JPS6378000A - Detergent composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition, and more particularly to a lipase-containing detergent composition having excellent detergency.

In recent years, due to the problem of eutrophication, the amount of condensed phosphates contained in heavy household detergents has been largely removed, and people have become impatient and phosphorus-free detergents that use zeolite as a builder have become mainstream. It has been reached. This zeolite removes calcium ions, which are the hardness component in the washing liquid, through ion exchange.
This prevents the anionic surfactant from turning into a dissolvable calcium salt and reducing detergency. In addition, as a phosphorus-free calcium capture builder other than zeolite,
So-called polycarboxylic acid salts, such as polyacrylic salts and copolymers of maleic anhydride and olefins, are used with zeolites. However, there is a need for further improvement in the cleaning power of detergents, and from the viewpoint of surfactants and builders,
Also, various studies have been made on the composition of detergents from the perspective of additives such as enzymes.

Research has also been carried out focusing on various dirt components based on cleaning theory, and among the dirt components, lipids, especially triglycerides, are considered to be difficult to clean. One possible method for efficiently washing these lipids is to decompose them using lipase, which is a lipolytic enzyme. but,
Conventional lipases have extremely low activity in an alkaline atmosphere, which is the washing condition for laundry detergents, and are deactivated in the presence of surfactants, making it impossible to obtain sufficient cleaning effects.

The present invention aims to further improve the detergency of enzyme-containing detergents.

The cleansing composition of the present invention is characterized by containing the following components (a) to (c).

(a) Surfactant: 10-40% by weight.

(b) Zeolite and/or water-soluble phosphorus-free calcium trapping builder with an average particle size of 5 μm or less: 5 to 30% by weight.

(c) Lipase produced from Pseudomonas sp. &924 (Feikoken Bacteria No. 8879): Cleaning Composition 1
10,000 to 2 million lipase activity units (LU) per kg.

The present invention will be explained in more detail below.

Various types of surfactants can be used as component (a), but anionic surfactants and nonionic surfactants are particularly preferred.

Examples of anionic surfactants include the following.

1) Straight-chain alkylbenzene sulfonate having an alkyl group with an average carbon number of 10 to 16, 2) Olefin sulfonate having an average carbon number of 10 to 20, 3) Straight-chain or branched alkyl having an average carbon number of 10 to 20 or an alkyl ether sulfate having an average of 0.5 to 8 moles of ethylene oxide, and 4) an alkyl sulfate having an alkyl group having an average of 10 to 20 carbon atoms.

5) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22; 6) α-sulfofatty acid salt or α-sulfofatty acid ester salt represented by the following general formula.

R-CHCO, Y S○, Z (In the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z is a counter ion, and R is an alkyl group or alkenyl group having 10 to 22 carbon atoms.) Here As the salt (counter ion) in the anionic surfactant, an alkali metal salt such as sodium or potassium is usually suitable. The anionic surfactant is blended in the cleaning composition in an amount of lO to 40 wt%, preferably 15 to 30 wt%. This amount is 1
If it is less than 0wt%, sufficient cleaning power cannot be obtained, and
If it exceeds 40 wt%, it will be difficult to manufacture.

Among the anionic surfactants, olefin sulfonates, especially α-olefin sulfonates (including sulfonates of vinylidene-type olefins), work synergistically with the lipase enzyme and builder of the present invention to provide high detergency. show. It is desirable to blend the active agent so that 50% or more of the total active agent is olefin sulfonate.

Olefin sulfonates are neutralized and hydrolyzed products of sulfonated α-olefins (including vinylidene type olefins) or internal olefins having 10 to 20 carbon atoms, and in addition to alkenesulfonates, hydroxyalkanesulfonates are also used. included.

Suitable counter ions for the olefin sulfonate include potassium, magnesium, ammonium, and the like in addition to sodium.

Examples of nonionic surfactants include the following. It is desirable to use the nonionic surfactant in combination with the above-mentioned anionic surfactant.

1) An EO-added nonionic surfactant in which an average of 7 to 20 moles of ethylene oxide (EO) is added to a primary or secondary alcohol having 8 to 18 carbon atoms.

2) EO-PO addition type nonionic surfactant in which an average of 7 to 20 moles of ethylene oxide (EO) and an average of 3 to 15 moles of propylene oxide (PO) are added to a primary or secondary alcohol having 8 to 18 carbon atoms. agent.

As the builder for component (b), zeolite or a water-soluble phosphorus-free calcium-trapping builder is used.

As the zeolite, crystalline or amorphous aluminosilicates represented by the following general formula (1), or mixtures thereof are suitable.

x (M, O or M' O) - AM20! −y(SiO,
)-W(HlO)...(I) (In the formula, M is a 1M alkali gold atom, 1M' is an alkaline earth metal atom that can be exchanged with calcium, and X, y, and W are each of the respective components. Represents the number of moles, generally or 0.7
~1.5, y is 1 to 3, and W is an arbitrary number. ) The average particle size of zeolite is 5 μm or less in terms of cleaning power.
Preferably, it needs to be 1 μm or less.

Examples of water-soluble phosphorus-free calcium scavenging builders include 1 aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, 5 diethylenetriaminepentaacetate;
Polyhydric carboxylates such as citrates; polyacrylates, hydroxypolyacrylates, polyitaconates, polyacetal carboxylates, salts of copolymers of acrylic acid and maleic anhydride, maleic anhydride and methyl vinyl ether Polymer electrolytes such as salts of copolymers of maleic anhydride and olefin, salts of copolymers of acrylic acid and methacrylic acid, and the like can be mentioned.

The above chelate builders may be used alone or in combination of two or more.

The amount of the builder component (b) required is 5 to 30% by weight, preferably 10 to 20% by weight.

If the blending amount is less than 5% by weight, the detergency improvement effect will be poor;
If it exceeds 0% by weight, manufacturing becomes difficult.

As the lipase component (C), one produced by a specific strain belonging to the genus Pseudomonas is used. This strain is Schnathmonas sp. Nn924 (P
sudomonas sp, Na924),
It has been deposited with the Institute of Microbial Technology, Agency of Industrial Science and Technology under the accession number FERM P-8879.

This Pseudomonas SP, 1lh924, has the following mycological properties.

(1) Morphology (a) Cell shape and size: Bacillus, approximately 0.5 μ x 1.0
〜2.5μ (b) Presence of polymorphism: None c) Mobility: Yes, extremely benign hairs (d) Spores: None e) Gram staining: Negative (f) Acid-fastness : Negative (2) Growth status in each medium (a) Broth agar plate culture: Round, smooth, gold-rimmed, flat to slightly curved, translucent, mixed light, colorless to pale yellowish brown (b) Broth agar slant culture : Moderate growth, filamentous, flat, translucent, colorless to pale yellowish brown (c) Meat juice liquid culture Medium growth, uniform turbidity, without sediment d) Meat juice gelatin puncture culture Liquefy gelatin.

(e) Lidmus milk Slightly alkaline, peptonized Ru.

(3) Physiological properties (a) Nitrate reduction: Positive (b) Denitrification reaction: Negative (c) MR test: Negative (d) VP test: Negative (e) Indole formation: Negative (f) Hydrogen sulfide Production: Negative (g) Hydrolysis of starch: Negative (h) Utilization of citrate: Positive with Koser's medium and Christensen's medium.

(i) Utilization of inorganic nitrogen sources: Ammonium sulfate and sodium nitrate Take advantage of.

(j) Production of pigment No pigment formation in King A medium.

Produces a light reddish-brown water-soluble pigment in King B medium.

(k) Urease: VA property (1) Oxidase: Positive (m) Catalase: Positive (n) Range of growth.

p) Grows from 15 to 9.

It grows at 37°C but not at 42°C.

(0) Attitude regarding oxygen: aerobic (ρ) O-F test acid from glucose under aerobic conditions generate.

(q) Generation of acid and gas from sugars: arabinose,
It produces acids but not gases from xylose, glucose, mannose, fructose, galactose, malts, sucrose, lactose, trehalose, sorbitol, mannitol, inosit, and glycerin, and neither acids nor gases from starch.

The above properties (Buchanan, R.E., and
Gibbons.

N, H,: Bergey's Manual of D
eterminative Bacteriology,
8th, ed., Williams & Wilkins
Go.

(1974)), [Translated by Toshi Sakazaki: Handbook of Medical Bacteria Identification (2nd edition), Kindai Shuppan, (1974)), etc., search results include: ■ Gram-negative, ■ Bacillus, ■ Aerobic, ■ Extreme Ben. It is classified as a member of the genus Pseudomonas because it is motile due to hair, ■ catalase positive, ■ oxidase positive, and ■ produces acid under aerobic conditions.

Therefore, this production strain was used as Pseudomonas sp, Nα924 (
It was named Pseudomonas sp, N[L924).

The culture medium used to cultivate this strain and produce lipase AML includes polysaccharides such as soluble starch granules, disaccharides such as dextrin and maltose, and monosaccharides such as glycose as carbon sources, and monosaccharides such as glycose as nitrogen sources. Examples include cornstarch liquor, peptone, meat extract, casein, amino acids, and yeast extract. Inorganic salts and trace nutrients include phosphoric acid and magnesium.

In addition to salts such as potassium, iron, calcium, and zinc, vitamins, nonionic surfactants, antifoaming agents, and other substances that promote the growth of bacteria and the production of lipase AML may be used as necessary. The culture is carried out under aerobic conditions, and the culture temperature is within a range that allows the bacteria to grow and lipase AML to be produced, preferably 25 to 40°C. Cultivation time varies depending on conditions, but
It is sufficient to culture until the time when lipase AML is produced the most, which is usually about 1 to 3 days. After completion of lipase AML culture, bacterial cells and solid matter are separated from the culture fluid, and the culture filtrate is collected.

To obtain lipase AML from culture filtrate, any method commonly used for enzyme purification can be used.

For example, treatment with organic solvents such as ethanol, acetone, isopropyl alcohol, salting out with ammonium sulfate, common salt, etc.
Various purification methods such as dialysis, ultrafiltration, ion exchange chromatography, etc. can be performed.

Next, the enzymatic chemical properties of the thus obtained partially purified lipase AML product will be described.

(1) Effect on various oils and fats: As shown in Table 1, it acts well on various oils and fats. Note that the action conditions of lipase AML on various fats and oils are 50°C and 30 minutes (Po 7.0).

Table-1 = Effect of lipase AML on various oils and fats (2)
Effect on fatty acid methyl ester: As shown in Table 2, it can act on various fatty acids ranging from short chains to long chains. Note that the action conditions of lipase AML on various fatty acid methyl esters are 40° C. and 30 minutes (pl+ 7.0).

Table 2: Effect of lipase AML on various fatty acid esters (3) Effect ρ■: Can act in a wide pH range from PH4 to 12.

(shown in Figure 1) (4) Range of stability: It is stable in a wide pH range of 3 to 12.

(See Figure 2) (5) Optimal temperature: (6) Metal salts that have an optimum temperature around 50°C and have a specific activity of 60% or more even at 70°C (shown in Figure 3). Effect: As shown in Table 3, it is only slightly inhibited by Fe''+.The concentration of the various metal salts is 1 mN.

Table 3 = Influence of metal salts (7) Activity measurement method: 1mM of purified water and enzyme solution 111Q were added to 3mA of olive oil emulsion as a substrate, and after incubating at a temperature of 37°C for 20 minutes, 1 mfl of 2N sulfuric acid was added to stop the reaction. Heptane-isopropanol mixture (11:4) 15n
After adding Q and extracting the released fatty acids by shaking for 30 seconds, the upper J! The 6-activity display method involves separating J 5 m Q and titrating it with N/100 alcoholic KOH using thymol blue as an indicator.
The amount of enzyme that releases fatty acids corresponding to le was defined as 1 unit.

However, sufficient cleaning power cannot be obtained by simply adding lipase AML to a detergent composition, and a detergent composition that combines a surfactant and a zeolite or a water-soluble non-phosphate calcium scavenging builder in a specific amount This is the first time that it has sufficient cleaning power for objects. Lipase AML is 20,000 to 20% lipase activity in 1kg of detergent.
It is formulated to have 00,000 LU (lipase activity units). If the lipase activity unit is less than 20,000, the effect of improving detergency will be poor, while if it exceeds 2,000,000, it will be disadvantageous in terms of cost.

The cleaning composition of the present invention may further contain, if necessary, alkali builders such as carbonates and silicates; bleaching agents such as sodium percarbonate and sodium perborate; reducing agents such as sodium sulfite and sodium bisulfite. ; Re-staining prevention agents such as carboxymethyl cellulose and polyethylene glycol 1 Soap, fluorescent bleach, perfume, etc. can also be blended.

According to the present invention, by blending (a) a surfactant, (b) a calcium-trapping builder such as zeolite, and (c) lipase AML in specific amounts, the effect of this lipase can be sufficiently enhanced. The cleaning power of the cleaning composition can be greatly improved. This effect is particularly significant when α-olefin sulfonate is used as the surfactant.

EXAMPLES Below, the effects of the present invention will be explained in more detail with reference to Examples. Prior to this, a method for producing lipase AML, a method for measuring lipase activity units, and a method for evaluating detergency will be explained.

(1) Production of lipase AML Soluble starch 2wt%, defatted soybean flour 2wt%, urea 0.3
wt%, dipotassium phosphate 0,5 wt%.

and 50 mΩ of liquid medium containing soybean oil lut%.
Pseudomonas sP was placed in a 01IQ Yosaka flask and sterilized at 121°C for 20 minutes.

One platinum loop of Nα924 was inoculated and cultured at 30° C. for 48 hours in a reciprocating shaking incubator at a shaking width of 51 and 30 times per minute. After the culture was completed, the cells and solids in the culture were removed using a centrifuge to obtain a 40 mQ supernatant.

The lipase activity of this liquid was 380 LU/a+n.

This crude lipase solution was cooled to 5°C and added to 200 QtttlA of ethyl alcohol cooled to -10°C, and the resulting precipitate was separated and dried under reduced pressure to give 26,800 L.
U/g of lipase AML powder was obtained.

(2) Measurement of lipase activity (LU) A reaction solution having the following composition was prepared. here.

The olive oil emulsion was prepared as follows.

First, 100 iQ of 20% gum arabic solution and 50 mn of olive oil were homogenized for 30 minutes, and the pH was adjusted to 1.
Set to 0. 1 part of 1M glycine buffer (pH 10, O) was mixed with 2 parts of this emulsion, and the pH was readjusted to ρ before use.

Purified water 1mA Enzyme solution 1+au Olive oil emulsion 3n+Q After reacting this reaction solution at a reaction temperature of 37°C for 20 minutes,
The reaction was stopped by adding 1 mQ of 2N sulfuric acid, a heptane-impropatol mixture (IC405m) was added, and the liberated fatty acids were extracted by shaking for 30 minutes.

5 mQ of the upper layer was separated and titrated with 0.0 IN alcoholic KOH using thymol blue as an indicator.

The activity was expressed as 1 unit (ILU), which was the amount of enzyme that released fatty acids equivalent to 1 μmol per minute under the above conditions.

(3) Evaluation of detergency (i) Preparation of artificial dirt Clay containing crystalline minerals such as kaolinite and vermiculite as main components was heated to 30°C at 200°C.
The time-dried product was used as an inorganic stain.

After dissolving 3.5 g of gelatin in 950 cc of water at about 40°C, it was
0.25 g of carbon black was dispersed in water using a carbon black (manufactured by NEMATICA).

Next, 14.9 g of inorganic dirt was added and emulsified with a polytron, and 31.35 g of organic dirt was further added and emulsified and dispersed with a polytron to prepare a stable dirt bath. L in the filth bath with
A predetermined cleaning cloth (cotton cloth No. 60 designated by Japan Oil Chemists' Association) measuring 20 cm x 20 cm was immersed, and the water was squeezed using two rubber rolls to equalize the amount of dirt attached. 1 of this dirty cloth
After drying at 05℃ for 30 minutes, dry both sides of the dirty cloth.
I rubbed it 5 times each. This was cut into 5cm x 5cm pieces with a reflectance in the range of 42±2% and used as a dirty cloth. The soil composition of the artificially soiled cloth thus obtained is shown in Table 1.

(it) Organic dirt 60rn1 shown in Table-1 was attached to each sheet of Sebam rare W-seated cloth (cotton knitted 5cm x 5cn+).

(iii) Washing knitted fabric Cotton knitted fabric (same as used for sebum cloth) (iv) Cleaning method The cleaning device was Terg-0- manufactured by U, S, Testing.
Using Tometer, put 10 pieces of artificially soiled cloth and 3 pieces of Sebam cloth, and then add washed knitted cloth and adjust the bath ratio to 30 times.

Wash at 25° C. for 10 minutes at 120 rpm. A cleaning solution of 900mQ with a detergent concentration of 0.167% is used, and rinsing is performed for 3 minutes with 900mQ of water. Water used is 3°DH
I used the one from

(v) Detergency evaluation method R is the reflectance (%) measured by a Cari Zaiss ELREPHO reflectance meter.

The detergency was evaluated using the average value of 10 artificially soiled cloth samples.

Examples Cleaning compositions shown in Table 2 below were prepared and their cleaning power was evaluated. The abbreviations and details in the table are as follows.

AO8: C, ..., 6α-Sodium olefin sulfonate LAS: Sodium linear alkylbenzene sulfonate whose alkyl group has 10 to 14 carbon atoms AS: C1□ to 1. Sodium alkyl sulfate AES
: Sodium alkyl ethoxy sulfate with an alkyl group having a carbon number of C12-151 and an average number of added moles of ethylene oxide of 3 Nonion: E O addition type nonionic surfactant Zeolite with an average of 15 moles of ethylene oxide added to a C,,0, alcohol: Zeolite A type Synthetic zeolite (average particle size 0.9 μ resistant PAS: Sodium polyacrylate (Mv = sooo) MAloL: i-water maleic acid/olefin copolymer (M
W = 10000) NTA: Sodium nitrilotriacetate (reagent) Na silicate: Na, O: SiO, = 1:2.2 N carbonate
a: N a 2 C03 (reagent) PEG: Polyethylene glycol average molecular weight sulfite W: N a z
S O3 (reagent) Lipase MY: Lipase (trade name,
Tetrasaccharide industry■) (blank below)

[Brief explanation of the drawing]

Figures 1, 2 and 3 show lipase AML of the present invention.
In Figure 0, which shows the optimum pH curve, pH stability curve, and optimum temperature curve, respectively, 141 is O, IN hydrochloric acid-sodium acetate buffer, and -rho is 0. IN Tris-
Hydrochloric acid buffer and -.- are the curves when using 0.1N glycine-NaOH buffer, respectively. Figure 1 Figure 2

Claims (1)

[Claims] 1. A cleaning composition characterized by containing the following components (a), (b) and (c). (a) Surfactant: 10 to 40% by weight, (b) Zeolite with an average particle size of 5 μm or less and/or water-soluble phosphorus-free calcium trapping builder: 5 to 30% by weight, (c) Pseudomonas sp. Lipase produced from No. 924 (Feikoken Kyoiku No. 8879): 10,000 to 2,000,000 lipase activity units per 1 kg of cleaning composition.