JP3429682B2 - Enzyme granules - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an enzyme granulated product.

[0002]

2. Description of the Related Art When an enzyme granule is blended in a detergent composition as a cleaning aid, it is colored with a pigment depending on the type of enzyme in order to prevent accidental ingestion and to emphasize its beautiful appearance. It is being appreciated.

However, some of these components have poor dispersibility in water or detergent solutions, so that when a detergent composition containing such enzyme granules is used, the components may be washed depending on the method of use. There was a considerable risk that the clothes would be stained and spots would appear on the dried clothes.

[0004]

The object of the present invention is that it has good solubility in water and detergent solutions, and does not have dyeability on clothes.
In addition, the enzyme granulated product is excellent in appearance.

[0005]

The present invention provides an enzyme granulated product containing at least one selected from anthraquinone dyes having at least one sulfonic acid group and carbonium dyes having at least one sulfonic acid group, and an enzyme granule containing the same. A detergent composition containing the same is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned anthraquinone dye is an anthraquinone derivative or anthrone derivative having one or more sulfonic acid groups in terms of water solubility.
CIAcid Blue 25, CIAcid Blue 127, CIAcid Blu
e 112, CI Acid Blue 62 and the like. Further, the carbonium dye has a sulfonic acid group of 1 in view of water solubility.
One or more diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye, etc.,
Specifically, CI Acid Blue 9, Blue No. 205, Kayacyl Pu
Examples include re Blue FGA and Kayanol Cyanine G. In the present invention, the anthraquinone dye is CI because of its solubility in water and the beautiful appearance when blended in a detergent composition.
Acid Blue 112 and carbonic acid dye CIAcid
It is preferable to use Blue 9.

To make the color of the enzyme granules softer, the detergent composition can be given a refreshing feeling by mixing a yellow dye. Specifically, CI Acid Y as an azo dye
Examples include ellow 17 and CI Acid Red 27. Also, such an effect can be obtained by changing the ratio of CIAcid Blue 9 and CIAcid Blue 112 and mixing them. Although the phthalocyanine dye has a sulfonic acid group in its structure,
As extreme dyeing occurs on cotton cloth, linen cloth, etc.,
Alternatively, it is not preferable to use it by mixing it with another coloring agent.

The content of the colorant used in the present invention is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.5% by weight, based on the enzyme granulated product. Within this range, the appearance of the product will be good and appropriate coloring without color transfer will be possible.

Further, the enzyme used in the present invention is at least one selected from the group consisting of cellulase, protease, lipase and amylase. The type, origin, and purity are not particularly limited, but for example, a filtrate or a concentrate obtained by culturing a microorganism can be used as it is. However, the combination of protease and cellulase is particularly preferable in consideration of the dispersibility of the colorant at the time of enzyme granulation and the dyeing property to clothes. The reason for this is not clear, but the effect of removing celluloses and keratin on the surface of the fiber by protease improves the effect of cellulase to remove sebum inside the fiber, thereby preventing the dye from remaining on sebum components. Guessed.

In the present invention, a binder, a bulking agent, an enzyme stabilizer, and a coating agent, if necessary, can be added as other granulation additives. Examples of the binder include starch, dextrin, cellulose derivatives such as hydroxypropyl cellulose, polyalkylene glycols such as polyvinyl alcohol and polyethylene glycol, or ethers thereof. In particular, it is preferable to use polyethylene glycol or a polyethylene glycol having a terminal hydroxyl group methoxylated in combination with the above colorant in order to suppress moisture absorption and deterioration due to a detergent component and to maintain the appearance.
The content of the binder is 5 to 30% by weight, preferably 5 to 20% by weight in the colored enzyme granulated product. Glauber's salt etc. are mentioned as an extender, and the content is 1-60 weight%. As the enzyme stabilizer, sodium borate, calcium chloride or the like can be used. The content of the enzyme stabilizer is 0.5 to 30% by weight in the colored enzyme granulated product. As the coating agent or coating aid, for example, amycol, titanium dioxide, talc and the like can be used. By combining the coating agent or coating aid with the colorant used in the present invention, a wider hue can be obtained than when the colorant alone is used. The content of the coating agent or coating aid is 1 to 40% by weight in the colored enzyme granulated product.

The method for producing the enzyme granules of the present invention is based on a known method, and examples thereof include the method for producing enzyme granules described in JP-A-62-257990.

The shape and average particle diameter of the enzyme granulated product of the present invention are preferably selected according to the shape and average particle diameter of the detergent particles used. The average particle size is preferably 100
~ 1000 μm.

The enzyme granulated product of the present invention is for granular clothes,
It can be added to detergent compositions or bleaching compositions for automatic dishwashers and households.

The surfactants used in the detergent composition for clothes include the following. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, alkane sulfonate, fatty acid salt, alkyl or alkenyl ether carboxylate. , Alkyl or alkenyl phosphoric acid esters or salts thereof, and the like. The anionic surfactant suitable for use in the present invention is an alkylbenzene sulfonate having 10 to 18 carbon atoms or an alkyl sulfate having 10 to 18 carbon atoms. The counter ion is preferably sodium, potassium or ammonium, and particularly preferably potassium or sodium. As the nonionic surfactant, for example, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide, or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoside, fatty acid glycerin monoester, alkyl Examples thereof include amine oxide. In the present invention, in particular, the total carbon number is 12 to 16 and the ethylene oxide addition mole number is 5 to 15
The polyoxyalkylene alkyl or alkenyl ether of is preferred from the viewpoint of oil stain cleaning power. In addition, betaine-type amphoteric surfactants, sulfonic acid-type amphoteric surfactants, cationic surfactants and the like may be added.

In the detergent composition for clothes, for example, alkali agents such as silicates, carbonates and sesquicarbonates, extenders such as mirabilite, crystalline aluminosilicates, orthophosphates, pyrophosphates, Divalent metal ion scavengers such as tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, isocitrate, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylate, acrylic acid-maleic acid Examples include anti-redeposition agents such as polymers or salts thereof, anti-caking agents, stabilizers for peroxides, antioxidants, fluorescent dyes, bluing agents, photo-activated bleaching agents, and fragrances.

The content of the detergent composition for clothes is 5 to 60% by weight, especially 5 to 40% by weight of a surfactant, and 1 to 50% of an alkaline agent.
% By weight, 1 to 50% by weight of divalent metal ion scavenger, 1 to 10% by weight of redeposition preventing agent, 1 to 10% by weight of fluorescent dye, 0.01 to fragrance
5% by weight is preferable, and the colored enzyme granulated product of the present invention is 1-10.
It is preferably blended by weight%.

[0017]

Examples [I] Colored enzyme granulated product (1) Preparation of colored enzyme granulated product The method for manufacturing the granulated product is as follows. JP-A-5
Average particle size obtained by adding calcium chloride and Glauber's salt to an aqueous solution of an alkaline protease obtained by culturing a Bacillus strain described in Japanese Patent No. 25492, and drying with a spray dryer.
35% by weight of 50 μm powder (The amount of calcium chloride and Glauber's salt is
0.5 wt% and 48 wt% of the dry product, 45 wt% sodium chloride with an average particle size of 610 μm, and a molecular weight of 60
Polyethylene glycol 15% by weight of 00 and titanium oxide 5
The weight% was put into a stirring and rolling device (Fukae Industry Co., Ltd .: high speed mixer FS-10 type), and mixed and stirred. When the temperature of the contents increased to 65 ° C, the contents were discharged from the mixer, immediately transferred to a fluidized bed and cooled to 30 ° C. The obtained granulated product was sieved, and 350 to 1000 μm particles were used as enzyme particles.

Next, water and glycerin (weight ratio 1: 4)
A mixed solution obtained by adding the dyes listed in Table 1 to 10 g of the mixed solvent of polyethylene glycol melted at 70 ° C (molecular weight
6000) 100 g to obtain a stirring dispersion liquid.

490 g of the above enzyme particles was placed in a stirring and rolling device (Fukae Industry Co., Ltd .: high speed mixer LFS-GS-2J type).
After charging, the temperature was raised to 60 ° C. Later the above stirring dispersion
11.25 g was added, followed by stirring and rolling to coat the particles. After the coating of the particles was completed, the particles were cooled to 45 ° C. and extracted from the apparatus to obtain an enzyme granulated product (a). In addition, JP-A-6-3434
An enzyme granule (b) was obtained in the same manner except that an aqueous solution of alkaline cellulase obtained by culturing a Bacillus strain described in JP-A No. 61 was used.

[0020]

[Table 1]

(2) Evaluation of Coloring State of Enzyme Granulated Product For each enzyme granulated product obtained in (1) above, 5 panelists visually determined the colored state and hue,
The coloring state was evaluated. As a result, the enzyme granulated product of the present invention using the carbonium dye or the anthraquinone dye,
In the case of any enzyme, the same evaluation as that of the phthalocyanine dye was obtained.

[II] Detergent particles (3) Preparation of detergent particles Detergent particles having the formulation shown in Table 2 were prepared by the following procedure.
3 of the compounding amounts of the nonionic surfactant in the components of Table 2
Water is added to the components except the amount corresponding to wt%, the amount corresponding to 8% by weight of the crystalline sodium aluminosilicate compounding amount, and the total amount of the crystalline silicate compounded, to prepare an aqueous slurry having a water content of 50% by weight. Prepared. The slurry is spray dried to obtain a bulk density
A 0.26 to 0.3 g / cm ³ detergent fabric was prepared. Next, these detergent fabrics are mixed with a high speed mixer (stirring granulator,
Fukae Kogyo Co., Ltd.) and added 5% by weight of the crystalline sodium aluminosilicate, a nonionic surfactant (3% by weight), and the total amount of the crystalline silicate. In addition, pulverization and stirring granulation was performed, and it was confirmed that the particles had grown (about 500 μm). Further, the remaining crystalline sodium aluminosilicate was added and stirred to coat the particle surface to obtain high-density detergent particles having a bulk density of 0.7 to 0.9 g / cm ³ .

[0023]

[Table 2]

The details of each raw material in Table 2 are as follows. -LAS-Na: straight-chain alkyl (carbon number 10 to 13) sodium benzenesulfonate-AS-Na: sodium alkylsulfate (sulfate of mixed alcohol of 50% C12 alcohol and 50% C14 alcohol) -Soap: sodium coconut oil-derived fatty acid-Nonionic surfactant: Polyoxyethylene (average number of moles of ethylene oxide added = 6) alkyl (carbon number 12
~ 13) Ether-Crystalline silicate: SKS-6 (manufactured by Hoechst) crushed (average particle size 40 μm) -Amorphous sodium silicate No. 1 sodium silicate (manufactured by Toso Sangyo Co., solid content 44%) ) ・ Crystalline sodium aluminosilicate: 4A type zeolite,
Average particle size 3 μm (manufactured by Zeo Builder) -Acrylic acid-maleic acid copolymer: sodium salt of maleic acid / acrylic acid = 3/7 (molar ratio), molecular weight 60
000 ・ Polyethylene glycol: average molecular weight 10000 ・ Fluorescent dye: Chinopearl CB-X (manufactured by Ciba Geigy) and Whitetex SA (manufactured by Sumitomo Chemical) are mixed in a weight ratio of 1/1.

(4) Dyeing property test The dyeing property was evaluated using the enzyme granules prepared in (1) above. First, a 32 cm × 16 cm cotton or linen cloth is prepared as a dyeability test cloth. Next, 10 g of the detergent particles obtained in (3) above was dry mixed with 0.1 g of either the enzyme granules (a) or (b) obtained in (1) above to form a single layer of a detergent composition. It was sprinkled on the test cloth so as to be uniform. Place the test cloth on top of this detergent layer and let it stand still in a 35 cm x 23 cm vat, and gently pour 400 cc of water so that the test cloth will fluff so that no air bubbles will enter it. After rinsing for 5 minutes and after dehydration, the total score visually evaluated by 5 panelists on a scale of 5 is shown in Table 3. [Visual judgment criteria] 5: No dyeing is observed 4: Slight dyeing is observed 3: Some dyeing is observed 2: Dyeing is observed 1: Large stain is observed

[0026]

[Table 3]

As is clear from the results shown in Table 3, the enzyme granulated product of the present invention has a beautiful appearance and is not dyed to clothes.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 61-92570 (JP, A) JP-A 9-48996 (JP, A) JP-A 10-183181 (JP, A) JP-A 1- 113498 (JP, A) JP-A-1-113499 (JP, A) JP-A-63-137997 (JP, A) JP-A-10-110189 (JP, A) Actual development Sho-60-189550 (JP, U) JP-B-49-26286 (JP, B1) JP-A-8-507098 (JP, A) JP-A-7-500013 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C11D 3/386 C11D 7/42 C12N 9/96-9/98

Claims (5)

(57) [Claims] 1. (A) One or more colorants selected from anthraquinone dyes having one or more sulfonic acid groups and carbonium dyes having one or more sulfonic acid groups , (B)
It flops protease and cellulase, (C) a cellulose derivative
And polyalkylene glycol or its ether
5 to 30% by weight of binder to be treated, 1 to 60 weight of (D) extender
%, 0.5 to 30 weight% of (E) enzyme stabilizer, and
(F) An enzyme granulated product containing 1 to 40% by weight of a coating agent or coating aid . 2. The enzyme granulated product according to claim 1, which contains 0.001 to 1% by weight of a colorant. 3. A detergent composition containing the enzyme granulated product according to claim 1 or 2 . 4. The detergent composition according to claim 3, which contains the enzyme granulated product in an amount of 1 to 10% by weight. 5. A surfactant, 5 to 60% by weight, an alkaline agent, 1 to 50% by weight, a divalent metal ion scavenger, 1 to 50% by weight, a redeposition inhibitor, 1 to 10% by weight, and a fluorescent dye. The detergent composition according to claim 3 or 4 , which comprises 1 to 10% by weight and 0.01 to 5% by weight of the fragrance.