethylene oxide addition mole number 3 to 300) alkyl (C ₈ to
C ₂₂₎ ethers, polyoxyethylene (ethylene oxide addition mole number 10 to 300) alkyl (C ₈ -C ₁₄₎ phenol ethers, or Pluronic, Tetronic (Adeka (strain) non-commercially available under the trade name of products) Examples thereof include ionic surfactants and fatty acid glycerides having 8 to 20 carbon atoms. Among these water-soluble organic binders, melting point 20-80
More preferred are polyethylene glycols, polypropylene glycols and nonionic surfactants at ° C. They are,
It does not melt at temperatures below 20 ° C, and has tackiness or film-forming properties at temperatures above 20 ° C. Since the product temperature during granulation is not preferable when it exceeds 80 ° C from the viewpoint of thermal decomposition of the peroxo acid precursor, the water-soluble organic binder preferably has a melting point of 20 to 80 ° C, more preferably 30 to 70 ° C. A substance having a melting point of is used.

The amount of the water-soluble organic binder used is, in weight ratio, [water-soluble organic binder] / [peroxo acid bleach precursor], preferably 0.005 to 0.2, more preferably
It is 0.05 to 0.1.

In producing the granulated product in the present invention, the obtained granulated product is granulated by a granulating method which easily disintegrates or dissolves in a solution. As the granulation method, a fluidized granulation method,
The tumbling granulation method, the stirring tumbling granulation method, the extrusion granulation method and the like are used. In the tumbling granulation method, it is also possible to use appropriate core particles that do not interact with the peroxo acid bleach precursor. Glauber's salt is the most excellent core particle.

[Component (b)] In the present invention, as the component (b), sodium percarbonate having an effective oxygen content of 9% or more is granulated in the presence of a water-soluble organic binder to adjust the average particle size to 350 to 1000 μm. The granulated product is used.

If the average particle size of the component (b) is less than 350 μm, the storage stability of the powder bleaching composition will be reduced, while (b)
If the average particle size of the component exceeds 1000 μm, the solubility of the powder bleaching composition in water is lowered, and as a result, the bleaching power is lowered.

The kind of the water-soluble organic binder used in this case, the granulation method, and the like are the same as those described for the component (a).

The amount of the water-soluble organic binder used here is [water-soluble organic binder] / weight ratio.
[Sodium percarbonate] is preferably 0.0001 to 0.1, more preferably 0.0005 to 0.5.

[Powder bleach composition] In the present invention,
In the mixing of the components (a) and (b), any conventionally known blender such as a Henschel mixer, a ribbon blender or a U-shaped blender may be used.

The components (a) and (b) are mixed in a weight ratio of [(a)
In order to obtain a desired bleaching power in the powder bleaching agent composition, it is necessary to mix them in such a manner that the component] / [(b) component] = 1/10 to 1/3 .

If desired, a surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants may be added to the present invention. Examples of these are alkylbenzene sulfonates,
Anionic surfactants such as alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkyl or alkenyl ether carboxylates, α-sulfo fatty acid salts, or α-sulfo fatty acid esters, polyoxyethylene Or polyoxypropylene or copolymers thereof, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides, or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glucosides Amphoteric surfactants such as ionic surfactants, amine oxides, sulfobetaines and carbobetaines, or cationic surfactants such as quaternary ammonium salts Can be given.

Of these, alkylbenzene sulfonates having 10 to 20 carbon atoms, alkyl alkenyl sulfates having 10 to 20 carbon atoms, alkyl or alkenyl ether sulfates having 10 to 20 carbon atoms, and oxy groups having 10 to 20 carbon atoms. Particularly preferred are polyoxyethylene alkyl or alkenyl ethers having an ethylene addition mole number of 4 to 30, and sulfobetaine or carbobetaine having an alkyl group of 8 to 20 carbon atoms.

The method of adding the surfactant is as follows:
(b) It may be mixed in the component and granulated, or may be blended separately, and the blending amount in the composition is 0 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight. Weight% is good.

If desired, a sequestering agent may be added to the composition of the present invention. As the sequestering agent, 1) a phosphoric acid compound such as phytic acid or an alkali metal salt, an alkaline earth metal salt, an ammonium salt or an alkanolamine salt 2) ethane-1,1-diphosphonic acid, ethane-1,1 Phosphonic acids such as 2,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, or their alkali metal salts and alkaline earth metals. Salts, ammonium salts or alkanolamine salts 3) Polymers such as acrylic acid, maleic acid, itaconic acid, aconitic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid, citraconic acid, etc., or copolymers of two or more types, average These carboxes have a molecular weight of 500 to 100,000. Polycarboxylic acid which may be an alkali metal salt, an alkaline earth metal salt, an ammonium salt or an alkanolamine salt in part or all of the silyl group 4) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane- Phosphonocarboxylic acids such as 2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 5) Aspartic acid, glutamic acid, glycine 6) Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodimine, etc., or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts Acetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencholic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 7) Succinic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid , Citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, and other organic acids or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 8) Examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts of aluminosilicate represented by zeolite A.

Of these, one or a mixture of two or more selected from 2), 3), 6), 7) and 8) is particularly preferable. The amount of such a sequestering agent is 0 to 30% by weight, preferably 0.0005 to 30% by weight, more preferably 0.0005 to 30% by weight, based on the bleaching composition.
0.1 to 20% by weight is desirable. As for the method of adding the sequestering agent, similar to the surfactant, it may be mixed with the component (a) and the component (b) for granulation, or may be added separately.

Further, in the present invention, in addition to the above-mentioned components, known components usually added to bleaching agents can be added. Alkaline agents such as sodium carbonate, and Tinopearl CB as a fluorescent whitening agent to enhance the bleaching effect on bleached fibers.
S, Tinopearl SWN (manufactured by Ciba Geigy), fluorescent whitening agents such as color index fluorescent whitening agents 28, 48, 61, 71, etc., and conventionally known enzymes (cellulase, amylase for improving bleaching performance. , Protease, lipase) can be added as required.

The bleaching agent composition of the present invention may contain various trace amounts of additives such as coloring agents such as dyes and pigments, fragrances, silicones, bactericides and ultraviolet absorbers.

When an optional component is added to the component (a) and / or the component (b) to obtain a granulated product, the average particle size of the granulated product containing them is expressed by the above formula (I). Need to meet.

[0033]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a bleaching composition which has an extremely excellent bleaching power for lipophilic stains and is excellent in storage stability.

[0034]

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.

[1] Peroxo Acid Precursor-Containing Granulated Material <Granulation Method I> Component (a) shown in Tables 1 and 2 and other components are mixed by a mixer (Fukae Industry Co., Ltd .: High Speed Mixer FS).
-GC-10 type) mixing, mixing at a jacket temperature of 80 ° C, a spindle speed of 200 rpm, and a grinding blade speed of 1500 rpm,
The temperature was raised, and the mixture was extracted when the temperature of the powder reached 70 ° C.

Next, the obtained mixture was extruded and granulated (Fuji Paudal Co., Ltd .: Pelleter Double EXD-100).
The mold was extruded and compacted through a screen having a pore size of 800 μm.

The extrudate obtained was pulverized with a vibration cooler (manufactured by Fuji Paudal Co., Ltd .: knife cutter FL-200 type). The obtained crushed material is classified by a classifier (manufactured by Tokuju Manufacturing Co., Ltd.
Particle size 350-1200μ
m (average particle diameter 800 μm) was used.

<Granulation Method II> The components (a) shown in Tables 1 and 2 and other components were charged into a mixer (Fukae Industry Co., Ltd .: high speed mixer FS-GC-10 type), and the jacket temperature was adjusted.
80 ℃, Spindle speed 200rpm, Grinding blade speed 1500rp
Granulated for about 20 minutes as m 2. After the granulation is finished, cool water (15 ℃) is poured into the jacket to cool the granulation product, and after the granulation product temperature reaches 40 ℃ or less, the granulation product is sieved to give a particle size of 350 ~
The one with 1000 μm (average particle diameter of 710 μm) was used.

The following I to VI (V and VI are comparative products) were used as the peroxo acid precursor of the component (a).

[0040]

[Chemical 4]

The surfactants A, B and C are as follows.

[0042]

[Chemical 5]

[2] Sodium percarbonate granulated product <Sodium percarbonate granulated product> Sodium percarbonate obtained by crystallization of sodium carbonate and hydrogen peroxide is dehydrated,
PEG600 to be 0.5% by weight in sodium percarbonate granulation
Added 0. This is kneader (Satake Chemical Machinery Co., Ltd.)
Manufacture: 1600-65CVJA-3.7 type), and the resulting product is extruded through a granulator (Fuji Paudal Co., Ltd .: Pelleter Double EXD-100 type) through a screen with a pore size of 800 μm to form consolidation. I went.

The extrudate thus obtained was vibrated and cooled (by Fuji Paudal Co., Ltd .: Vibro Flow Dryer VDF-60).
00 type), then sifted, particle size 350-1000μm
(Average particle size 800 μm) was used. The amount of available oxygen was 11.2% as measured by the following measuring method.

<Sodium percarbonate granulated product> Pore size 1000μ
Granulation was carried out in the same manner as described above using a screen of m. A particle size of 500 to 1200 μm (average particle size 950 μm) was used. The amount of available oxygen was measured by the following measuring method,
It was 11.5%.

<Sodium Percarbonate Granules> The sodium percarbonate granules were put into a household juicer mixer, crushed, sieved, and the particle size was 100 to 500 μm (average particle size 350 μm).
m) was used. The amount of available oxygen was 11.1% as a result of measurement by the following measuring method.

* Effective oxygen measuring method 0.1 g of a sample was precisely weighed, 10 ml of 20% sulfuric acid was added and dissolved therein, and titrated with N / 10 potassium permanganate, and the effective oxygen was determined from the following formula.

[0048]

[Equation 1]

[3] Measurement of bleaching performance Various bleaches were prepared by blending the (a) component-containing granules and (b) component granules prepared as described above with sodium carbonate and protease in the ratios shown in Tables 1 and 2. An agent composition was obtained. The bleaching performance of the obtained bleaching agent composition was evaluated by the following method.

(I) Bleaching rate 10 g of the bleaching agent shown in Table 1 was added to a 2 liter aqueous solution containing 25 g of a commercially available detergent, and 5 pieces of curry-contaminated cloth, which is a representative of lipophilic stains, was prepared as follows. Soaked for 15 minutes. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula.

[0051]

[Equation 2]

The reflectance is NDR-101D manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at P using a 460 nm filter.

* Preparation of Curry Contaminated Cloth "Bon Curry" manufactured by Otsuka Foods Co., Ltd. was heated at 80 ° C. for 30 minutes, filtered through a colander, and soaked in cotton gold cloth # 2003 in a liquid from which solids were removed, and heated for 15 minutes. . After leaving it as it was for about 2 hours, the cloth was taken out from the liquid to remove excess water, and naturally dried.
After pressing, it was used in an experiment as a 10 cm × 10 cm test piece.

(Ii) Storage stability measurement 10 g of each of the bleaching agent compositions shown in Table 1 was stored in a 50 ml plastic container at 40 ° C./80% RH for 4 weeks. The residual amount of the peroxo acid bleach precursor precursor of the sample before and after storage was determined by the following titration method, and the residual rate was calculated by the following formula.

[0055]

[Equation 3]

<Titration method> 5 g of the bleaching composition was added to 1 part of water at 20 ° C.
Dissolve well in liter, stir for 10 minutes, add 10 ml of 0.3% catalase solution, and stir for 1 minute. 10% in this solution
Add 10 ml of potassium iodide solution and 20 ml of 20% sulfuric acid solution.
Titrate with 1N sodium thiosulfate solution.

[0057]

[Table 1]

[0058]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-64-6097 (JP, A) JP-A-5-202395 (JP, A) JP-A-6-136390 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C11D 3/395 C11D 17/06 D06L 3/02

Claims (3)

(57) [Claims] 1. A composition comprising the following components (a) and (b):
The average particle size A of the component and the average particle size B of the component (b) satisfy the following formula (I), and the weight ratio of the components (a) and (b) is [(a) component] / [(b)
Ingredient] = 1/10 to 1/3, a granular bleaching composition. | A-B | / A ≦ 0.2 (I) [component (a)] was granulated formula (II) peroxyacids bleach precursor represented by the presence of a water-soluble organic binder, the average particle diameter of 350 1
Granules 000 μm 0.1 to 50% by weight [Chemical formula 1] [Wherein R: -SO ₃ M, -OH, a substituent selected from -COOM or a linking group selected from -COO-, -OCO-, -NHCO-, and -CONH- Good straight or branched chain carbon number 5
22 is an alkyl group or an alkenyl group, or is an aryl group which may be substituted with a linear or branched alkyl group having 5 to 22 carbon atoms. Here, M represents an inorganic or organic cation. X: indicates -SO ₃ M or -COOM. Here, M has the above-mentioned meaning. [(B) component] Granules obtained by granulating sodium percarbonate having an effective oxygen content of 9% or more in the presence of a water-soluble organic binder to have an average particle size of 350 to 1000 µm 1 to 95 % by weight 2. A granulated product of (a) component or (b) composition.
Granules minute contains sequestering agents, claim 1 granular bleach composition. 3. A granulated product of component (a) or (b)
The granulated product of the components contains one or more kinds of surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. 2. The granular bleaching composition according to item 2.