JP3513361B2 - Bleaching detergent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition having excellent bleaching and detergency and excellent storage stability.

[0002]

2. Description of the Related Art Bleaching detergents are classified into chlorine type and oxygen type. However, chlorine type bleaching agents are limited in the fibers that can be used, and also cannot be used for colored patterns and have a peculiar irritating odor. Therefore, oxygen-based bleaching detergents which do not have these drawbacks have been remarkably popular recently. As the oxygen-based bleaching detergent, sodium percarbonate and sodium perborate are commonly used as bleaching bases from the viewpoint of bleaching performance and stability.

Oxygen-based bleaching detergents have weaker bleaching power than chlorine-based bleaching detergents and are therefore used together with various bleaching activators. As typical bleach activators, tetraethylenediamine, acetoxybenzenesulfonic acid, tetraacetylglycolyluril, glucose pentacetate and the like are used. In addition, Japanese Patent Laid-Open No. 59-22999 discloses that
Hydrogen peroxide and the following formula: R-C (= O) -L (wherein R is an alkyl group having about 5 to 18 carbon atoms, and the longest linear alkylalkyl chain containing a carbonyl carbon has 6 to 10 carbon atoms). A bleaching agent having a molar ratio of hydrogen peroxide and bleaching activator produced by a peroxygen bleaching compound of greater than 1.5. It is disclosed.

Recently, a bleaching agent for refilling, which is packed in a thin plastic pouch, has been desired due to the problems of resource saving and dust in packaging containers. As such a bag-shaped container made of plastic for refilling, those disclosed in Japanese Patent Publication No. 3-505322 and Japanese Utility Model Publication No. 3-123847 can be mentioned. Such a plastic container is provided with a ventilation hole for releasing oxygen released by the gradual decomposition of the hydrogen peroxide releasing substance contained in the bleaching agent to the outside and preventing the container from bursting. ing.

[0005]

However, since the plastic container as described above has a vent hole, the oxygen-based bleaching detergent containing a bleaching activator causes powder particles to aggregate during storage. It may cause caking, which becomes a lump. If caking occurs in this way, not only will it be difficult to use, but it will also be unattractive and will not be shipped as a product.

Therefore, the present invention provides a bleaching detergent composition filled in a plastic container, which has an excellent bleaching detergency and can be stably stored without causing caking even when stored for a long period of time. The purpose is to provide.

[0007]

Therefore, as a result of intensive studies, the present inventors have found that by adjusting the moisture permeability of a plastic container having a vent, caking does not occur even when stored for a long period of time. It was found that the present invention has been completed.

That is, the present invention comprises (A) 1-80% by weight of a component that releases hydrogen peroxide in water, (B) the following general formula (I):

[0009]

[Chemical 4]

[In the formula, R represents a linear alkyl group having 7 to 15 carbon atoms, and Y represents -SO ₃ M or -COOM (where M is
Represents a hydrogen atom or an alkali metal atom). ] 0.1-20% by weight of granules containing a bleach activator represented by
And (C) Sodium carbonate is contained, and the water vapor permeability is 1
The bleaching detergent composition is characterized in that it is filled in a plastic container having a ventilation hole of g / m ² · 24 hr or more and a thickness of 20 to 500 μm.

The term "moisture permeability" in the present invention means the amount of water vapor which passes through a membranous substance (a plastic film constituting a container in the case of the present invention) which is a test sample in a certain period of time. It is measured by the cup method specified in Z0208-1976. That is, when the plastic film is used as a boundary surface at a temperature of 25 ± 0.5 ° C., the air on one side is kept at 90 ± 2% relative humidity, and the air on the other side is kept dry by a hygroscopic agent (anhydrous calcium chloride). The amount of water vapor passing through this boundary surface in 24 hours is converted into the moisture permeability per 1 m ² of the plastic film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (A) for releasing hydrogen peroxide in water used in the present invention, an inorganic peroxide salt such as a percarbonate, a perborate or a superphosphate is exemplified. Of these, percarbonates and perborates are preferable, and percarbonates are particularly preferable.

The average particle diameter of the component (A) is preferably 200 to 500 μm, particularly preferably 250 to 4
It is 00 μm. The content of the fine powder that passes through a sieve having a pore size of 125 μm is preferably 20% by weight or less, particularly preferably 10% by weight or less in order to prevent caking of the bleaching detergent composition. , And more preferably 5% by weight or less.

The content of the component (A) in the bleaching detergent composition is from 1 to 80% by weight, and preferably from 1 to 80% by weight, in order to facilitate the blending with other components and impart a sufficient bleaching detergency. 5 to 70% by weight, particularly preferably 20 to 60
% By weight.

The granular material containing the bleaching activator of the component (B) used in the present invention has the following general formula (I):

[0016]

[Chemical 5]

[In the formula, R represents an alkyl group of 7 to 15 and Y represents -SO ₃ M or -COOM (where M represents a hydrogen atom or an alkali metal atom). ] It is a granular material containing the bleach activator represented by these.

In the general formula (I), the straight-chain alkyl group represented by R ¹ ensures sufficient solubility under ordinary washing conditions in Japan and imparts sufficient adsorbing power for stain components. As described above, the carbon number is 7 to 15. Examples of the alkali metal atom represented by M include sodium atom and potassium atom.

As the bleach activator represented by the general formula (I), those represented by the following formula (II) or (III) are preferable.

[0020]

[Chemical 6]

[In the formula, R represents a straight-chain alkyl group having 11 to 15 carbon atoms, and M represents a sodium atom or a potassium atom] or

[0022]

[Chemical 7]

[In the formula, R represents a linear alkyl group having 7 to 11 carbon atoms].

The blending ratio of the bleaching activator in the component (B) is preferably 10 to 9 in order to smoothly granulate and not generate fine powder and to impart sufficient bleaching performance.
It is 5% by weight, particularly preferably 20 to 80% by weight, further preferably 30 to 70% by weight.

The granular material containing the bleaching activator as the component (B) is a granulated product obtained from a bleaching activator, a water-soluble binder and water, and optionally other components or a crushed product thereof. When the component (B) is such a granulated product or a crushed product thereof, the stability of the bleach activator which is unstable alone can be enhanced.

Examples of the water-soluble binder include water-soluble polymers, nonionic surfactants and inorganic binders. Examples of the water-soluble polymer include polyethylene glycol, polypropylene glycol, carboxymethyl cellulose, and polycarboxylic acid salts such as sodium polyacrylate. Polyethylene glycol and polypropylene glycol have a molecular weight of 400
Those in the range of up to 20,000, preferably 600 to 10,000 are suitable. As the nonionic surfactant, polyoxyethylene (number of moles of ethylene oxide added = 3 to 30)
0) To mention alkyl C ₈ -C ₂₂ ether, polyoxyethylene alkylphenyl ether, sucrose fatty acid ester, alkyl glucoside, polyoxyethylene alkylamine, polyoxyethylene-polyoxypropylene glycol, fatty acid monoethanolamide, fatty acid diethanolamide. You can Examples of the water-soluble inorganic binder include sodium silicate and the like. Among these water-soluble binders, polyoxyethylene glycol and polypropylene glycol having a melting point of 20 to 80 ° C. are preferable.

The mixing ratio of the water-soluble binder and water in the component (B) is preferably 0.1 to 40% by weight, particularly preferably 0.3 to 30% by weight, and further preferably 0.3. Is about 20% by weight.

Further, in order to improve the solubility of the granulated product of the component (B) or its crushed product, an anionic surfactant can be added. 1 carbon atom as an anionic surfactant
A straight-chain or branched-chain primary or secondary alcohol sulfate ester salt of 0-18, an ethoxylate sulfate ester salt of an alcohol having 8 to 20 carbon atoms, an alkylbenzene sulfonate, a paraffin sulfonate, an α-olefin. Sulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, in particular, a linear alkylbenzene sulfonate having a carbon number of 12 to 14 and an alkyl sulfate having a carbon number of 12 to 18 are preferable, and the counter ion is preferably an alkali metal, particularly sodium or potassium. preferable.
The compounding ratio of the anionic surfactant in the component (B) is preferably 0 to 40% by weight, particularly preferably 0.3 to 30% by weight, and further preferably 1 to 20.
% By weight.

Further, in order to further enhance the storage stability of the granulated product of the component (B) or the crushed product thereof, an acidic substance can be added. As the acidic substance, formic acid, propionic acid, citric acid, succinic acid, fumaric acid and other organic acids, phosphoric acid,
Inorganic acids such as sodium sulfite, zeolites showing solid acidity and the like can be mentioned. Among these, fumaric acid,
Succinic acid and zeolite showing solid acidity are preferable.
The blending ratio of the acidic substance in the component (B) is preferably 0 to 40% by weight, particularly preferably 0.1 to 3%.
It is 0%.

Next, a method of granulating and crushing the granular material as the component (B) will be described. As a granulation method, it is preferable to apply a consolidation forming method in order to easily disintegrate or dissolve the obtained granules in a solution, but it is not limited to this. As the consolidation forming method, a method of forming a columnar compacted body such as granules having a major axis of 500 μm or more, particularly preferably a major axis of 500 to 3000 μm, and further preferably a major axis of 700 to 2000 μm, by an extrusion granulator. A method in which a plate-shaped compact formed body having a thickness of preferably 200 to 1000 μm, particularly preferably 500 to 5000 μm is compacted into two rotating roll tubes, and the diameter is preferably 500 to 10000 μ depending on a briquette.
It is possible to use a method of forming a tablet-shaped compacted body having m, particularly preferably 500 to 5000 μm in diameter. In the case where the granular material is formed into a cylindrical compact, the surface area is made as small as possible by moving the particle shape away from the spherical shape, thereby reducing the contact area with the component (A) and improving stability. The major axis is preferably 1.1 times or more of the minor axis, more preferably 1.2 to 3 times, and most preferably 1.3 to 2 times.

As an extrusion granulator used in the consolidation forming method,
Examples include pelleter made by Fuji Paudal, granulator made by Kikusui, and briquette machine made by Shinto Kogyo, tableting machine made by Kikusui.
Of these, the extrusion granulator is preferable because it has good solubility and fluidity of the granulated product and excellent productivity. The screen diameter of the extrusion granulator is preferably 20 as the weight average diameter.
The particle size is 0 to 5000 μm, preferably 500 to 5000 μm, and particularly preferably 500 to 3000 μm in order to suitably produce a granular granulated product.

In order to obtain a crushed product, it is possible to apply a method of sizing after compaction molding to a weight average particle size of 200 to 5000 μm by a sizing machine, or a method of granulating and molding using a Marumerizer or the like. it can.

The content of the component (B) in the bleaching detergent composition is 0.1 to 20% by weight, and preferably 0.5 in order to impart sufficient bleaching detergency and to prevent caking. 10% by weight, particularly preferably 1
It is 5% by weight.

The component (C) sodium carbonate used in the present invention acts as an alkaline agent on the bleaching detergent composition. The content of the component (C) in the bleaching detergent composition is 1 to 60% by weight, preferably 5 to 5%, in order to sufficiently exhibit the performance of the component (B) in consideration of economy.
It is 40% by weight, particularly preferably 10 to 30% by weight.

The content ratio of the fine powder (passing through a sieve having a pore size of 125 μm) in the bleaching detergent composition is 20% by weight or less, preferably 15% by weight in order to prevent caking and increase the stability of the composition. % Or less, particularly preferably 10% by weight or less. Further, the content of the organic component in this fine powder is preferably 20% by weight or less, particularly preferably 10% by weight or less, and further preferably, in order to prevent caking and enhance the stability of the composition. It is 5% by weight or less. Here, the organic component means a bleach activator, a water-soluble binder (excluding an inorganic binder), and a surfactant which may be added as an optional component.

The amount of water in the bleaching detergent composition is 5% by weight or less, preferably 1 to 5% by weight, particularly preferably 1 to 5% in order to prevent caking and enhance the stability of the composition. It is 3% by weight.

The bleaching detergent detergent composition of the present invention may contain general cleaning ingredients. Examples of the cleaning component include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants, and of these, anionic surfactants are preferable,
It is a nonionic surfactant. Examples of the anionic surfactant include a sulfuric acid ester salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, a sulfuric acid ester salt of an ethoxylate compound of an alcohol having 8 to 20 carbon atoms, and an alkylbenzene sulfonic acid. Salt, paraffin sulfonate, α-
Olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt or fatty acid salt is preferable. Particularly in the present invention, the number of carbon atoms in the alkyl chain is 12 to 14
Straight-chain alkylbenzene sulfonate with 12 to 1 carbon atoms
Alkyl sulfate of 8 is preferable, and as the counter ion, alkali metals are preferable, and sodium or potassium is particularly preferable. As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, as the nonionic surfactant, an HLB value (Griffin method) obtained by adding 4 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms is used. Is calculated from 10.5
Polyoxyalkylene alkyl ethers such as 15.0, preferably 11.0 to 14.5 are preferred.

A crystalline silicate can be added to the bleaching detergent detergent composition of the present invention. The crystalline silicate is preferably an alkali metal salt of silicic acid (SiO ₂ ), 0.1%
The maximum pH value of the dispersion is 11 or more (25 ° C.),
For 1% dispersion liquid 1, use 0.1N hydrochloric acid aqueous solution to p
It requires more than 5 ml to reduce to H10, and is excellent not only in alkalinity but also in alkaline buffering capacity. Above all, Si of alkali metal silicate
O ₂ / M ₂ O (M represents an alkali metal) is preferably 0.5 to 2.6, particularly preferably 1.5 to 2.6. The conventionally known crystalline silicate has a SiO ₂ / Na ₂ O content of 1.9 to 4.0, but a crystal silicate having a ratio of more than 2.6 is suitable for blending a high-density detergent targeted by the present invention. It may not be suitable.

The crystalline silicate of the present invention has an ion exchange capacity of at least 100 CaCO ₃ mg / g or more,
It is preferably one having 200 to 600 CaCO ₃ mg / g, which is one of the substances having an ion trapping ability in the present invention. The crystalline silicate has an average particle size of 0.1.
The thickness is preferably -100 μm, particularly preferably 1-60 μm. The average particle size referred to here is
It is the median diameter of the particle size distribution. The crystalline silicate having such an average particle size and particle size distribution can be prepared by pulverizing with a pulverizer such as a vibration mill, a hammer mill, a ball mill and a roller mill.

The crystalline silicate suitable for use in the present invention has the following formula (IV): x (M ₂ O) .y (SiO ₂ ) .z (Me _m O _n ) .w (H ₂ O) (IV) [In the formula, M represents an Ia group element of the periodic table, and Me represents one element selected from the IIa group element, the IIb group element, the IIIa group element, the IVa group element, or the VIII group element of the periodic table, or Shows a combination of two or more kinds, y / x = 0.5 to 2.6, z / x = 0.01
.About.0.9, w = 0 to 20, and n / m = 0.5 to 2.0. ] It has a composition represented by.

Me is selected from the IIa group element, the IIb group element, the IIIa group element, the IVa group element or the VIII group element of the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr and Fe. You can These are not particularly limited, but from the viewpoint of resources and safety, preferably Mg,
It is Ca. These may be used alone or in admixture of two or more, for example MgO, CaO or the like may constitute the Me _m O _n component are mixed.

In the general formula (IV), y / x prevents the alkaline ability from becoming insufficient and becoming insufficient as an alkaline agent, and also the ion exchange ability from becoming insufficient as an ion exchanger, and water resistance. It is preferably 0.5 to 2.6, and particularly preferably 1.5 to 2.6, in order to prevent the solubility from being insufficient and significantly affecting the caking properties, the solubility, and the powder physical properties of the composition. Is. Further, in the general formula (IV), z / x is preferably 0 in order to prevent the on-exchange ability from becoming low and preventing it from becoming insufficient as an ion exchanger and preventing the water resistance from becoming insufficient. .0
It is 1 to 0.9, and particularly preferably 0.02 to 0.5.

X, y, z are not particularly limited as long as they have the relations shown by the above-mentioned y / x ratio and z / x ratio. Note that, as described above, x (M ₂ O) is, for example, x '(Na ₂ O) xx ((K
₂ O), x becomes x '+ x ". Such a relationship is the same in z in the case where the z (Me _m O _n ) component is composed of two or more kinds. n / m represents the number of oxygen ions coordinated to the element, which is substantially 0.5,
It is selected from the values of 1.0, 1.5 and 2.0.

Further, the following formula (V): M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (V) [wherein M represents an alkali metal, x ′ = 1.5 to 2.6, y '
= 0 to 20 is shown. ] A crystalline silicate having a composition represented by the following can also be used.

In the general formula (V), M is selected from the group Ia elements of the periodic table, and examples of the group Ia elements include Na and K. These may be used alone or as a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Also, x'and y '
It is preferable that 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and a cation exchange capacity of 100 to 400 CaCO ₃ mg / g can be used, which is one of the substances having an ion trapping capacity in the present invention. .

The crystalline silicate represented by the general formula (V) is generally an amorphous glassy sodium silicate of 200 to 100.
It is obtained by firing at 0 ° C. to make it crystalline. For details of the synthesis method, see, for example, Phys.Chem.Glasses.7, p127-p1.
38 (1966), Z. Kristallogr., 129, p 396-p404 (1969) and the like. Further, the crystalline silicate represented by the general formula (V), for example, trade name "Na-SKS-6" from Hoechst
As (δ-Na ₂ Si ₂ O ₅ ), powdery and granular ones are available.

In the present invention, the crystalline silicates represented by the general formulas (IV) and (V) may be used alone or in combination of two or more kinds. The compounding amount of the crystalline silicate is preferably 0.1 to 10% by weight, particularly preferably 1 to
It is 5% by weight.

The bleaching detergent detergent composition of the present invention may contain a carboxylic acid polymer such as a copolymer or homopolymer having a molecular weight of several hundred to 100,000. Carboxylic acid-based polymer is a component that not only has the function of sequestering metal ions, but also acts to disperse solid particle dirt from clothes into the washing bath and to prevent the particles from redepositing (recontaminating) on clothes. . The copolymer is generally random polymerization. Among these carboxylic acid-based polymers, salts of acrylic acid-maleic acid copolymers and polyacrylic acid salts (Na, K, NH ₄ ) are preferable and have a molecular weight of 1.0.
It is preferably from 80 to 80,000. The carboxylic acid-based polymer can usually be easily obtained by polymerizing an unsaturated organic carboxylic acid or organic polycarboxylic acid, but has a molecular weight of 2,000 or more and a carboxyl group of 10 or more. If so, the unsaturated carboxylic acid monomer as the raw material is not limited.
In addition to the above carboxylic acid-based polymers, polymers such as polyglycidyl acid salts, cellulose derivatives such as carboxymethyl cellulose, and aminocarboxylic acid-based polymers such as polyaspartic acid salts also have sequestering ability, dispersing ability and anti-soil redeposition ability. Therefore, they can be used together in the present invention.

If necessary, the bleaching detergent composition of the present invention may further contain the following components.

(1) Sequestering Agents As the sequestering agents other than the aluminosilicates, crystalline silicates and carboxylic acid type polymers mentioned above, there may be mentioned organic chelating agents such as diglycolic acid, oxydisuccinic acid and citric acid. Polycarboxylic acid salts such as acids or salts thereof,
Nitrilotriacetic acid, ethylenediaminetetraacetic acid, iminodiacetic acid, hydroxyiminodiacetic acid, aminopolycarboxylic acids such as hydroxyiminodisuccinic acid or salts thereof, ethane-1,
Salts of phosphonic acids such as 1-diphosphonic acid and ethane-1,2-triphosphone are preferable, and organic chelating agents having a pKCa value of 4 or more are particularly preferable. Examples of the inorganic sequestering agent include phosphates such as orthophosphate, pyrophosphate, and tripolyphosphate. In the case of salt, sodium and potassium are preferable as counterions.

(2) Phosphorus Compound As the phosphorus compound, a conventionally known compound that complements a metal ion is preferable. Especially tripolyphosphate,
Orthophosphate and metaphosphate are preferable, and sodium tripolyphosphate is particularly preferable.

(3) Enzymes Enzymes (which are enzymes that inherently perform an enzymatic action during the washing step) are classified according to the reactivity of the enzymes, such as hydrolases, oxidoreductases, lyases, transferases and isomerases. Although the above can be mentioned, any of them can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain,
Promelin, carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B, which are commercially available products such as sabinase, alcalase (Novo Industry Co., Ltd.), API21 (Showa Denko KK), Maxacar (Gistprocay). (Death), JP-A-5-2549
Protease K-14 or K-16 described in JP-A-2 can be mentioned. Specific examples of esterases include:
Examples thereof include gastric lipase, buncreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotase. Specific examples of lipases include commercially available lipases such as lipolase (Novo Industry Co., Ltd.) and liposam (Showa Denko KK). Also, as cellulase, commercially available cellzyme (Novo Industry Co., Ltd.), JP-A-6
Examples thereof include cellulase according to claim 4 of JP-A-3-26469, and examples of amylase include commercially available Termamyl (Novo Industry Co., Ltd.). The enzyme is separately granulated as stable particles and used in a dry blended state with detergent dough (particles).

(4) Fluorescent dye As a fluorescent dye, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-) is used.
Sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbenzylsulfonic acid derivative, Whitex SA ( Sumitomo Chemical Co., Ltd.), Chino Pearl CBS (Ciba Geigy Co., Ltd.) and the like can be mentioned. One or two or more of these fluorescent dyes can be added to the composition in an amount of 0 to 2% by weight.

(5) Fragrance As a fragrance, a fragrance that has been conventionally blended in detergents, for example, the fragrance described in JP-A-63-101496, dimethylbenzylcarbinyl acetate, tricyclo [5.2.1.0]
^2,6 ] -dec-3-en-8-yl acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-en-8-isopropionate, 3-amyl-4-acetoxytetrahydropyran, 4-tert-butylcyclohexyl acetate, 2
-Tert-butylcyclohexyl acetate, p-tert-
Butyl-α-methylhydrocinnamic aldehyde, 4
-(4-Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, α-amylcinnamic aldehyde, α, α′-dimethyl-p-ethylhydrocinnamic aldehyde, etc. Can be mentioned. Of course, in order to prevent deterioration due to other detergent components, the type of each fragrance component to be blended and, depending on the case, the blending ratio and blending amount are considered.

(6) Defoaming Agent As the defoaming agent, conventionally known ones, for example, silicone / silica type defoaming agents can be mentioned. The defoaming agent is described in JP-A-3-186307 described below. A defoaming agent granulated product produced by the method described in the lower left column of page 4 of the publication may be used. First, 20 g of Dow Corning silicone (compound type, PS antifoam) as an antifoaming component is added to and mixed with 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nippon Starch Chemical Co., Ltd. to obtain a homogeneous mixture. Next, 50% of the obtained homogeneous mixture, 25% of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% of neutral anhydrous Glauber's salt are mixed at 70-80 ° C., and then extrusion granulated by Fuji Paudal Co., Ltd. Granulate with a machine (model EXKS-1) to obtain granules.

The bleaching detergent composition of the present invention has a moisture permeability of 1
It is filled in a plastic container having a ventilation hole of 20 to 500 μm in thickness of g / m ² · 24 hours or more. The water vapor permeability of this plastic container is preferably 1.1 g / m ² · 24 hr or more, particularly preferably 1.5 g / m ² · 24 hr or more. Vents are formed, for example, in the upper part of the container (near the opening when in use) in order to ensure appropriate ventilation between the desired part of the container, usually the external atmosphere, but its shape and size are It is not particularly limited. The ventilation holes preferably have a diameter of 0.1 to 5 mm, particularly preferably a circular ventilation hole having a diameter of 0.1 to 1 mm, or preferably have a width of 0.
It is possible to form linear ventilation holes having a width of 1 to 5 mm, particularly preferably 1 to 3 mm. Further, the plastic container preferably has a light transmittance of 200 to 800 nm of 30% or less, particularly preferably 20% or less,
It is more preferably 10% or less.

As a plastic material used for such a plastic container, linear low density polyethylene,
One or more selected from low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate can be mentioned. Also,
Besides, a plastic film having a multilayer laminated structure can also be used. As the plastic film having this multilayer laminated structure, for example, a linear low density polyethylene is used inside the container, and a plastic having mechanical strength such as stretched nylon or stretched polypropylene is used as the outermost layer. Can be mentioned. The thickness of each of these layers is preferably about 5 to 300 μm. Further, the plastic container may be provided with a barrier layer, a pinhole resistant layer, a tear guide layer and the like.

The plastic film forming the plastic container can be easily manufactured by a known method. For example, as a method for producing a laminated film, a dry laminating method, a T-die method, a co-extrusion laminating method, an inflation method, a tandem laminating method and the like can be mentioned. The form of the plastic packaging container is not limited, but it is preferable to use a container in the shape of a bag (small bag) having a desired capacity by heat-sealing the periphery of a plastic film of a desired size.

[0059]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Production Example 1 (Production of bleach activator (a)) 100 g (0.46 mol) of sodium p-phenolsulfonate (manufactured by Wako Pure Chemical Industries) dehydrated in advance was dispersed in 300 g of dimethylformamide (DMF). Then, while stirring with a mechanical stirrer, lauric chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at 50 ° C. over 30 minutes. After completion of dropping, an aging reaction was performed for 3 hours. DMF under reduced pressure (
0.5-1mmHg), distilled off at 100 ℃, washed with acetone,
Recrystallization was carried out in a water / acetone (1/1 mol) solvent.
Yield 85%.

Production Example 2 (Production of Bleach Activator (b)) A bleach activator was prepared in the same manner as in Production Example 1 except that myristic acid chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of lauric acid chloride. Obtained. Yield 75%.

Production Example 3 (Production of bleach activator (c)) Bleach activation was carried out in the same manner as in Production Example 1 except that p-phenolcarboxylic acid dehydrate was used instead of sodium p-phenolsulfonate. I got an agent. Yield 65%.

Production Example 4 (Production of Component (B)) 2.7 kg of each of the bleach activator obtained in Production Examples 1 to 3 and TAED (manufactured by Hoecst) as a bleach activator for Comparative Examples are used. Glycol (Molecular weight 6000, PEG6
000) 0.6 kg, sodium alkylsulfate (C ₁₂ ) 1.7 k
g, 5 kg in total is charged into a mixer (Fukae Kogyo, high speed mixer, FS-GC-10 type) and the jacket temperature is 80
℃, spindle speed 200rpm, crushing spatter speed 1500
Mixing was carried out at rpm and the temperature was raised, and the mixture was extracted when the temperature of the powder reached 70 ° C. Then, the obtained mixture was extruded and granulated (made by Fuji Paudal, Pelletable EXD-10
(0 type) was extruded through a screen having a pore size of 800 μm for consolidation. The obtained granules were cooled with a vibration cooler (Fuji Paudal, Vibro Flow Dryer VDF / 6000). After cooling, it was crushed with a particle sizer (Fuji Paudal, knife cutter FL-200). The obtained granules are classified by a classifier (Dokuju Seisakusho, Kotobuki type vibrating sieve) to obtain a particle size of 350 to 1400 μm (weight average 900 μm, 125 μm pass 2).
Granules containing (wt%) bleach activator were obtained.

Production Example 5 (Production of Plastic Pouch 1) A stretched nylon having a thickness of 20 μm, a linear low-density polyethylene having a thickness of 100 μm and a stretched nylon having a thickness of 15 μm are laminated in this order to form a rectangular shape. Two sets were prepared, and the drawn nylons each having a thickness of 15 μm were overlapped so that they were on the inside, and the three sides were heat-sealed, and
Vents having a diameter of 5 mm were formed to obtain a pouch 1 having a volume of 500 ml. The moisture permeability of this pouch 1 was measured to be 12.5 g /
It was m ² · 24 hr.

Production Example 6 (Production of Plastic Pouch 2) A stretched nylon having a thickness of 20 μm, a linear low density polyethylene having a thickness of 50 μm, and a stretched nylon having a thickness of 15 μm are laminated in this order to form a rectangular shape. Prepare two pairs,
Each layer of stretched nylon with a thickness of 15 μm is placed inside and heat-sealed on three sides, 0.5 mm
Vents having a diameter were formed to obtain a pouch 2 having a volume of 500 ml. When the moisture permeability of this pouch 2 was measured, it was 32 g / m ² · 24h
It was r.

Production Example 7 (Production of plastic pouch 3) Stretched nylon having a thickness of 20 μm, linear low density polyethylene having a thickness of 100 μm, aluminum foil having a thickness of 10 μm and thickness of 15
Prepare two sets of rectangular shapes by stacking stretched nylon of μm in this order, and stack them so that each stretched nylon of 15 μm thickness is on the inside, and heat-seal the three sides to 0.5 mm. Vents having a diameter were formed to obtain a pouch 3 having a volume of 500 ml. The moisture permeability of this pouch 3 was measured and found to be 0.03 g / m ² · 24 hr.

Production Example 8 (Production of Plastic Pouch 4) A stretched nylon having a thickness of 20 μm, a linear low density polyethylene having a thickness of 100 μm and a stretched nylon having a thickness of 15 μm are laminated in this order to form a rectangular shape. I prepared two pairs. In addition, an oxidized silicate was vapor-deposited on the surface of the stretched nylon having a thickness of 20 μm to be each outer layer. next,
Each layer of stretched nylon with a thickness of 15 μm is placed inside and heat-sealed on three sides, 0.5 mm
Vents having a diameter were formed to obtain a pouch 4 having a volume of 500 ml. When the moisture permeability of this pouch 4 was measured, it was 4g / m ² · 24hr.
Met.

Examples 1 to 11 and Comparative Examples 1 to 4 As shown in Table 1, the components (A) to (C) and further other components were filled in sachets 1 to 4, and the bleaching of Examples and Comparative Examples was performed. A cleaning composition was obtained. A caking property test was performed on these compositions by the following method. In Table 1, Softanol 120 (manufactured by Nippon Shokubai) is a nonionic surfactant. The results are shown in Table 1.

(Caking Property Test) 200 g of each of the bleaching detergent compositions of Examples and Comparative Examples packed in sachets 1 to 4
Was stored in a thermo-hygrostat at a temperature of 30 ° C. and a humidity of 60% for 4 weeks. Then, each composition was taken out from the pouches 1 to 4 and gently dropped on a sieve having a sieve opening of 1 × 1 cm. Then, the weight of the sample remaining on the sieve was measured, and the caking rate was calculated by the following formula. Caking rate (%) = weight of sample remaining on the screen x 10
0 / Sample weight

[0070]

[Table 1]

As is clear from Table 1, Examples 1 to 11
The compositions of all had a low caking rate and kept a good state as a product. On the other hand, Comparative Example 1 using a bleach activator different from the present invention, Comparative Example 2 using a plastic container having a water vapor transmission rate lower than the value specified in the present invention, the blending amount of the component (B) is The compositions of Comparative Example 3, which is outside the scope of the present invention, and Comparative Example 4, in which the content ratio of the component (A) is outside the scope of the present invention, all have a caking rate of more than 10%, which is a poor product. Became. After the test was completed, when the composition of Examples 1 to 11 was used to wash acrylic, polyester, polyamide, etc. synthetic fiber clothing with a commercially available washing machine, an excellent bleaching and washing effect was exhibited.

[0072]

The bleaching detergent composition of the present invention hardly causes caking even when stored for a long period of time. Therefore, the stability of the bleach activator can be ensured, and thus the excellent bleaching detergency can be maintained for a long period of time. In addition, the manufacturer can easily store the product before shipping, reduce the occurrence of defective products after manufacturing, and improve the product yield. Also for consumers,
Since the quality is stable during normal use, the bleaching cleaning power at the time of purchase can be secured for a long time.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sourou Aoyagi 1334, Minato Minato, Wakayama, Wakayama Kao Corporation (56) References JP-A-9-194884 (JP, A) JP-A-9-20899 (JP, A) JP-A-6-32027 (JP, A) JP-A-8-174742 (JP, A) JP-A-6-106681 (JP, A) JP-A-8-58807 (JP, A) JP-A-8 -244172 (JP, A) JP-A-58-213099 (JP, A) Actually developed 56-72747 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 3/395 C11D 3/10 C11D 3/20 C11D 3/34 C11D 3/39

Claims (3)

(57) [Claims] 1. A bleaching detergent comprising a bag-like container filled with a bleaching detergent composition, wherein the bleaching detergent composition comprises (A) a sodium percarbonate 20 having an average particle size of 200 to 500 μm.
-80% by weight, (B) the following general formula (I): [In the formula, R represents a linear alkyl group having 7 to 15 carbon atoms,
Y denotes a -SO ₃ M or -COOM (wherein M represents a hydrogen atom or an alkali metal atom). ] 0.1 to 20% by weight of a bleaching activator-containing granule and (C) sodium carbonate are contained, and the bag-shaped container is a linear low-density polyethylene, low-density polyethylene, unstretched. Made from one or more materials selected from polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate, with a water vapor transmission rate of 1 g / m ² · 24 hr
As described above, the bleaching detergent comprising a plastic film having a thickness of 20 to 500 μm and having a circular ventilation hole having a width of 0.1 to 1 mm or a linear ventilation hole having a width of 1 to 3 mm. 2. The bleaching detergent composition contains 10% by weight or less of fine powder that passes through a sieve having a pore size of 125 μm or less.
The bleaching detergent described. 3. The bleaching detergent according to claim 1, wherein the bleaching detergent composition has a water content of 5% by weight or less.