JPH02178397A - cleaning composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to detergent compositions containing lipase as an enzyme.

In recent years, due to the problem of eutrophication of environmental waters, the amount of condensed phosphates contained in household heavy detergents has been significantly reduced or eliminated, and now phosphorus-free detergents that use zeolite as a builder has come to dominate. This zeolite removes calcium ions, which are the hardness component in the washing liquid, by ion exchange, and prevents the anionic surfactant from turning into a poorly soluble calcium salt and reducing the washing power.

In addition, so-called polymer builders such as polyacrylates and copolymers of maleic anhydride and olefin are used together with zeolites as phosphorus-free calcium ion-trapping builders other than zeolites.

However, it is desired to further improve the detergency, and studies have been conducted from the viewpoint of surfactants, builders, and additives such as enzymes.

Research is also being conducted focusing on various dirt components based on cleaning theory, and among the dirt components, proteins, lipids,
In particular, triglycerides are said to be difficult to wash. Among these, the use of protein-degrading enzymes (proteases) has been considered for some time, and there are many examples of their use in detergents. Furthermore, it is possible to decompose lipids with a lipolytic enzyme (lipase) and remove them as fatty acids.

However, simply adding lipase to ordinary detergents did not provide a sufficient effect of improving detergency. For this reason, when clothes that had been washed and dried using conventional detergents were stored for a long period of time, a strange odor was observed, which was thought to be caused by the oxidation and decomposition of the remaining lipids.

SUMMARY OF THE INVENTION The object of the present invention is to provide a lipase-containing detergent composition that generates less odor from clothes after washing and drying.

The cleaning composition of the present invention contains the following components (a), (b), and (C), and the ratio of Na ions to + ions in the entire composition is by weight. Na":K+=4:1
It is characterized by being in the range of ~1:4.

(a) Anionic surfactant.

(b) Alkaline lipase 6 whose lipase activity at pH 9 is 30% or more of the lipase activity at pi (7) (C) Contains one or more flavor components with a boiling point of 230°C or higher at 1 atm, and whose blending amount is Perfume that accounts for 30% or more of the perfume: 0.05 to 1% by weight Below, the present invention will be described in more detail.

Examples of the anionic surfactants as the (,) components include the following, which may be used alone or as a mixture.

1) Linear alkylbenzene sulfonate having an alkyl group with an average of 8 to 16 carbon atoms, 2) Olefin sulfonate with an average of 10 to 20 carbon atoms, 3) Alkyl sulfate with an average of 10 to 20 carbon atoms, 4) Average Alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 0.5 to 8 moles of ethylene oxide added, 5) The following general formula α-sulfofatty acid salt or α-sulfofatty acid ester salt represented by:

R-CHCOOY SO□Z (wherein, Y: alkyl group having 1 to 3 carbon atoms or counter ion 2: counter ion R: alkyl group or alkenyl group having 10 to 22 carbon atoms) Anionic surfactant as component (a) is preferably 10 to 50% by weight, more preferably 20 to 4% by weight in the cleaning composition.
0% by weight is added.

In the present invention, the ratio of Na+ ions to Na+ ions contained in the entire cleaning composition, including not only the counter ion of the anionic surfactant but also optional components such as alkali builder, is Na'' in terms of weight ratio. : K+=4 : 1~1 :
4, preferably in the range of 3:1 to 1:3. If the amount of + ions is less than this ratio, the storage stability of component (b) alkaline lipase will be lowered, and the removal rate of lipids will be lowered, so that the effect of preventing the generation of off-flavors will be lost. On the other hand, if there are more + ions than the above ratio, the manufacturing efficiency of the detergent will decrease.

(b) As for component alkaline lipase, the lipase activity at pH=9 is 30% of the lipase activity at pH=7.
Above, preferably 50% or more is used. This is because the detergent solution is alkaline, and when lipase breaks down triglycerides to produce fatty acids,
This is because it is saponified by the alkaline content in the system, and the surface activity of this saponified fatty acid salt facilitates the removal of stains and suppresses the generation of unpleasant odors in clothing after storage.

As the lipase suitable for the present invention, Candidacy
lindracea, Humicola lanug
inosa.

Psdomonas, Mucor sp,, Chr.
omobacterium viscosum, Rh1
There are those of microbial origin such as zopus japonics, lipase AY, lipase OF (Meito Sangyo ■
Made by Candida cylindracea),
Lipase CE (manufactured by Amano Pharmaceutical Co., Ltd., Origin Humicolal)
anuginosa), lipase P, lipase CES
(The above, manufactured by Ohno Pharmaceutical ■, origin Pseudononas)
, Lipase SP (manufactured by Novo, origin Mucor sp,
), ribolase (manufactured by Novo, Asp by genetic recombination)
ergillus Or/Zae), lipase (
Manufactured by Toyo Jozo■ Origin: Chromobacterium
viscosum), Lipase LPL (manufactured by Oriental Yeast ■), Olivase (Osaka Bacteria Research Institute, origin Rh1)
zopus japonics), Lipase B (made by Salapol Beer, origin Pseudomonas), and the like.

The amount of component (b) alkaline lipase is 1 kg of detergent.
It is preferable to mix in an amount of 10,000 to 1,000,000 lipase units (LU) per lipase unit.

Examples of the fragrance component having a boiling point of 230°C (1 atm) or higher in component (c) include the following. These fragrance components can be used alone or in combination of two or more, and the total amount thereof is 30% by weight or more based on the entire fragrance. If this amount is less than 30% by weight, the effect of preventing strange odors from clothes after storage is insufficient.

2-trans-3+ 7-dimethyl-2,6-octanonin-1-ol 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)- 2-Butan-1-ol α-Methyl-P-isopropylphenylpropionaldehyde α-n-hexylcinnamic aldehyde α-n-amylcinnamic aldehyde α,α-dimethylnyl-ethylhydrocinnamic aldehyde o-tert-butylcyclo Hexyl acetate naphthalene-2-acetyl-1,2,3°4.6,7.
8-octahydro-2,3,8゜8-tetramethyl5-
(2-methylene-6゜6-dimethyl-cyclohexyl)
-4-Penten-3-one 7-acetyl-1,1,3,4,4,6-hexamethyltitrahydronaphthalene6.7-sihydro1.1,2,3.3-pentamethyl-4(5H) -Indanone 2.6-Sinitro 3,5.
-dimethyl-4-acetyl-tert-butylbenzeneallylcyclohexanepropionate 2-methyl-4-(2,2,3-trimethyl-3-cyclopentenyl)-2-buten-1-olmethylnonylacetaldehydropropenylphenyl Methyl ether 3-phenyl-
2-Propen-1-ol methyl-2-aminobenzoate p-tert-butyl-α-methylhydrocinnamic aldehyde 3-(5,5,6-)-dimethyl-norbornane-2-
cyclohexane-1-ol Ethyl-3-phenylpropionate 2-methoxy-4-propenylphenol 4-(4-hydroxy-4-methylpentyl)-3-cyclohexane-1-carboxaldehyde 3-methoxy-4-hydro Mexibenzaldehyde Belt Fix 3.7-Simethyl-2,6-Octazininal Methyl Dihydrodiasmonate In addition to the fragrances mentioned above, the fragrance of component (C) may also include the following fragrances as optional ingredients. It can also be blended.

2 Fragrance 3.7-Simethyl-6-octen-1-ol 3,7-cytyl-1,6-octadien-3-ol 3.7-dimethyloctano-3 2-cis-3,7-dimethyl-2 , 6-octadien-1-ol n-decylaldehyde 10-undecen-1-al 3.7-dimethyl-6-octen-1-al benzyl acetate cis-3-hexenol 2-methyl-6-methylene-two-octen-2-ol 1-Methyl-4-isopropyl-1-cyclohexene-
8-olbornyl alcohol β-phenylethyl alcohol methylphenylcarbinyl acetate 3,7-dimethyl-1,6-octanonin-3-yl acetate 3,7-dimethyl-2,6-octagenal 2-(2-methyl- 1-propenyl)-4-methyltetrahydrophyllan 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde tart-butylcyclohexyl acetate lemon oil orange oil lime oil bergamot oil lavender oil patchouli oil sandalwood oil cedarwood Oil lavender oil elimi oil methyl diphenyl rubinyl acetate 3,7-dimethyloctano-3 benzyl acetate 2-methyl-6-methylene-2-octen-2-ol 3,7-dimethyl-6-octen-1-al 1- Methyl-4-isopropyl-1-cyclohexene-
8-ol 2-cis-3,7-dimethyl-2,6-octadiene-
The fragrance as the 1-ol (c) component is blended in an amount of 0.05 to 1% by weight, preferably 0.1 to 0.3% by weight, based on the total amount of the fragrance component. If the blending amount is less than 0.05% by weight, the effect of preventing foreign odors in clothing will be insufficient, while if it exceeds 1% by weight, the aromaticity of the perfume will be too strong, which is not preferable.

Various optional components can be added to the above-mentioned cleaning composition as necessary. Optional ingredients include other surfactants such as nonionic surfactants and cationic surfactants, zeolites, water-soluble phosphate-free calcium-trapping chelate builders; other enzymes other than the alkaline lipase of the present invention; sodium percarbonate, Bleach agents such as sodium borate, reducing agents such as sulfites, anti-recontamination agents such as carboxymethyl semerose and polyethylene glycol, soaps, optical brighteners,
Bentonite etc. can be used as needed.

Examples of nonionic surfactants include the following.

(1) An E〇-addition type nonionic surfactant in which an average of 10 to 30 moles of ethylene oxide (E〇) is added to a primary or secondary alcohol having 8 to 18 carbon atoms.

(2) E○-P○ addition, in which an average of 7 to 20 moles of ethylene oxide (E○) 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. Type nonionic surfactant.

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

x (M2O or M'O) ・A Q203 ・y
(S iOJ・W(H2C)-(IT) (In the formula, M is an alkali metal atom, M' is an alkaline earth metal atom exchangeable with calcium, and X+ y and 2 represent the number of moles of each component. , - in the shell X is 0.7 to 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.
The thickness is preferably 1 μm or less.

Water-soluble phosphorus-free calcium ion scavenging builders include, for example, aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, and diethylenetriaminepentaacetate; polyhydric carboxylates such as citrate; polyacrylic acid salts, hydroxy polyacrylates, polyitaconates, polyacetal carboxylates, salts of copolymers of acrylic acid and maleic anhydride, salts of copolymers of maleic anhydride and methyl vinyl ether, salts of copolymers of maleic anhydride and olefins, and polymer electrolytes such as salts of copolymers of acrylic acid and methacrylic acid, and salts of copolymers of acrylic acid and methacrylic acid.

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

In addition to the alkali metal enzyme of the present invention, other enzymes such as protease, cellulase, amylase, etc. can be added as enzymes. In particular, when used in combination with protease, the cleaning power can be significantly improved. As a result, the off-odor of clothing after storage is reduced.

Examples of the fluorescent whitening agent include the following (a) to (e).

The cleaning composition of the present invention can take a variety of forms, such as a granular detergent in the form of hollow beads, such as conventional spray-dried detergents. Also, JP-A-60-9
As shown in Japanese Patent No. 6698, it is also possible to produce a high bulk density granular detergent in which the detergent components are packed even inside the detergent particles.

In the case of a high bulk density cleaning composition, the bulk density is 0.5 to
1.2 g/cc is suitable, and such compositions are disclosed, for example, in Japanese Patent Application Laid-open No. 60-96698 and No. 60-96698.
As described in Publication No. 2-597, each detergent component is kneaded and mixed in a kneader, then crushed and granulated in a cutter mill type crusher, and then coated with water-insoluble fine powder. It can be manufactured by It is also possible to supply some or all of the detergent ingredients in the form of a spray-dried product and to knead it.

According to the present invention, by blending a specific alkaline lipase into a specific detergent composition and adding a specific fragrance to the detergent composition, an unpleasant odor is generated in clothes after storage. It is possible to realize an oxygen-containing cleaning agent that can significantly suppress the

Hereinafter, the present invention will be described in more detail with reference to Examples, but prior to this, the measurement methods and evaluation methods used in the Examples will be explained.

(1) Lipase activity measurement method Using olive oil as a substrate, the fatty acids liberated by the action of lipase are quantified by alkaline titration, and the lipase activity is determined from the numerical value.

One enzyme unit is an enzyme that releases 1 μM fatty acid per minute from the substrate olive oil at 37°C.

4mQ of olive oil emulsion and 0.1M phosphate buffer (pH 7)
, 0) 4 m f;A into a 50 m 11 volume stoppered Erlenmeyer flask, mix well, and preheat for 10 minutes using a 37°C constant temperature water bath. Add exactly 1 m2 of the sample solution to this, mix well, and add the acetone/ethanol mixture after exactly 20 minutes. Then, phenolphthalene solution 5
Using the drop as an indicator, titrate with 0.05N sodium hydroxide test solution.

Separately, accurately add 4 m Q of olive oil emulsion 5IIIQ and 0.1 M phosphate buffer (p) 17.0) to a 50 m Q volume stoppered Erlenmeyer flask, heat at 37°C for 30 minutes, and then add 20 m Q of acetone/ethanol mixture. Then, add exactly 1 ml of the sample solution, use 5 drops of phethanolphthalene test solution as an indicator, and titrate with 0.05N sodium hydroxide test solution to use as a control solution.

Calculation of enzyme units Note that in the measurement at pH=9, 0.2M Tris buffer was used to adjust the pH to 9, and the other procedures were carried out in accordance with the above method.

(2) Method for evaluating off-odor after storage of clothing [Preparation of soiled cloth] A 10 wt% benzene solution of organic soil containing the following soil components was added to cotton knitted cloth to a concentration of 0.45 wt% based on the weight of the fibers. A soiled cloth was prepared by applying it evenly to a skin shirt and air-drying it.

゛ J dirt m or ← μU oleic acid
40.6 Triolein
22.4 Cholesterol oleate 175
Liquid paraffin 3.6 squalene
3.6 cholesterol
23 Gelatin 100 [Evaluation method] Using a washing machine and 3°DH water, the organic 10 skin shirts with dirt on them
Washed for 1 minute and dehydrated for 1 minute.

Then, rinsing for 3 minutes with water at 3°DH and 125°C and dehydration for 1 minute were repeated twice. After that, wash the cloth for 48 minutes.
After air drying indoors, each sheet was placed in a plastic bag, sealed, and left in a constant temperature room at 35°C.

After being left in a constant temperature room for one month, the skin shirts were taken out from one bag, and the degree of off-odor generation after storage was evaluated according to the following criteria.

Evaluation - Isshiki There is no off-odor at all 5 There is a slight off-odor 4 There is an off-odor 3 There is a somewhat strong off-odor 2 Yes 1 Large - J is a nonionic surfactant from the high bulk density detergent particles shown in Table 1 below by Takumi. , using each component except for a part of zeolite as a flavoring agent and a grinding aid.

A detergent slurry with a solids content of 45% was prepared. This detergent slurry was dried using a countercurrent spray drying tower at a hot air temperature of 380°C to a moisture content of 5%.

A spray nvt product was obtained.

This spray-dried product has an average particle size of 350 μm and a bulk density of 0.3.
5 g/■ and an angle of repose of 45 degrees, indicating good fluidity.

Next, the above dried product, nonionic surfactant and water were added,
The mixture was introduced into a continuous kneader (manufactured by Kurimoto Iron Works, KRC Nida Model I2) to obtain a dense and uniform kneaded product.

A perforated plate (thickness: 10 rm) with 80 holes of 5 m + φ was installed at the outlet of this kneader, and the kneaded material was placed on about 5 φ holes.
It was made into a cylindrical pellet with a diameter of 10 nm.

These pellets are crushed with twice the amount (weight ratio) of 15℃ cooling air (speed mill ND-10 model, Okada Seiko ■
) was introduced. At the same time, as a grinding aid, an average of -
4 parts by weight of zeolite (water content 15%) having a sub-diameter of 1 μm was added to 100 parts by weight of the pellets.

The crusher has cutters with a length of 15 cm arranged in 4 cross stages, rotates at 3000 rpa+, and has a screen of 360 rpm.
Made of highly perforated metal. Three stages of this crusher are connected in succession, and the hole diameter of each stage screen is set as follows: 3.
5m+φ, 2nd stage = 2Iφ, 3rd stage: 1.5mmφ. After separating the particles that have passed through three stages of the crusher from the cooling air, they are sprayed with fragrance and have the composition shown in Table 1 below.
Detergent particles with a bulk density of 0.8 g/cc were obtained.

Add to this the various lipases shown below in the amounts shown in Table 1 [
The detergent composition of the present invention was prepared by adding 0 to 100,0 OOLU/Kg (0 to detergent), and the off-odor prevention property was evaluated.

Details of the components used in the table are shown below.

AOS-K; C10-4, a-potassium olefin sulfonate AO8-Na; C engineering. 18α-Sodium olefin sulfonate LAS-; Linear alkyl benzene sulfonate potassium LAS-Na whose alkyl group has 10 to 14 carbon atoms; Linear alkyl benzene sulfonate sodium nonionic surfactant whose alkyl group has 10 to 14 carbon atoms A; C1□~, EOp = 20 mol adduct of 31st alcohol; nonionic surfactant B; C1, -□ EOβ = 30 mol adduct of 31st alcohol; nonionic surfactant C; C; 2-131st alcohol EOi5 = 20 mol, pop = 5 mol adduct soap; tallow soap zeolite; A-type synthetic acid zeolite (average particle size 0.9 μI
! 1) Na silicic acid; Na2O:5iOz=1:2.2 carbonic acid; 2C○, (reagent) carbonic acid Na; Na2COz (reagent) sulfite
Na; Sodium sulfite (reagent) Protease; Savinase 4. OT (manufactured by Novo) Lipase ■; Lipolase (
Novo) Activity ratio = 100% (PH = 9/pH = 7) Lipase ■;
Lipase GE (manufactured by Amano Pharmaceutical) Activity ratio = 70% (PH = 9
/PH=7) Lipase ■; Lipase OF (manufactured by Meito Sangyo)
Activity ratio = 50% (PH = 9 / PH = 7) Lipase ■; Lipase AP (manufactured by Amano Pharmaceutical) Activity ratio = 20% (PH = 9 /
P) I = 7) Fragrance A; as per the table below (perfume composition) Fragrance B; as per the table below (perfume composition) Perfume C; as per the table below (perfume composition)

Claims (1)

[Claims] 1. (a) an anionic surfactant; (b) an alkaline lipase whose lipase activity at pH 9 is 30% or more of that at pH 7; and (c) an alkaline lipase whose boiling point at 1 atmosphere is 230°C or higher. A fragrance that contains one or more types of fragrance ingredients and whose blending amount accounts for 30% or more of the total fragrance: Contains 0.05 to 1% by weight, and contains sodium ion Na^+ and potassium ion K^ of the entire composition. + is the weight ratio, Na^+
A cleaning composition characterized in that: K^+ is in the range of 4:1 to 1:4.