JPH08165493A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent composition having excellent stability in washing liquids, preferably exhibiting good washing power in warm water, and maintaining the good activity even in bleaching agent compositions by compounding an alkali protease produced from a specific microorganism. CONSTITUTION: The detergent composition contains an alkali protease produced from at least one of Bacillus sp. P strain (FERM 8090), Bacillus sp. K strain (FERM 8091) and Bacillus sp. X strain (FERM 8092). And a bleaching detergent composition contains the enzyme, and an oxygen peroxide compound or the oxygen peroxide compound and an organic peracid precursor.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent composition containing a novel alkaline protease having good stability in a washing solution and having excellent detergency, and a novel alkaline protease and an oxygen-based peroxide or oxygen. The present invention relates to a bleaching detergent composition, which is characterized by blending a system peroxide and an organic peracid precursor.

[0002]

2. Description of the Related Art Conventionally, it has been well known that an enzyme such as amylase, protease, cellulase or lipase is blended in order to obtain a cleaning composition having an improved cleaning power against dirt on clothes (Japanese Patent Publication No. 47-47). 45802, 48-30646, JP-A-473733, JP-A-56-129298, JP-A-2-1783.
No. 97). Among them, especially Bacillus
Alkaline protease produced from llsS) is generally used, and “Alcalase” and “Esperase” (Es) manufactured by Novo Industry Co., Ltd.
perase), "sabinase" (Savinas
e), “Durazyme”, Gist's “Maxacal”, “Maxapem”, Genencore's “Purafect”, Solvay's “Opticlean”, Showa Denko. Company "A
P-21 "and the like are commercially available.

[0003]

Currently, clothes are washed with normal temperature water, but the washing power is insufficient to remove stubborn stains, and hot water may be used to increase the washing power. . However, when hot water is used, many commercially available alkaline proteases become unstable in the washing solution, and the enzyme washing effect cannot be sufficiently exerted. Esperase is the only alkaline protease with high thermostability, but Esperase has a low detergency, and even if it has high stability, the detergency of the enzyme cannot be demonstrated. In addition, oxygen-based peroxides such as sodium percarbonate and sodium perborate are particularly used as bleaching agents for bleaching clothing. Moreover, in order to further enhance the bleaching effect, organic peracid precursors such as TAED (tetraacetylethylenediamine), PAG (pentaacetylglucose) and OOBS (sodium octanoyloxybenzenesulfonate) may be used together as a bleach activator. Became. These organic peracid precursors react with hydrogen peroxide compounds such as sodium percarbonate to generate organic peracids having a high bleaching effect, and effectively remove stains such as food stains and yellowing adhering to clothes. However, in detergents and cleaning liquids containing a bleaching agent and further a bleaching activator, most of the detergent enzymes are unstable, and the cleaning effect of the enzymes is not sufficiently exerted. Therefore, an alkaline protease that is highly resistant to organic peracid obtained from a bleaching agent and a bleaching activator was developed and put on the market as a product of Durazyme and Maxapem. However, durazyme and maxapem had a problem color of low detergency. In order to solve these problems, an alkaline protease having high resistance to bleaching agents and bleaching activators and having high detergency is desired.

[0004]

Means for Solving the Problems As a result of intensive studies to solve these problems, the inventors of the present invention have an excellent stability in a washing liquid by incorporating an alkaline protease produced by a specific microorganism. However, it has been found that it preferably exhibits good detergency in warm water and has excellent resistance to an organic peracid obtained from a bleaching agent and / or a bleaching activator, and based on this finding, the present invention Came to make.

That is, the present invention relates to Bacillus sp.
No. 90), Bacillus SP
sp. ) K strain (Microtech Lab. No. 8090), Bacillus
Detergent composition comprising an alkaline protease produced from at least one species of SP (Bacillus sp.) X strain (Microtechnology Research Institute No. 8092), the alkaline protease, and oxygen-based peroxide The present invention provides a bleaching detergent composition characterized by blending a substance or an oxygen-based peroxide and an organic peracid precursor.

The detergent composition according to claim 1 of the present invention is characterized by containing the following components. The present invention will be described in more detail below. The alkaline protease used in the present invention is a novel enzyme (hereinafter referred to as P enzyme, K enzyme, X enzyme), and is widely found in nature as a result of searching for alkaline protease-producing bacteria.
strain belonging to Bacillus sp.
illus sp. ) P strain produces P enzyme, and Bacillus sp. K strain produces K enzyme.
The enzyme is produced and Bacillus sp.
s sp. The X enzyme is produced from the X strain. The Bacillus sp. P strain is designated as Microtechnological Research Institute No. 8090, the Bacillus sp. K strain is designated as Microtechnical Research Institute No. 8091, and the Bacillus sp.
The number has been deposited with the Institute of Microbial Technology, Institute of Industrial Technology. Regarding the Bacillus sp. P strain, Bacillus sp. K strain, Bacillus sp. X strain, and alkaline protease P enzyme, K enzyme, and X enzyme produced from these strains, see Japanese Patent Publication No. 3-79987. It is listed.

Bacillus sp. (Bac) exemplifying the above-mentioned method for preparing alkaline protease from microorganisms
illus sp. ) Alkaline protease P enzyme produced by P strain Bacillus sp.
s sp. ) Alkaline protease K enzyme produced by strain K, Bacillus sp.
p. ) The alkaline protease X enzyme produced by strain X is Bacillus sp.
P strain or Bacillus sp.
sp. ) K strain or Bacillus sp.
lus sp. ) Strain X was inoculated into a liquid medium containing 2% soluble starch, 0.5% yeast extract, 0.5% polypeptone, 0.1% dipotassium phosphate, 0.02% magnesium sulfate and 1% sodium carbonate. Then, at 30 ℃ 3
After shaking culture for 1 day, collect the supernatant by centrifugation and 70%
Salting out with ammonium sulfate, dialysis, and 10 mM borate buffer (pH 9.
The dialysate was developed on a column packed with DEAE-53 equilibrated in 3) and eluted with the same buffer to collect non-adsorbed active fractions.

The proteolysis rate, that is, the protease activity was measured according to the modified Anson-Hagiwara method. After the reaction, the absorbance of the reaction solution filtered was measured at 275 nm. The enzyme activity for releasing 1 μg of tyrosine in 1 minute was defined as 1 alkaline protease unit (1 APU). The amount of the alkaline protease P enzyme, K enzyme and X enzyme of the present invention is not particularly limited, but preferably 100 to 100,000 APU, and more preferably 1 per 1 g of the detergent composition.
It is from 00 to 10,000 APU. If it is 100 APU or less per 1 g of the cleaning composition, the detergency cannot be expected, and if it is 100,000 APU or more per 1 g of the cleaning composition, a detergency higher than that cannot be expected.

Further, the bleaching detergent composition of claim 2 is characterized by containing the following components in addition to the alkaline protease which is the essential component of claim 1.
As the oxygen-based peroxide, hydrogen peroxide, sodium percarbonate, hydrogen peroxide adduct such as sodium sulfate, or inorganic peroxide such as sodium perborate and potassium persulfate can be used. It is 0.1 to 50% by weight, preferably 1 to 20% by weight. As a bleach activator, organic peracid precursors such as TAED (tetraacetylethylenediamine), PAG (pentaacetylglucose) and OOB
S (sodium octanoyloxybenzene sulfonate) sodium P-nonanoyloxybenzene sulfonate, sodium P-nonanoyloxybenzoate, triacetin, etc. can be raised, as long as they can activate the oxygen-based peroxide, It is used in an amount of 1.5 mol or less of the oxygen-based peroxide.

In addition to the above-mentioned essential components, known detergent components can be used in combination with the detergent composition of the present invention, if necessary. Examples of the anionic surfactant include the following. 1) a linear alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16; 2) an α-olefin sulfonate having an average carbon number of 10 to 20; 3) a fatty acid lower alkyl ester represented by the following chemical formula 1. Sulfonate or fatty acid sulfonate di-salt

Embedded image (R; alkyl group or alkenyl group having 8 to 20 carbon atoms Y; alkyl group having 1 to 3 carbon atoms or counter ion Z; counter ion) 4) alkyl sulfate having an average carbon number of 10 to 20, 5) average carbon number Alkyl ether sulphate or alkenyl ether sulphate having 10 to 20 straight or branched chain alkyl or alkenyl groups and having an average of 0.5 to 8 mol of ethylene oxide added, 6) Average carbon number 10 to 22 Saturated or unsaturated fatty acid salt, substituted or unsubstituted ammonium salt or amine salt, wherein the fatty acid residue has 8 to 22 carbon atoms, particularly 12
Those of -20 are preferable. Examples of the salt include alkali metal salts such as sodium and potassium, ammonium salts, substituted ammonium salts such as methylammonium, diethylammonium and trimethylammonium, and monoethanolamine salts.
Particularly preferred are sodium salt and potassium salt. This fatty acid salt directly saponifies natural animal fats, vegetable fats such as beef tallow, palm oil, coconut oil, palm kernel oil and similar substances, or neutralizes fatty acids derived from them or synthetic fatty acids. Manufactured by.
Alkali metal salts such as sodium and potassium are usually suitable as counterions in these anionic surfactants.

Examples of the nonionic surfactant include the following. 7) An EO-addition type nonionic surfactant (alkyl ether ethoxylate) obtained by adding 4 to 25 mol of ethylene oxide (EO) on average to a primary or secondary alcohol having 8 to 18 carbon atoms. 8) EO-PO-added nonionic surfactant obtained by adding an average of 4 to 25 mol of ethylene oxide (EO) and an average of 3 to 15 mol of propylene oxide (PO) to a primary or secondary alcohol having 8 to 18 carbon atoms. . 9) Alkyl glucoside represented by Chemical formula 2

Embedded image (Z: a residue derived from a reducing sugar having 5 to 6 carbon atoms R ¹ ; an alkyl group, an alkenyl group, an alkylphenyl group, a hydroxyalkyl group, a hydroxyalkylphenyl group, or a mixture thereof, which has an alkyl group or an alkenyl group. alkylene group having 2 to 4 carbon atoms y;; R ² 8 to 20 carbon atoms 0 to 30 x; from 1.0 to 1.42) as the sugar residue, glucose, galactose, xylose, mannose, lyxose, Monosaccharides such as arabinose,
Polysaccharides such as maltose, xylopyose, lactose and sucrose are mentioned. 10) Sugar fatty acid ester-based surfactant represented by the following chemical formula 3

Embedded image (R ₁ : linear or branched alkyl or alkenyl group having 5 to 17 carbon atoms R ₂ : hydrogen atom or alkyl group having 1 to 4 carbon atoms) 11) Ester type nonionic surfactant represented by Chemical formula 4

[Chemical 4] (R ₁ CO: C 6-22, preferably C 10
-18 saturated or unsaturated fatty acids, which may be linear or branched. R ₂ : It has 2 to 4 carbon atoms, and it is preferable that OR ₂ is formed by adding ethylene oxide alone or by mixing ethylene oxide and propylene oxide. R ₃ : an alkyl group having 1 to 4 carbon atoms, preferably 1 carbon atom
Alkyl group of 2 to n represents the average number of moles of addition of OR ₂ and is a number of 5 to 30, preferably n = 5 to 20) The ester-based surfactant of Chemical formula 4 above is structurally a fatty acid alkylene oxide. It is an alkyl ether of an adduct and can be obtained by a two-step method such as adding alkylene oxide to alcohol by a conventional method and then esterifying with a fatty acid, but trivalent aluminum (Al) ion,
Gallium (Ga) ions, indium (In) ions,
A catalyst made of magnesium oxide to which one or more metal ions selected from thallium (Tl) ions, cobalt (Co) ions, scandium (Sc) ions, lanthanum (La) ions and divalent manganese (Mn) ions are added. Fatty acid alkyl ester R ₁ COO in the presence of
Those produced by a one-step method of reacting R ₃ with an alkylene oxide are preferred. (JP-A-4-279552
(See the official gazette). These anionic surfactant and nonionic surfactant may be used alone or may be mixed in an appropriate ratio.

Examples of the alkali include sodium carbonate, potassium carbonate, sodium silicate, crystalline silicate and the like. As the aluminosilicate, a crystalline or amorphous aluminosilicate represented by the following chemical formula 5 or a mixture thereof is suitable.

Embedded image (M in the formula is an alkali metal atom, M'is an alkaline earth metal atom that can be exchanged with calcium, and x, y and z are any numbers.) The average particle size of the aluminosilicate is in terms of detergency. To 5 μm or less, preferably 1 μm or less.

Further, other additives include inorganic builders such as sodium tripolyphosphate and sodium pyrophosphate; sodium citrate, sodium ethylenediaminetetraacetate, nitrilotriacetate, sodium polyacrylate, sodium acrylate-maleic anhydride. Sodium acid copolymer, calcium ion trapping builder such as polyacetal carboxylate; Alkali builder such as silicate; Anti-redeposition agent such as carboxymethyl cellulose, polyethylene glycol; paratoluene sulfonate, toluene sulfonate, xylene sulfonate Viscosity modifiers such as urea; quaternary ammonium salts, softening agents such as bentonite; sodium sulfate, sodium sulfite, optical brighteners, fragrances, enzymes, dyes, white carbon, etc. can be used. As the enzyme, hydrolase, oxidase, reductase, transferase, lyase, isomerase, ligase, synthetase and the like can be added. More preferably, a protease other than the present invention,
Keratinase, lipase, esterase, cellulase,
Examples include amylase, pullulanase, pectinase, cutinase, glucosidase, glucanase, cholesterol oxidase, and peroxidase. As protease, commercially available alcalase, esperase,
Savinase, durazyme, maxacalc, maxapem,
Purefect, Opticlean, API-21 and the like may be added.

The granular detergent composition of the present invention is obtained by forming the above components on a slurry and then spray-drying to obtain a bulk density of 0.2-.
It is obtained by using a hollow beaded detergent composition of 0.5 g / ml. In addition, the bulk density is obtained by granulating each component.
It is also possible to make a bulk density granular detergent composition of 0.6 to 1.2 gml. This granulation method is disclosed in JP-A-60-96698.
The kneading and kneading of a detergent raw material such as a surfactant with a kneader, crushing and granulating with a cutter mill type crusher, and further mixing with water-insoluble fine powder Thereby, the detergent composition of the present invention is obtained. Also,
It is also possible to spray-dry some or all of the detergent components in advance and knead and mix the spray-dried product with the remaining detergent components to produce bulk-density detergent particles. Alternatively, the spray-dried particles and, if necessary, other detergent components can be granulated with stirring to produce high-bulk-density detergent particles. Components such as enzymes and builders may be powder-blended with a granular detergent. As the stirring granulator, a high speed mixer (stirring rolling granulator), a Henschel mixer (high speed stirring granulator), a horizontal mixer (Ledige mixer), or the like can be used.

[0015]

According to the detergent composition of the present invention, Bacillus sp. P strain and / or Bacillus sp. K
Strain and / or Bacillus sp. Strain X produced a novel detergent composition containing alkaline enzymes P, K and X enzymes, which surprisingly exhibits sufficient detergency enhancing effect during hot water washing. Furthermore, they have found that they exhibit excellent resistance to organic peroxides generated by oxygen-based peroxides or oxygen-based peroxides and organic peracid precursors. Next, the present invention will be described in more detail by way of examples. The evaluation in each example was performed according to the following test methods.

Detergency US. Testing's Terg-O-Tomet
er is used as a cleaning device, and 10 pieces of protein-containing wet artificial dirt cloth, sebum cloth, and clean knitted cloth are put therein, and the bath ratio is adjusted to 30 times. p. m. Wash at 50 ° C for 10 minutes. The cleaning liquid has a predetermined cleaning concentration of 900 m
1) and rinse with 900 ml of water for 3 minutes. The water used was 3 ° DH (German hardness). Detergency is calculated by the following formula. In addition, this detergency test method is based on Oil Chemistry 30,432 (198
1) According to “Research on new artificial dirt (method 1)”.・ Enzyme stability evaluation method Add about 400 APU / ml of enzyme to each washing solution and
After 10 minutes of treatment and ice-cooling, the activity was measured. The stability was expressed as a percentage of the residual activity ratio after the heat treatment with respect to the activity before the heat treatment in the cleaning liquid. In addition, the measurement of the enzyme activity is described in "Enzyme Research Method 2" (edited by Shiro Akakawa), No.
It was carried out according to Casein-275 nm absorption A method described on page 38 below.

[0017]

[Examples] Prior to Examples, a method for producing a cleaning composition and raw materials used will be described. (Manufacturing method of cleaning agent) 60% solid content cleaning using each component excluding nonionic surfactant, part of zeolite, enzyme, fragrance, oxygen peroxide, organic peracid precursor from cleaning agent composition An agent slurry was prepared and adjusted to an appropriate viscosity with tap water. This cleaning agent slurry was heated at a hot air temperature of 200 using a countercurrent spray drying tower.
It was dried at ˜300 ° C. so that the water content was 5% to obtain a spray-dried product. Then, this dried product, nonionic surfactant and water were continuously kneaded (Kurimoto Tekko Co., Ltd., KRC Kneader #
2 type) to obtain a dense and uniform kneaded product. A cylindrical pellet of 5 mmφ × 10 mm was formed at the outlet of this kneader. The pellets were introduced into a crusher (Speed Mill ND-10 type, Okada Seiko Co., Ltd.) together with a double amount (weight ratio) of cooling air at 15 ° C. At the same time, an average primary particle size of 1 μm was used as a grinding aid. 4 parts by weight of zeolite (water content 10%) was added to 100 parts by weight of pellets.The crusher has a cutter with a length of 15 cm in four stages of cross,
3000r. p. m. Rotated in, the screen is made of 360 degree punched metal. This crusher is continuously connected in three stages, and the hole diameter of each stage screen is the first stage; 3.5 m
mφ, step: 2 mmφ, third step: 1.5 mmφ. Particles that have passed through the crusher in three stages are separated from the cooling air, and an oxygen peroxide, an organic peracid precursor, a fragrance, and an enzyme are added to the particles, and the bulk density of 0.6 to 1.2 g / ml is washed. An agent composition was obtained. As the enzyme, a powdered sample of P enzyme, K enzyme or X enzyme was separately used for 5000 APU / g, alcalase,
Esperase or Durazyme is also 5000 AP
U / g was added. Further, P enzyme, K enzyme or X enzyme and alcalase, esperase or durazyme were added at the same ratio to give 5000 APU / g. The detergent composition was dissolved in 3 ° DH hard water so as to be 25 g / 30 L to prepare a detergent solution.

Anionic surfactant SF-Na: α-sulfofatty acid (C12-18) methyl ester sodium AOS-K: C14-18 potassium α-olefin sulfonate LAS-Na: linear alkyl (C10-14) benzenesulfone Sodium acid AS-Na: alkyl (C12,14) ether (EO
= 3) Sodium sulfate Soap: Sodium fatty acid (80 fatty acids with 18 carbon atoms
%, Of which 60% unsaturated fatty acid content)

Nonionic Surfactant Nonion (1): C13 EO of primary alcohol = 20
Molar adduct Nonion (2): C12-13 EO of primary alcohol
= 10 mol adduct The meaning and details of the abbreviations in the table are as follows. EO represents the average number of moles of ethylene oxide added.

Optional component Silicate: Na ₂ O · 2.2 SiO ₂ Zeolite: A type synthetic zeolite Fluorescent agent (1): 4,4-bis (2-sulfostyryl) biphenyl disodium (Tinopearl CBS) Fluorescent agent (2 ): 4,4-bis [(4-torzino 6 monoforino 1,3,5-triazin-2yl) amino]
Stilbene-2,2-disulfonic acid disodium (Whitetex SKC) PAA-Na: sodium polyacrylate (weight average molecular weight 5000) A enzyme: Bacillus licheniformis (Bacillu)
Alkaline protease (trade name Alcalase, Novo Co.) isolated from s Iicheformis B enzyme: Esperase C enzyme: Durazyme

(Example 1) The numerical values in Table 1 indicate the weight% of each compounding component. The numerical values in Table 2 represent the residual activity ratio of alkaline protease. The numerical values in Table 3 represent detergency.

As can be seen from Tables 2 and 3, P enzyme, K
It was found that the enzyme activity and the X enzyme had higher residual activity of the enzyme in warm water washing than Alcalase and were superior in stability, and the detergency of P enzyme, K enzyme and X enzyme was superior to Alcalase and Esperase. I understand.

[Table 1]

[Table 2]

[Table 3]

(Example 2) The numerical values in Table 4 represent the weight% of each compounding component. The numerical values in Table 5 represent the residual activity ratio of alkaline protease. The numerical values in Table 6 represent detergency.

As can be seen from Tables 5 and 6, P enzyme, K
It was found that the enzyme and the X enzyme had a higher residual activity ratio of the enzyme in the bleaching agent than Alcalase and were superior in stability,
Also, it can be seen that the detergency of P enzyme, K enzyme, and X enzyme is superior to that of alcalase and dezyme.

[Table 4]

[Table 5]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 7:38)

Claims (2)

[Claims] 1. Bacillus sp.
sp. ) P strain (Microtech Lab. No. 8090), Bacillus sp. K strain (Microtech Lab. No. 8091), Bacillus sp.
illus sp. ) A detergent composition comprising an alkaline protease produced from at least one strain of strain X (Microtech Lab. No. 8092). 2. (A) Bacillus sp.
us sp. ) P strain (Microtech Lab. No. 8090), Bacillus. Bacillus sp. K (Microtechnology Research Institute, No. 8091), Bacillus sp.
illus sp. ) Alkaline protease produced by at least one kind of strain X (Microtechnology Research Institute No. 8092) (B) Oxygen-based peroxide, or an oxygen-based peroxide and an organic peracid precursor are blended. A bleaching detergent composition containing.