JPS6291598A - Detergent 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] [Industrial Field of Application] The present invention is directed to a phosphorus-free detergent composition characterized by containing an enzyme having pectinase activity, particularly as a laundry detergent for use against inorganic stains attached to clothing. The present invention relates to a cleaning composition that exhibits remarkable cleaning power.

[Conventional technology]

Dirt that adheres to clothing can be broadly divided into metabolic substances (sebum stains) secreted from the human body when worn, and inorganic stains such as dirt brought in from the living environment.

Among these, sebum stains can be considerably removed by combinations of various surfactants and combinations of these with virgoo, protease, or bleaching agents.

On the other hand, inorganic stains behave differently from organic sebum stains and are not as effectively affected by surfactants, so they are easier to remove than sebum stains, and are superior to inorganic stains. There is a desire to develop a cleaning composition that has a removal effect, and various techniques have been developed. For example, JP-A No. 57-36198 describes that a soap composition containing araminosilicate bilgu and a high concentration of unsaturated fatty acids is effective against granular stains. Also, U.S. Patent No. 39
No. 29678 and No. 3925262 contain amphoteric surfactants;
No. 2905 states that a combination of selected cationic and nonionic activators exhibits superior detergency against particulate dirt (clay). Furthermore, in Japanese Patent Publication No. 3811/1989, it is stated that thiourea dioxide is effective (reducing action) against contamination by iron compounds.
No. 49279 describes that when cellulase is blended into a detergent composition, the detergency against mud and stains is improved.

However, since the method described in JP-A-57-36198 uses soap, there is a problem that yellowing of the items to be washed due to the soap is unavoidable, and the cleaning effect is as low as that of conventional soap powder. .

Furthermore, methods using amphoteric activators and cationic/nonionic mixed activators have low inorganic stain removal effects, and also have problems in raw material supplyability and cost.

On the other hand, reducing agents such as thiourea dioxide can provide excellent effects if soaked for a long time, but there is a problem that bleaching of dyed clothing cannot be avoided. In the method using cellulase,
When clothes (cotton products) with mud on them are immersed in an aqueous solution containing cellulase at the optimum pH, it is certainly effective in removing mud stains, but at the same time, cellulase significantly reduces the strength of cotton fibers (cellulose) and causes the fibers to deteriorate. There is a problem with damaging it.

In addition to the above-mentioned problems, in recent years, from the viewpoint of preventing eutrophication, there has been a trend toward phosphorus-free products that do not contain phosphate bilge, making it even more difficult to improve the detergency against mud stains. In other words, phosphates such as sodium tripolyphosphate have excellent dispersion power against inorganic substances as one of various virgoo effects, so phosphate-containing detergents themselves have excellent detergency against mud stains; The dispersing power of zeolites and polycarboxylate salts used as salt substitutes for inorganic substances is inferior to that of phosphates, so it is technically more difficult to improve the detergency against mud stains with phosphorus-free detergents. This is because

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a phosphorus-free detergent composition that does not damage fibers or adversely affect dyed products and exhibits extremely excellent detergency against mud stains. shall be.

[Means for solving problems]

The present invention is based on the finding that a phosphorus-free detergent composition containing an enzyme having pectinase activity surprisingly has extremely excellent detergency against mud stains and can effectively solve the above problems. It was done.

Examples of enzymes having pectinase activity used in the present invention include the following enzymes and mixtures thereof. The first is an enzyme called polygalacturonase that hydrolyzes the α-1,4 glycosidic bond of galacturonic acid.The second is an enzyme that hydrolyzes the C1,4 glycosidic bond of galacturonic acid and its decomposition product is uronic acid. 04 and C at the non-reducing end
An enzyme called pectic lyase that creates a double bond between 5. The enzymes shown in the first and second sections are further divided into two, depending on whether they use pectin directly as a substrate or pectic acid as a substrate, and either act on the end of the substrate or randomly cleave the inside. It's divided into two depending on whether you do it or not.

Third, there is an enzyme called pectin esterase that breaks down methyl esters of galacturonic acid.

Generally, it is known that most of the enzymes having pectinase activity produced by microorganisms are a mixture of the above-mentioned enzymes, and the composition ratio thereof differs depending on the originating microorganism.

Regardless of the composition ratio of each of the above-mentioned enzymes, the titer of the enzyme having the essential pectinase activity in the present invention is 1 unit (for the activity measurement method, (described in detail in Examples), an enzyme having a titer of at least 5 units/mg solid content is preferred, and more preferably 10 units/mg solid content.

The cleaning composition of the present invention contains the enzyme having pectinase activity in any amount, but preferably 0.1 to 30% by weight (hereinafter abbreviated as %), preferably 0.1 to 10%. Good. Further, the cleaning composition of the present invention has a content of 1 β per 1 β of water.
．． It is preferable to use 33 to 26.6 g, and it is preferable to make sure that the enzyme having pectinase activity is contained in an amount of 6.65 units)/A or more during washing.

Since enzymes exhibit maximum enzymatic activity at optimum pH, it is desirable to select enzymes of appropriate origin in the cleaning composition according to the present invention depending on the pH of the cleaning composition in water. In other words, enzymes with pectinase activity (hereinafter referred to as pectinase) include acid pectinase, which has an optimum pH in the acidic range, alkaline pectinase, which has an optimum pH in the alkaline range, and neutral pectinase, which has an optimum pH in the vicinity of neutrality. It is known that acidic pectinase is used in weakly acidic detergent compositions and alkaline pectinase is used in alkaline detergent compositions.

Next, the originating bacteria of acid pectinase and neutral pectinase are illustrated.

Bacillus polymyxa
yxa), Bacillus subtilis
5ubtilis), Bacillus pumilus (Bacillus
llus pumilus), Cytophaga johnsonii, Cytophaga debrimata (Cytophaga dep.
rimata), Pseudomonas marginalis (Ps.
eudomonas marginalis), Pseudomonas fluorescens (Pseudomonas
fluorescens) Penicillium chrysogenum, (t'enicillium chrysogen
um), Heni/rium expansum (Penici)
llium expansum), Erwinia
Brwinia aroideae
, Erwinia ca.
rotovora), Erwinia chrysanthemum (
8rwinia chrysanthemi), Flavobacterium pectinovolum (Flavoba-ct
erium pectinovorum), Clostridium multifermentans (Clostri
dium multi-rmenta S), Xanthomonas siatubusidis (Xanthomonas
s cyanopsidis), Aeromonas l1quefaciens
iens), Bacillus sphaericus (Bacillus
- Xanthomonascampestris
estris), Bacteroides ruminicola (B
Acteroides ruminicola), Clostridium ferruginium (Clostridium ferruginium)
m felsineum>, Clostridium butyricum
, Fusarium tara (formerly Fusariumsofa), Aspergillus fonsecaeus (Aspergillus)
illus fonsecaeus), Fusarium oxysporum (Fusarium oxysporum)
um), Pseudomonas prunicola (Pseud
omonas prunicola), Monilia laxa (Monilia 1axa), Rhizoctonia cod (Rhizoctonia 5olani)
, Diplodia gossypina
gossypina), Ce/l/] Cercosporel 1aher
potrichoides), Acrocillinthrium (
Acrocylindrium), Pellicularia filamentose
amentose), Aspergillus foetidus, Aspergillus saitoi
5aitoi), Aspergillus soi (8spe
rgillus 5 ojae), Aspergillus oryzae (8 spergillus oryzae A-3)
, Aspergillus japonicus
sjapan 1cus), Aspergillus niger (
Aspergillus lusniger), Aspergillus flavus (Aspergillus flavus)
), Corticium rolfushi (Corticiu
mrolfsii), Saccharomyces fragilis
, Colletotrichum Iindemuth
ianum), Coniotycum diplodiella (C
oniothyrium diplodiella), Fusarium moniliforme (Fusarium moniliforme)
iliforme), Soufflerotinia libertinia (
Sclerotinia 1ibertiana), Agaricus capen
tris), Alternaria batachikola (81te
rnaria bataticola), Alternaria citri (81ternaria citri)
, Taladosarum olibasium (Cladsaru
m olivaceum), Tarabaria musida (Cl
avaria mucida), Colletotrichum phomid
es), Corticum centrifugum (Corticum
umcentrifgum), Corticumyagum, Polystictus sanguineus
uineus), Boria bavolaria (Poria v.
aporaria), Pluraria pullulans (P
ulularia pullulans), Fusarium 1ini, Gibberella 5aubin
etti), Hybokaunas centrifugus (Hy
pocaunas centrifugas), Penicillium cit
rium), Penicillium luteum (Penicillium
lium luteum), Penicillium sclerothiorum (Penicillium scleroti)
orum), Pytium ultimum (Pytium ultimum)
ultimum), Penicillium digitatum, Geotrichum candium
candidum), Curbararia lunata (Cur
valaria 1unata), endothia varasitica (Bndothia parasitica),
Foetidus candum (Foetidus)
candidum), Arthrobacter species (^rthr)
obacter sp, ), Aspergillus n1dulans
), Aspergill
us varians), Aspergillus fumigatus, Penicillium n.
otatum>, Penicillium nigricans (Pen
icillium nigricans), Penicillium italicum (Penicillium 1talic)
u+n), Fusarium roserum (Fusarium
roseum), and Bacillus P-4N ([]acillus P-4N) as alkaline pectinase originating bacteria.
4-N: Japanese Patent Publication No. 48-6557) is exemplified.

In the present invention, the following commercially available pectinases using these various originating bacteria can be used.

Sucrase N (manufactured by Sankyo Co., Ltd.), Ultra Vectinex (manufactured by Novo Industries), Soluble Pectinase (manufactured by Tanabe Pharmaceutical Co., Ltd.), Pectinase A (manufactured by Amano Pharmaceutical Co., Ltd.), Pectolyase (manufactured by Seishin Pharmaceutical Co., Ltd.),
Pectinase (manufactured by Nagase Co., Ltd.), Pectinase SS1
Pectinase 3B (manufactured by Yakult Co., Ltd.) and the like.

The detergent composition of the present invention basically contains the enzyme having the above-mentioned pectinase activity, but may further contain various components.

○Surfactants Examples of anionic surfactants include alkylbenzene sulfonates whose alkyl group has 8 to 15 carbon atoms, alkyl sulfates whose alkyl group has 8 to 18 carbon atoms, and alkyl sulfates whose alkyl group has 8 to 18 carbon atoms. Salts of sulfates of ethoxy compounds obtained by adding an average of 1 to 8 moles of ethylene oxide to alcohols, salts of sulfonates of alpha olefins having 12 to 22 carbon atoms (this is alkenesulfonates, tohydroxyalkanesulfonic acids) salts), alkanesulfonates derived from paraffins having 12 to 22 carbon atoms, higher fatty acid salts, salts of condensates of higher fatty acid salts and taurine (N-acylamino ethanesulfonate), salts of dialkyl sulfosuccinates, α-sulfo fatty acid esters having 12 to 22 carbon atoms, disulfonates of unsaturated fatty acid esters having 12 to 22 carbon atoms, and the like. All of these salts are preferably alkali metal salts, ammonium salts, or ethanolamine salts, and in the case of sulfonic acid or sulfate type anion activators, magnesium salts can also be used.

In addition, as a nonionic activator, polyoxyethylene (C
1o-C38) alkyl ether, polyoxyethylene (C6-C,,) alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, sugar fatty acid ester, fatty acid alkylolamide, etc. can be used. As the amphoteric active agent, betaine type such as lauryldimethylcarboxymethylammonium betaine, alanine type, and imidacilline type can be used. In the detergent composition of the present invention, any of anionic active agents, nonionic active agents, and amphoteric active agents may be used alone or in a mixture of two or more thereof.

As the builder building goo, it is preferable to use the building goo that does not contain phosphorus shown below.

(1) Aminopolyacetate such as nitrilotriacetate, ethylenediaminetetraacetate, iminodiacetate, hydroxyethyliminodiacetic acid, etc. (2) Amino acids such as aspartic acid, glutamic acid, glycine, etc. (3) Oxalic acid, malonic acid, Kono 1 Salts of dicarboxylic acids such as phosphoric acid, curtaric acid, adipic acid, etc. (4) Glycolic acid, malic acid, tartaric acid, citric acid, curconic acid,
Salts of oxycarboxylic acids such as curcuronic acid, mucic acid, glyceric acid, tartronic acid, carboxymethyltartronic acid, dicarboxymethyltartaric acid, and derivatives thereof (5)
itaconic acid, maleic acid, fumaric acid, aconitic acid,
Butanetetracarboxylic acid, trimesic acid, pyromellitic acid (6) Salts of sulfonated carboxylic acids, etc. (7) Aluminosilicate (Special Type 1A type zeolite) (8) Reducing alkali metal salts such as NaiSOs (9) Alkaline agents , inorganic electrolyte silicate, carbonate, sulfate, triethanolamine, monoetharylamine, jetanolamine, triisovaropanolamine, etc. The above virgoos (1) to (7) should be used in the acid state. However, as a counter ion, it can be used as a salt having an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, or an alkanolamine having 2 to 3 carbon atoms.

○High molecular compound carboxymethylcellulose (carboxymethylation degree 0)
．． 2-0. 9), carboxybutyl cellulose (
degree of carboxybutylation 0.2 to 0.9), polyethylene glycol, polyvinyl alcohol (including partially saponified), polyvinylpyrrolidone, polyacrylic acid, polyitaconic acid, polyfumaric acid, polymaleic acid, polyhydroxyacrylic Acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoamylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, anhydride Maleic acid-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer,
Maleic anhydride-acrylic acid ester copolymer, acrylic acid-styrene sulfonic acid copolymer, itaconic acid-ethylene copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, ethylene glycol- Examples include ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, dicarboxymethyl starch, and gelatin. Among these, the degree of polymerization is 2 to 50
00 is preferred.

Other Enzymes Other enzymes may be used together with pectinase in the cleaning composition of the present invention. Specifically, they include alkaline protease, lipase, amylase, etc., which can be easily produced manually as the following commercial products.

(i) Alkaline proteases Alcalase, Esperase, Savinase (manufactured by Novo Industries) Maxacal, Maxatase, Hyalkaline protease (manufactured by Gist Prokate) Optimase (Miles) Alkaline protease (Showa Denko K.K.) Bioplase (Nagase Co., Ltd.) Brozyme (Amano Pharmaceutical Co., Ltd.) Actinase (Kaken Pharmaceutical Co., Ltd.), etc.

1ii1 Lipase Termamil (Novo), Lipase (Gistbrocade), Olivase (Nagaushi), Lipase AP (Ohno Pharmaceutical), Talipase (Tanabe Seiyaku), Lipase (Toyo Jozo), Godo B-5L (Godo Shusei), etc.

Other additives Various components commonly used in detergent compositions such as fillers such as sodium sulfate, fluorescent whitening agents, foam control agents, pigments, and fragrances can be added.

A preferred cleaning composition containing the above components basically contains 0.1-30% enzyme having pectinase activity, 5-40% surfactant, 5-50% phosphorus-free bilge, and 0-10% polymer compound. Preferable compositions include those containing the above ingredients.

Next, preferred embodiments of the present invention will be described.

(1) A combination of the following surfactant and an enzyme having pectinase activity is particularly preferred, as it provides even better mud and dirt cleaning power.

That is, (i) C, -C22α-olefin sulfonate, [1ilCa ~C1, alkyl ethoxy (1-8
mol) sulfate, [1iil poly(5-20 mol)
5 to 40% of one or more surfactants selected from oxyethylene (C,, -C,,) alkyl ethers,
This corresponds to a detergent composition consisting of 0.1 to 30% of an enzyme having pectinase activity, 5 to 50% of phosphorus-free bilge, and the balance of detergent additives, Glauber's salt, and water.

Practically speaking, it is preferable to use the above surfactants in the following combinations.

■ Alpha olefin sulfonate/alkylbenzene sulfonate 1/9 to 9/1 ■ Alkylbenzene sulfonate/alkyl ethoxy ether sulfate ratio 179 to 9/1 ■ Alcohol sulfate/alkyl ethoxy ether sulfate ratio 1/9 to 9/1 ■ Alkyl ethoxy ether sulfate/ Polyoxyethylene alkyl ether ratio 1/9 to 9/1 (2) Another preferred embodiment includes a combination of 0.1 to 30% of an enzyme having pectinase activity and a water-soluble polymer compound; This provides superior dirt cleaning power.

In particular, water-soluble polymer compounds include carboxyl methyl cellulose, polyethylene glycol, polyvinyl alcohol, zetine, polyacrylic acid or its salt, acrylic acid-methyl acrylate copolymer, maleic acid-isoamylene copolymer, maleic anhydride-methyl vinyl ether Preferably, a salt of the copolymer is used, with 0.2
It is appropriate to contain up to 10%.

Add 5 anionic activators or nonionic activators to the above two components.
This corresponds to cleaning compositions containing 5 to 50% of phosphorus-free virgool.

(3) Yet another preferred embodiment includes a combination of 0.1 to 30% of an enzyme having pectinase activity and other enzymes, which provides excellent dirt cleaning power.

As the other enzyme, alkaline protease is preferred, and the composition contains 0.1% to 5%, more preferably 0.3% to 3%.
% is preferable.

Add 5 to 5% of anionic activator or nonionic activator to the above two components.
This corresponds to a cleaning composition containing 40% and 5 to 50% of phosphorus-free bilgu.

(4) In yet another preferred embodiment, a combination of an enzyme having pectinase activity, alkaline protease and a water-soluble polymer compound provides particularly excellent detergency against mud stains.

Specifically, this composition includes 5 to 40% of anionic activator or nonionic activator, 5 to 50% of phosphorus-free virgoo,
Enzyme with pectinase activity 0.1-30%, alkaline protease 0.1-5%, polymer compound 0.2-1
A cleaning composition containing 0% as a basic component is exemplified.

The cleaning composition of the present invention can take various forms such as granules, powders, liquids, and pastes.

In the present invention, the mechanism of the enzyme having pectinase activity that has excellent detergency against mud stains has not yet been completely elucidated, but is presumed as follows.

First, as a result of a detailed study of the mud surface in order to elucidate the cause of mud stains, we discovered that the mud surface surprisingly contains a large amount of organic matter. It is presumed that this organic substance interacts with clothing fibers and colloids (mud particles), making it difficult to remove dirt, but enzymes with pectinase activity work together with other detergent ingredients to It was thought that because it works to destroy the interaction, it has an excellent removal effect on mud.

〔Effect of the invention〕

The detergent composition of the present invention exhibits extremely excellent detergency against mud stains even though it does not contain phosphate virgoos. Further, there is an advantage that fiber damage does not occur as in the case of using cellulase.

In addition to the above-mentioned advantages, the detergent composition of the present invention has excellent detergency against sebum stains, so it can be used not only for clothing but also as a detergent for various purposes.

Next, the present invention will be specifically explained with reference to Examples.

〔Example〕

The method for preparing the artificially contaminated cloth, the washing conditions, the washing method, and the enzyme activity measurement method used in the examples are shown below.

(1) Creation of artificial mud-contaminated cloth Mud particles with an average particle diameter of 1 μm obtained by dry-smoking, crushing, and classifying red loess from the Mikatagahara Diluvial Plateau in Shizuoka Prefecture were ultrasonically dispersed in ion-exchanged water to give 1% It was made into a suspension. Next, Yukakyo cotton cloth was brought into contact with this suspension, air-dried for 30 minutes, and then dried at 105° C. for 30 minutes. Next, remove excess dirt by brushing and clean the 10cm x 10C1
A test fabric of n was obtained.

(2) Cleaning conditions, cleaning method, evaluation method A cleaning composition was dissolved in 3° DH hard water to prepare a 0.8% cleaning agent aqueous solution 11. Add 5 muddy artificially contaminated cloths to an aqueous detergent solution, immerse them at 40°C for 1 hour, and then add the aqueous solution to National's product name \l1ni Mini Washe.
r, and the cleaning composition concentration was 0.133% with tap water.
After adjusting the temperature to 25°C, the mixture was stirred for 1° and washed. After rinsing under running water, it was pressed with an iron and used for reflectance measurement.

Hunter white discoloration of the original fabric before washing and the contaminated fabric before and after washing was measured using a color difference meter made by Nippon Heavy Industries, and the cleaning rate was calculated using the following formula.

Note that the cleaning rate is shown as the average value of 5 sheets.

(3) Enzyme used and method for measuring its enzyme activity O Enzyme A Sucrase N (Sankyo Co., Ltd., source bacteria, Conio
thyrium diplodiella) activity: 6
1.6 units/mg solid matter B Ultra Pectinex 5P-L (Novo Industries, originating bacteria, ^sp
ergillus niger) Activity: 54.1 units/mg solid content C pectinase (Nagase Co., Ltd.) Activity: 10 units/mg solid content 1ml of solution! was added and reacted at 40°C for 30 minutes. After stopping the reaction, 0. 6 mi of IN iodine solution was added. After standing in a dark place for 30 minutes, 2M 6Iri sulfuric acid was added, and iodine titration was performed with 0.1N sodium thiosulfate using starch as an indicator. Let this titration amount be 8-. Separately, as a blank test, the enzyme was deactivated in advance and then iodine titration was performed in the same manner. This titration amount is B
−. The titer was defined as the power of 1 unit to produce 1 μmol of galacturonic acid when 1 g of the enzyme acts on pectic acid.

Therefore, titer = (B - A) X513 xx dilution factor. 1 mg equivalent of reduced iodine corresponds to 0.513 mg equivalent of galacturonic acid.

Incidentally, the activities of the enzymes A to C above were measured by the final method.

Example 1 Compositions (1-1 to 1-4) shown in Table 1 were prepared and their performance was evaluated. The results and composition are summarized in Table-1. still,
The values for the composition are in weight percent, and the mirabilite balance is 10
It was set to 0% (the same applies below).

Table 1 shows that the products of the present invention (1-1 to 1-4) have improved detergency against mud stains.

Example 2 Compositions using various types of surfactants were prepared and their performance was evaluated. The results are shown in Table 2 along with the composition. Note that 100 in the table indicates the average number of moles of ethylene oxide added (the same applies hereinafter).

From Table 2, it can be seen that even with the products of the present invention, those using Na alkylbenzenesulfonate alone as a surfactant (2
-6) and the combination of Na alkylbenzenesulfonate and alkyl sulfate (2-5), the preferred surfactant Na α-olefin sulfonate alone (2-1) and other preferred surfactants Those used in combination with a surfactant (2-2 to 2-4) are all (2-5
) (2-6).

Example 3 Cleaning compositions were prepared using different types of water-soluble polymer compounds, and their performance was evaluated. The results and composition are summarized in Table 3. Regarding enzymes, in addition to A, B, and C described in Example 1, enzymes derived from Bacillus subtilis (contains a large amount of pectic lyase, hereinafter abbreviated), and Bacillus P-4
-N-derived alkaline pectinase (hereinafter abbreviated as E) was used.

For this additional enzyme, the buffer for enzyme activity measurement was changed from acetate to 0.1M glycine-NaO)I-N.
The buffer was changed to aC1 pH9. The units (potency) were unified.

From Table 3, it can be seen that even with the products of the present invention, the products containing water-soluble polymers (3-2 to 3-9) are more cleansing than those that do not contain water-soluble polymers (3-1). It can be seen that the power improves. Among these, as the water-soluble polymer, sodium polyacrylate and carboxymethyl cellulose are particularly preferred, and in combination with a preferred surfactant (3-7 to
3-9), it can be seen that the cleaning power is further improved.

Example 4 A detergent composition was prepared by combining an enzyme having pectinase activity and another enzyme (alkaline protease), and its performance was evaluated. The results are summarized in Table 4.

Combine pectinase and protease from Table 4 (
4-2.4-3), it can be seen that the cleaning effect is improved.

Example 5 A composition combining an enzyme having pectinase activity, alkaline protease, and a water-soluble polymer compound was prepared and its performance was evaluated. The results and composition are summarized in Table 5.

From Table 5, combinations of pectinase and water-soluble polymers (5-
It can be seen that when protease is added to 5> (5-1 to 5-4), the detergency is significantly improved.

Claims (1)

[Claims] A phosphorus-free detergent composition containing an enzyme having pectinase activity.