JPH02255800A - Bleaching activating agent granule - Google Patents

Abstract

PURPOSE:To obtain the title granules containing a breaching activating agent, binder such as polyethylene glycol, carbonate and solid or powdery acid at a specific ratio and having excellent solubility and storage stability. CONSTITUTION:The aimed granules consisting of (A) 10-85wt.% breaching activating agent such as tetraacetylethylene diamine, preferably being solid at 80 deg.C, (B) 2-50wt.% one or more binder substances selected from a group consisting of polyethylene glycol, preferably having 35-80 deg.C melting point, non- ionic surfactant, long-chain fatty acid and high polymer compound, (C) 5-50wt.% carbonate such as sodium hydrogen carbonate or potassium carbonate and 5-50wt.% solid or powdery acid, preferably consisting of an organic acid such as succinic acid, fumaric acid or maleic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to bleach-activated pore-side granules with excellent solubility and storage stability.

[Conventional technology and its problems]

Conventionally, it has been proposed to use various bleach activators in combination with oxygen-based bleaches such as sodium percarbonate and sodium perborate in order to increase their bleaching properties. However, the functionality of bleach activators is significantly impaired during storage due to interactions with oxygen bleaches or other ingredients contained in detergents. Therefore, the bleach activator must be protected from the surrounding environment by means such as granulation or surface coating. However, any protective measures must not inhibit the dispersion solubility in the wash water. Many studies have been conducted to satisfy these conditions.

For example, in JP-A-48-8806, composite particles are prepared by mixing a bleach activator, a carrier material such as paraffin or long-chain fatty acids, and a dispersion aid such as sodium alkyl sulfate, and the particle surface is further coated with a polymer material. A granulated material coated with is described. JP-A-49-45107, JP-A-51-46
No. 304 describes activator granules obtained by spraying a mixture of a bleach activator, a long-chain fatty acid, a long-chain alcohol, or even (polyoxyethylene)alkyl sulfate. JP-A-56-55500 describes activator granules obtained by granulating tetraacetylethylenediamine having a specific particle size distribution, sodium triphosphate, and potassium triphosphate using water as bound water. . JP-A-56-149500 discloses a bleach activator,
Activated granules are described in which water or an aqueous solution of the granulation aid is sprayed onto a mixture of granulation aids such as water-soluble cellulose and starch, and the activated granules are dried after granulation. JP-A-57-192498 describes activator neck particles prepared by spraying an aqueous solution of sodium carboxymethylcellulose onto a dry mixture of tetraacetylethylenediamine and sodium triphosphate and drying the mixture. JP-A No. 59-135299 describes sodium ocukunoyloxybenzenesulfonate and a compound having a melting point of 4.
An activated granule is described in which a binder substance such as a nonionic surfactant, polyethylene glycol, an anionic surfactant, a long chain fatty acid, and a film-forming polymer is mixed substantially uniformly at a temperature of 0° C. or higher. ing. Japanese Patent Publication No. 61-11140
No. 0 describes an activator granule obtained by spray-drying a bleach activator and a water-soluble or water-dispersible inorganic hydrating substance.

Such activated granules are storage stable and dissolve relatively quickly in water under hot water washing conditions as in Europe and America.

However, under cold water weak agitation washing conditions like in our country,
Alternatively, if little stirring force is applied, such as under bleaching conditions, the dissolution rate is slow and the function of the activator cannot be fully utilized.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors found that
It has been discovered that by combining a carbonate and an acidic substance with an activator and granulating it using a suitable binder material, a granular bleach activator granule with excellent solubility can be obtained, and the present invention has been made based on the present invention. completed.

That is, the present invention provides: (a) Bleach activator 10-85% by weight
et al.) Polyethylene glyconeone one or more binder substances selected from the group consisting of nonionic surfactants, anionic surfactants, long chain fatty acids, and polymer compounds 2
~50% by weight (C) carbonate 5~
50% by weight (d) Solid or powdered acid 5-5
A bleach-activated pore-side granulate comprising 0% by weight is provided.

The bleach activator (a) used in the present invention includes various bleach activators, but those that are solid at 80°C are particularly desirable. Examples of such bleach activators include tetraacetyl ethylene diamine, glucose pentaacetate, tetraacetyl glycol urinopearkanoyloxybenzene sulfonate (alkyl group has 1 to 14 carbon atoms). Also desirable are a series of bleach activators represented by general formula (I) below.

+ R, -N-R, -C-L (I)
R,0 [In the formula, R11R2+ R3 represents an alkyl group, alkenyl group, or alkaryl group, R1 represents an alkylene group, cycloalkylene group, phenylene group, or alkylenephenylene group, and L is (W) a glycerin residue; (force) Sugar derivative residue.

(Rs, Re are alkyl groups, R8, Rt are H or alkyl groups, R is alkylene groups, alkenylene groups, 0
Represents Ra. ] In the above general formula (I), R1 is an alkyl group of 01 to +8, especially 01 to 0, R,, R, is a C1 to 2 alkyl group, and R1 is -(CH2) r 〜 + 2-, especially -(CH2) I
-s-, Shiga (a).

(b), (c), (d), (to), ()), (
Wa), (power).

Compounds represented by the structural formulas (Y) and (Y), in which R8 is an alkyl group of 01-2, Re and Rt are H or an alkyl group of C1-2, and R6 is an alkyl group of C1-2 are desirable, Compounds represented by the structural formulas (Y) and (Y) are particularly desirable. Bleach activator (a) is used in the granules in an amount of 10 to 85% by weight, preferably 30 to 70% by weight.

As the binder substance, a substance that does not melt at temperatures below 35°C and has adhesive or film-forming properties at temperatures above 35°C is used, preferably from 35 to 80°C, particularly preferably from 40 to 70°C. Substances with a melting point of °C are used. The binder substance (b) is selected from one or more substances selected from the group consisting of polyethylene glycol, nonionic surfactants, anionic surfactants, long chain fatty acids, and polymer compounds.

Polyethylene glycol has a molecular weight of 2.000 to 20,
000, preferably in the range of 4.000 to io, ooo.

Examples of nonionic surfactants include polyoxyethylene (100=15-300) alkyl (Ca-2□〉 ether,
Polyoxyethylene (p=15-300) alkyl (0
6-14) Nonionic surfactants commercially available under the trademarks of phenol ether, Pluronic, and Tetronic, fatty acid glycerides having 8 to 20 carbon atoms, and the like.

Examples of the anionic surfactant include alkylbenzene sulfonates having 9 to 22 carbon atoms, alkyl sulfates, alkyl ether sulfates, α-olefin sulfonates, soaps, and the like.

Examples of long-chain fatty acids include those having 8 to 24 carbon atoms.

Film-forming polymer materials include polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, polyalylate, polyhydroxyacrylate, salt of hydrolyzate of olefin/maleic anhydride copolymer, and polymaleate. Polymers can be mentioned. Especially preferred binder substances (b)
are polyethylene glycol with a melting point of 35 to 80°C, a nonionic surfactant, and a higher fatty acid. Anionic surfactants and polymeric materials often have very high melting or decomposition temperatures, so when they are used as binders they are generally used as aqueous solutions. Binder substance etc.]
is used in the granules in an amount of 2 to 50% by weight, preferably 8 to 30% by weight.

The carbonate (C) is one selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, potassium bicarbonate, potassium carbonate, potassium sesquicarbonate, ammonium bicarbonate Uno 4, ammonium bicarbonate, and ammonium sesquicarbonate. Or two or more compounds are used. Among these, sodium and potassium hydrogen carbonate, sodium carbonate and potassium carbonate are preferred, and sodium hydrogen carbonate is particularly desirable.

The carbonate (C) is blended in the granules in an amount of 5 to 50% by weight, preferably 10 to 30% by weight.

Organic acids and inorganic acids are used as solid or powdered acids (d).

Examples of organic acids include straight fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; oxalic acid, malonic acid, succinic acid,
Dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid; acidic amino acids such as glutamic acid and aspartic acid; gelcholic acid, lactic acid, hydroxyacrylic acid,
Oxyacids such as α-oxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid, citric acid, salicylic acid (01m, p), gallic acid, mandelic acid, trobic acid, ascorbic acid, gluconic acid; cinnamic acid, benzoic acid , phenylacetic acid, nicotinic acid, kainic acid, sorbic acid, pyrrolidonecarboxylic acid, trimellitic acid, benzenesulfonic acid, toluenesulfonic acid, and acid salts of these organic acids.

Inorganic acids include phosphoric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, potassium sulfite, and sodium pyrosulfite (sodium metabisulfite).
, pyrosulfite cormorant 1. (potassium metabisulfite),
Examples include acidic sodium hexametaphosphate, acidic potassium hexametaphosphate, acidic sodium pyrophosphate, acidic potassium pyrophosphate, and sulfamic acid.

Among these, organic acids are preferred, with succinic acid, fumaric acid, maleic acid, citric acid, malic acid, and tartaric acid being particularly preferred. The acid (d) is present in the granules in an amount of 5 to 50% by weight, preferably 10 to 50% by weight.
It is blended in an amount of 25% by weight.

A known method is employed as the granulation means for obtaining the bleach-activated pore-side granules of the present invention. Particularly suitable are the stirring transfer granulation method in which the components (a) to (d) are fed to a stirring transfer device and granulated into granules, or the extrusion granulation method in which the components are extruded axially or radially through a fine mesh under pressure. Extrusion granulators for extrusion granulation include screw type, ram type, roll type granulators, and the like.

The appropriate granulation temperature is 40 to 90°C, and at this temperature the binder material with a melting point of 35°C or higher melts or forms a film.
Acts as a binding agent. It is okay for some moisture to be present in the granulated product, but if the moisture is present in an amount greater than an allowable amount, the granulated product must be dried after granulation.

The particle size of the bleach-activated pore-side granules of the present invention is 125 μm to 3 mm, preferably 350 μm to l, using a sieve or sieve.
, so that the proportion of 5 mm particles is 90% or more.

The bleach activator (a) used in the present invention has a particle size of 1 to 2.
00μm1 preferably 5-100μm1 carbonate is 0.5
It is desirable to use a powder product with a particle size of ~1,000 μm, preferably 1 to 500 μm, and an acid of 0.5 to 300 μm, preferably 1 to 100 μm.

The granules of the present invention have the same storage stability as conventional products as they are, but if necessary, the storage stability can be further improved by coating the surface of the granules with the above-mentioned binder substance using a conventional method. can.

Furthermore, fluidity can be further improved by treating the particle surface with a water-insoluble or slightly water-soluble surface modifier such as finely divided zeolite, titanium oxide, or calcium carbonate.

The granules of the present invention may optionally contain a coloring agent and sulfuric acid.
Bulking agents such as Jum, fragrances, antioxidants, etc. may be added.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained with reference to examples, but the present invention is not limited to these examples.

Example 1 2.4 kg of tetraacetyl ethylene diamine (TAED), 0.42 kg of polyethylene glycol (PBG-6000), and nonionic 0.24 kg of surfactant polyoxyethylene alkyl ether manufactured by Kao (E-340), 1.74 kg of sodium bicarbonate, 1.2 kg of succinic acid, total 6.0 kg.
g, the jacket temperature is 70℃, and the spindle rotation speed is 3.
5 Orpm, chopper rotation speed 150 Orpm,
Granulation was carried out for 30 minutes. After granulation, pour cold water (1
5° C.) to cool the granulated material, and after the temperature reached 40° C. or lower, the granulated material was extracted. Next, this granulated material was passed through a sieve to obtain a product having a particle size of 350 to 1.500 μm. The product yield at this time was 93%.

Example 2 3.6 kg of TAED and polyethylene glycol (PB
0.6 kg of G-6000>, 0.3 kg of nonionic surfactant, and 0.75 kg of sodium hydrogen carbonate.

0.75 kg of succinic acid, total 6. After heating, the jacket temperature was set to 70° C., the spindle rotation speed was set to 20 Orpm, and the chopper rotation speed was set to 1.00 Orpm for 15 minutes.

This mixture was extruded and granulated using a horizontal extrusion granulator (Fuji Paudal ■; Beretter Double BXD-60 type, screen diameter 1.0 mm).

3.0 kg of this granulated material was sized using a Marmerizer (Fuji Paudal H; Q-400 type) at a rotational speed of 60 rpm for 5 minutes. Next, this granulated material was passed through a sieve, and the particle size was 350.
-1.500 μm was used as a product. The product yield at this time was 89%.

Example 3 Each granulation component was blended according to the composition shown in Table 1, and a bleach-activated pore-side granule was obtained by the same operation as in Example 1.

Comparative Examples 1 to 3 Comparative Examples 1 and 2 were prepared by blending each granulation component with the composition shown in Table 1.
In Example 1 and Comparative Example 3, bleach-activated pore-side granules were obtained by the same operations as in Example 2.

Using each of the bleach-activated pore-side granules obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the dissolution rate and storage stability of each were evaluated according to the criteria shown below.

The results are shown in Table 1. The physical properties listed in the table were measured as follows.

Pour 150 ml of water with a dissolution rate of 20°C into a 200 ml beaker and dissolve the sodium percarbonate so that the effective oxygen content is 0.05%.
．． After stirring for 3 minutes at 1100 rpm using a mechanical stirrer with a 2 cm stirring blade, 5 ml of 0.3% catalase solution was added and stirred for 1 minute.

Add 10ml of 10% potassium iodide solution to this solution! , 2
0% sulfuric acid solution 10! ne and 0. Titration is carried out with a sodium thiosulfate solution of IN. Further, titration was also performed after 10 minutes using the same method, and the dissolution rate (after 3 minutes) was calculated using the following formula.

Dissolution rate after 3 minutes (%) = Mixing ratio of sodium percarbonate and bleach activated pore side granules 1/1
Mix 10g of the following composition and store in a 50ml plastic container at 50°C for 2 weeks.

Using the mixed composition before and after storage, the titration number after 10 minutes was determined by the same titration method as the dissolution rate described above, and the residual rate of the activator was calculated using the following formula.

Survival rate (%) = Titration number before storage (ie)

Claims (1)

[Claims] 1 (a) 10 to 85% by weight of bleach activator (b) polyethylene glycol, nonionic surfactant,
One or more binder substances selected from the group consisting of anionic surfactants, long chain fatty acids, and polymeric compounds2~
Bleach activator granules consisting of 50% by weight (c) 5-50% by weight of carbonate (d) 5-50% by weight of solid or powdered acid. 2. The bleach activator according to claim 1, wherein the binder substance is one or more compounds selected from the group consisting of polyethylene glycol with a melting point of 35 to 80°C, a nonionic surfactant, and a long chain fatty acid. Granules. 3. The bleach activator granules according to claim 1, wherein the carbonate is one or more selected from the group consisting of sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate. 4. The bleach activator granules according to claim 1, wherein the solid or powdered acid is an organic acid. 5. The organic acid is selected from the group consisting of succinic acid, fumaric acid, maleic acid, citric acid, malic acid, and tartaric acid.
The bleach activator granule according to claim 4, which is a species or two or more kinds of compounds. 6. The bleach activator granules according to claim 1, wherein the bleach activator is solid at 80°C. 7. The bleach activator is one or more selected from the group consisting of tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, sodium alkanoyloxybenzenesulfonate, and a compound represented by general formula (I). The bleach activator granule according to claim 6, which is a compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 represents an alkyl group of C_1_ to _1_8, R_2 and R_3 represent an alkyl group of C_1 to _2, and R_4 is -(CH_2)_1_ to _1_2 -, L represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] 8. The bleach activator granulated material according to claim 1, wherein the granulated material is obtained by an extrusion granulation method or a stirring and rolling granulation method.