JPS5949279B2 - Low phosphorus powder detergent composition for clothing containing phosphate builder - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cleaning compositions. More specifically, the present invention relates to a cleaning composition characterized by containing cellulase. In recent years, significant advances have been made in the washing of clothing. In other words, washing clothes has become significantly easier due to the development of raw materials suitable for detergents, improvements in water quality, improvements and spread of washing machines, improvements in fibers, etc. In particular, improvements in raw materials for detergents have been remarkable, and it appears that the composition of laundry detergents has almost reached the point of perfection through modifications of surfactants, builders, dispersants, fluorescent dyes, bleaching agents, etc. be. However, the idea behind the development of laundry detergents is that by adsorbing surfactants and builders on the dirt and/or fiber surface, the interfacial tension between the dirt and/or fibers and water is reduced, and the 2) Disperse and solubilize dirt with surfactants and inorganic builders, 3)
Chemically decomposes dirt with enzymes such as protease, 4)
Bleaching colored stains with bleach, etc.; 5) whitening by adsorbing fluorescent dyes, etc. to the fiber surface; and 6) using a chelating agent to prevent precipitation caused by divalent metal ions, which are effective ingredients for cleaning. Summarized. That is, the basis of conventional clothing cleaning has been how to effectively incorporate ingredients that directly attack stains or ingredients that assist in the attacking power of the ingredients as a component of a detergent composition. At present, in a sense, the cleaning performance of cleaning compositions based on this basic principle has almost reached a saturation point, and great efforts are required to further increase the cleaning power. The present inventors have been actively investigating whether it is possible to grasp various phenomena related to washing clothes from a completely new perspective without being bound by conventional preconceptions, and recently, completely unexpectedly, an enzyme, cellulase, has been investigated. The present invention was completed by the coincidental discovery that, when incorporated into a cleaning agent, an extremely excellent cleaning effect can be achieved on unexpected stains that are completely unrelated to the enzyme activity of cellulase. The present invention provides a low-phosphorus powder detergent composition for clothing containing a phosphate builder, which is characterized by containing cellulase as one component of the detergent composition, and in particular has no relation to cellulase activity. The object of the present invention is to provide a cleaning composition that exhibits remarkable cleaning properties against inorganic stains. As mentioned above, the use of enzymes in the technical field of detergents is known, but only enzymes that are particularly effective against dirt are known. That is, protease is known for protein stains, amylase is known for starch stains, and lipase is known for oil and fat stains, all of which are enzymes that directly attack stains. The cleaning mechanism of cellulase in the present invention has not yet been completely elucidated, but it is not based on a mere swelling effect on fibers, the essence of which can be seen in surfactants. A great advantage of the present invention is that it is very useful in improving the cleaning power of low phosphorus detergents. Phosphate was effective in removing fine scale dirt that got between the fibers. However, due to the problem of eutrophication, the amount of phosphate added has been decreasing, and some products have been forced to be phosphorus-free, making it impossible to remove muddy dirt. It is well known that it is particularly difficult to remove muddy dirt that has penetrated cotton cloth. Also,
Housewives are also troubled by the muddy dirt that clings to zutsuku made of cotton blend fabric. The cleaning agent of the present invention brings light to the solution of these problems. That is, by applying the present invention to an alkaline low-phosphorus powder detergent when cleaning muddy stains on cellulose fibers and fabrics blended with other types of fibres, 2) weak alkaline or neutral liquid detergents can be removed. Applying the present invention to phosphorus detergent 25
By doing so, it is possible to obtain excellent cleaning power equivalent to or better than weak alkaline powder cleaning containing sufficient phosphate. Another advantage of the present invention is that the cleaning performance of mineral soils is not affected by the PH of the cleaning composition. As is well known, enzymes exhibit their maximum enzymatic activity at an optimum pH; however, even if a cellulase having an optimum pH in an acidic region is used, sufficient cleaning performance can be obtained in an alkaline environment. Furthermore, no difference was observed in the strength of the fibers to be cleaned compared to conventional cleaning agents. The essential cellulase of the present invention is one that is widely distributed in animals, plants, bacteria, and fungi, that is, an optimal pH of 8.
Those less than O can be used, and are not particularly limited. Examples 40 of the origins of cellulases are shown below. (a) Originating from protozoa (ciliates, flagellates, amoebae, etc.) (1) Endoprotenum neglectum (EndOpl-0dinumneg1ec)
tum), (2) Trichomonas thermocidus (Tri
chOmOnastermOpsidus)> Those originating from molluscs (snails, sea snails, giant snails, sea bream beetles, etc.) include (1) HelixpOnatia, (2) Stromonas gigas, (3)
) Dravetula auricularia solander (DOlab
ella auricula SOlander), (4)
Mytilus Ostera
, (5) XylOphag
adOrsalls), (6) Cryptochitonstelleri,
(7) Pteroceracr
(8) Caslatura hautec Oeuri
(9) Melanoides tuberculata (MelanOidestuberculata)
, (Main) Mia Arenaria (Myaaren-Aria)
), (own) Mactra Soliditessima
sOlidissima), ◎Pangia setacea (B
ankiasetacea), 03)/'< Bankiaindica, (own) TeredO, (own) modeiola modeiolus (
MOdiOlamO-DiOlus), CryptoOplaxjap
Onica), Hariotheis 8 Japonica (Ha
liOtisjapOnica), (Own) TurbOcOrnutus, (Own) Tegulapfeifferi,
(to) Remintina leibricata (Lemintin)
(21) FasciOlariatrapez
ium), Qtsu Dolabella 0 Auricula (DOlabel
C23) Homoiodris japonica (HOmOiOdOrisja-POnica)
), (2◆DendrOdOrisrubavar.nigr
G25) Onchidium verruculatum (Omaculata), G25)
m) 1 (g) Euhadra perionfuala (Euhad)
rape-110 mpha 1a), (27) Mytilus edulis, (28
) Meretricus meretricus lusoria (Mer
etrixmeretrixIusOria), (29
) Venerupisp filipinarum (Venerupisp)
hiIippinarum), (30) Octopus sp.
0ct0pussp. ) (c) Originated from nematodes: (1) Ditilenchus destorcutor (Dityle
(1NchusdeststructOr), (2)Ditylenchusdipsa
ci) (d) as originating from annelids;
5(1) Euni
ceaphrOditOis), (2) TylOrrhynchushet
erOchaetus), (3) Glycera Kirori (G
lycerachirOri), (4) Loimiamedusa, 10(5) Sabellastart
eindica), (6) Rhizodorillus sp.
Odrilus sp. ), (7) Fuereteina species (Ph
e-Retinasp. ) (e) S-derm animals (sea urchins, etc.)
15(1) Anthosidaris as originating from
Cratsisvina (AnthO101dariscras)
(2) PsemlOcentrOtusdepres
-Sus), (3) HemicentrOtuspulcherrimus
s), (4) Sam 20 Metinus Millianth (Psa)
mmechinus milians) (4) Originating from crustaceans (1) Mitella mitella
), (2) Megalygia exotheica (people4ega1i
giaex0tica). 25 (3) CaIappaIOpl.u, (4) Gaetice depressus (Su)
s), (5) Pacigrasus cratusipes (Pac-H
(6) Plagusia dentipes
s), (7) Gear Rib 30 Days Beres (Chary
bdismiles), (8) Carciplax longimanus
s), (9) Tiarinia cornigera (Tiarinia
iacOrnigera), LeftOmithrax Eduardosi (LeftOmithraxedwar)
dsi), 35a1) Naxiodes Historiques (N
axiOidesllystrix), (auto) Hapalogaster dentata (11-ApalOgasterde
ntata), (self) Aniculus Aniculus (Ani)
Dardanus crassimarl), σa Dardanus crassimanus
us), A5) 40 Upogebia ●Majiyoru (UpOge
biamajOr), (to) Panullus 3 japonicus (PanulrusjapO-Nicus), (5)
Penaois japonicus
cus), (self) Syladedes siebordei (Scy
llaridessieb Oldi), (PrOcambarusclar)
kii), g) Originating from insects (ants, beetles, etc.) (1) Termes Obesus
sus), (2) Tatenolepisma lineata (Cten
Olspismallneata), (3) Cerambixcerdo (Cer-AmbyxcerdO), (4
) Cestobium rufuovirosum (XestObiun)
(5) Nasutitermese
xitiOsus), (6) CoptOtermeslacteus, (7)
Stromateium fulvum
fulm), (8) Deixips 0 Morosus (4) Ix
ippusrr]0r0sus), (9) Limnoria・
Lignorm (LirrlnOriaLignOr1Um
) h Originating from bacteria (1) Bacillus hydrolyteix
h-YdrOlyticLls), (2) Cellulobacillus mucosus
Osus), (3) Cellulobacillus myxogenes (C
ellulObacillusmyx10genes)
, (4) Cellulomonas sp.
p. ), (5) Cellvibrio fulbus (Cellvi
briOfUlVLlS), (6) CellvibriOvulgaris, (
7) Clostridium celmocelllazoime (ClO
stridiurnth-ErmOcellulase
urr]), (8) Clostridium sermocellum (ClOStridiLlnlthermCCellL
(9) Corynebacterium sp.
bacteriurnsp. ), (CytOphagaglObulOsa),
(auto) Soidomonas fluorescens 0bal3 cellulosa (PseudOn)0nasf1u0r1Escen
svar. cellulcsa), PseudOmOnasSOlan
aCearUr]1), (auto) Bacterioides succinogenes
Ogenes), A4) Ruminococcus 3 Albus (R
L]Rr]InOcOccusalbus), (auto) Ruminococcus flabefuaciens (RLlnllnO
cOccusflavefaciens), Sorangium 6 Compositum (SOrangiun) COm
pOsitunl), (5) Butyrivibrio (Buty
rivibriO), (auto) Clostridium sp. (C
lOstridiLlrnsp. ), 09) Xanthomonas cyamosideis (X2TlthOmOnaSCya
ITX) PSidiS), (to) Scleroteium batateicola (SClerOtiU[11Batatic
Ola), (21) Bacillus sp.
．． ), (22) Selmoactenomyces sp. (Th5m
Oact-InOmycesssp. ), (23) ActinObifidasp. (
1-1) Fungi; originating from actinomycetes 5
(1) Actinomyces sp.
sp. ), (2) Strebtomyces sp.
Omycesssp. ) (i {) Fungi; Those originating from filamentous fungi (deuteromycetes, algal fungi, ascomycetes, etc.) include (1) Arthrobotrys superba (ArthrObOtrysl);
(Superba), (2) Aspergillus aurois, (3) Aspergillus 0 flavipes (Aspergillus f.
(4) Aspergillus flavus (
Aspergillus flavus), (5) Aspergillus fumigatus (Aspergillus f 1
gatus), (6) Aspergillus lucuenis (A
(7) Aspergillus luchuenis), (7) Aspergillus luchuenis
(8) Aspergillus niger (
Aspergillus niger), (9) Aspergillus oryzae (Aspergillus ory-
21zae), Aspergillus rugrosus (A
spe “GillussrugulOsus”, (self) Aspergillus sidbyi (AspergiIlussy)
ii)' Aspergillus tamarii
lIustamarii), (self) Aspergillus ◆ Tellurois (Aspergillus sterreus),
(self) Aspergillus anguis (Aspergillus)
Iusunguis), Aspergillus astus, Takamine-Cel! Ul
ase), (1n Aspergillus cytoi (Aspe
rgilIussaitOi), (self) Botrytiscinerea (BOtrytiscinerea), (
11 Botryodeiplodia Theopromae (BOtr)
yO-DiplOdiatheObrOn]Ae), (
2I Cladosporium cucumerinum (CladOsp
Oriumcucumerium), (21'y/Radosporium herbalum (CladOspO-Riun)
lherbarurn), (22) CoccOspOraagricOla, (
23) Curvularia L
urlata), (24) Chaetomium cermophyle bal coprophyle (ChaetOichi Miumthe
rmOphllevar. cOprOphile), (
25) Power 4 ChaetOmiumther (self) Phil
evar. (26)'. SpOrOtrichumumth
er (4) Phile), (27) Talomyces etal 1.゛2, Soniichi (TarOmycesemersOnii), (
28) Thermoax ● Auranteiax (Therm
Oascusau-Rantiacus), (29) Humicola 0 Grisea 0 Val 0 Selmoidea (Hunllc
Olagriseavar. therm-01dea)
, (30) Humicola insolens (Hunll-EO
lainsOlens), (31) 7 Le Branch Air
Pultiera bal sulfrea (Malbrarlch)
eapulc-Hellavarsulfurea),
(32) Myriocottum albomyces (MyriO
cOccumalbOmyces), (33) StiIbelIathermO
phile), (34) Torula, Selmophila (Tor
urathermOphila), Chaetomium
Globos 11 (ChaetOmiumglObOsun
l), (36) DictyOsteliurndiscOideu
m), (37) Fusarium sp.
．． ), Fusarium burbigenum (Fusari)
unlbulbigenu [n], (39) Fusarium equiseti
, (40) Fusarium lateritium (Fusari
umlateritium), (40FusariU[1111ni), (FusariumOxyspOru
m), (43) Fusarium bassinfuectum (FUS
ariUr[1vasinfectun1), (44)
Fusarium dimerium
rLlnl), (45) Fusarium japonicum (F
usariumjaPOniCL]In), (46) Fusarium scirpi
, (47) Fusarium 8 solani (Fusariums O
(9) Fusarium moniliforme (Fu
sariunlrnOnilifOrme), (49)
7 Thallium Rozoim (FusariUn) ROSeL
OTl), (50) Helminthosporium sp.
intbDspOr-Iumsp. ), (51) Mennoniellae
chinata), (52) Fumicola 3 Fucoatla (H
unllcOlafucOatra), (53) Humicola grisea, (5
4) Monllia sitophylla (MONllasitOp
hila), (55) Monotospora brevis (MOn
OtOspOrabrevis), (56) MucOrpusillus, φη MycOsphaerella citrullina (MycOsphaerllac)
(branch) MyrOth-Eciunlverrcaria
), (59) Papraspora species (Pa1,0Iasp0r
a8,. ), (Foundation) Penicillium species (Penici-1
11un1sp. ), (61) Penicillium capsulatum (PaicllllLlnlcapsulatuO
l), (65 Penicillium chrysogenum (P button 1ci
11iurnchrys0ger1-UrTl), (6
3) Penicillium frequentans (Penicillium)
llun] Fr duck Uentans), Penicillium jiancinerum (Foundation)
hine-11urn), (65) Penicillium lutoum (Penicillium-1un11uteum1), (
66) Penicillium pisarium
lunlPiSCariLtll), (67) PenicillumsOppi,
(b) Penicillium spinulosum
lurrlspinulOsum), (69) Penicillum [Nturb
(70) Penicillium daigitatum (P
enicllumdigitatLlnl), C7O
Penicilliu
rrlexpansurr]), (7 Penicillium
Penicillunlpusil-1U [
]1), (73) Penicillium rubrum (Penic
il-11un1rubru[n], (74) Penicillium waltmanii (PenicllllunlwO
rtmanii), (75) Penicillium variabile (PeniCllllL]Rllvariabile)
, (70 Pestaloteia palmarum (PestalO
(77) Pestalotiopsis westerdeikii (PestalOtiOps)
iswesterdijkii), Fuoma species (P
hOmasp. ), (79) Schizophyllum comune (
SchizOphyllurncOmmurle), (
80) Scopulariopsis brevicauris (ScOp
ulariOp-Sisbrevicaulis), (
81) Rhizopus sp. (RhizOp1 Ussp.), (8
Casporotrichum carnis (Sp-0r0triCL
1rr] CarniS), (83) SporOtrichum 0 pruinOs
(84) Stachy
bOtrysatra), (85) Torula species (TOru
lasp. ), (8Q Trichoderma viride (Tric
hOdermaviride), (87) Trickles
Cylindricus (Trichuruscylndri)
cus), (b) Erticillium albo atrum (Ertici-111uma1b0atrun1),
(89) Aspergillus cellulosae (Aspergl
(90) Penicillium glaucum (PC!11Ci111Um1g1aU
CL1m), (90 Curlni
ngha [Tllellasp. ) (95 MucOrmucedO, (93) RhyzOpuschinensis, (9
◆Coremiella sp., (9
5) Kalingia rosea (KaI-11ngiar0
sea), 10 Phytofuso'7 Rocactrum (Rhyt
OphthOracactOrum), (b) Phytophthora citricola
rilla), (98) Phytophthora parasitica (
PhytOphthOraparasitica), (
g) Pythium sp., α(1) SaprOlegniaceae
), αO) Ceratocystasis urumi (CeratOc)
ystisulmli), (102) ChaetOmiumglObcsum,
α03) Chaetomium indicum
iurnindi-CUIT]), 004) NeurOs-POracrassa
, (105) Scleroteium ● Rolfushi (Scle)
rOtiunlrOlfsii), (100 Aspe J
Aspergillus sp., (107
) Chrysosporium lignorum (ChrysOspO
riurr] 11gn0run1), (108) Penicillium notatum (PenicilliunlnOt
atLlrr%), (109) Pyricularia Oryzae (i{) Fungi; as those originating from Basidiomycetes (1) Collybiavelti-Pes,
(2) Coprinus scleroteigenus (COPrin
(3) HydIlUnlhennings
ii), (4) Irpex lacteus (Irpex
lacteus), (5) Polyporus sulfurois (
POlyPOrLlSsulfhr-Eus), (6)
Polyporus betrois (POlypO-Rusbet)
reus), (7) Polysteitus 0 Hilftus (P
Olystictushirfutus), (8) Trametesvitata, (
9) IrpexcOnsO
lus), Lentinus lepidois (Lent)
inuslepideus), POriavapOraria, FOmespinicOla, Lenzitestyra
cina), A4) Merlius 6 Lacrimance (Mer
uliuslacry-Man8), (to) Polyporus palstris (POly-POruspalstri)
s), (to) Polyporus Annosus (POlypOr
usarlrlOSUS), (17) Polyporus 0versicOlOr)
, (self)Polysteitus Sanguinois (POly
stictus sanguineus), σ9) POichi Riavailantii
, (to) Puccinia graminis (Pucciniagr)
aminis), 21) Trichloma Humosum (Tri
chOlOmafumOsum), (2 trichlomas 0
Nudoum (TrichOlOmanLldUη), 23
) Trametessanguinea (Trametessan)
guinea), Polyporus scubainichii FR. (POlyp Orusschweinitzii
FR. ), (25) Conidiophora cerebella (CO
(1) Cladophora rupestris, (2
) Ulvalactuca, (
3) Laminaria daigitata
igitata), (4) Rhodeimenia palmata (R
(h) Dymenia palmata) (k) As originating from lichens (1) Usneacae
eae), (2) Cladoniae
ceae), (3ν Parmaliaceae)
aceae), (4) Urnb
ilicariaceae) (1) Those originating from terrestrial plants include (1) tobacco, (2) pinea tuple stem (
Pineapple stem), (3) Acerpse-UdOplatanus stem (4) Kidney bean leaf, (5) Chard, (6
) Spinach, (7) Solanum dourcamara root (
(8) Western squash, (9) end of asparagus, (dairy) barley, (auto) malt The present invention can use, for example, the following commercially available cellulases using these various sources. (1) Cellulase AP (Cellulase AP) Amano Pharmaceutical Co., Ltd. (2) Cellulosin AP (CellulO
sinAP) Ueda Chemical Co., Ltd. (3) Cellulosin AC
(Cellj-10sinAC) Ueda Chemical Co., Ltd.
(4) Cellulase-0
n0zL1ka) Kinki Yakult Manufacturing Co., Ltd., (Pan6ella Se) Kinki Yakult Manufacturing Co., Ltd., (6) MacerOzyme
) Kinki Yakult Manufacturing Co., Ltd., (7) Mycellase (M
eicelase) Meiji Seika Co., Ltd., (8) Celluzyme Nagase Co., Ltd., (9) Solublesclase Sankyo Co., Ltd., Sankyo Co., Ltd. (Own) Cellulase A- 12-C(Cellul-A
seA-12-C) Takeda Pharmaceutical Co., Ltd., TOYO-Cellulase, Toyo Jozo Co., Ltd., Driseras
e) Kyowa Hakko Kogyo Co., Ltd., Luisam
yme) Luip Oldwerk
), (auto) Takamine cellulase (Takamine-
Cellulase) Chemistry Fabric Co., Ltd. (C
hemischeFabrik), Wallerstein-Cel
lulase) Sigma Chemicals (SignlaC)
(5) Cellulase type I (C
ellulaseType I) Sigma Chemicals (
SigmaChemicals, CellulaseServa, ServaLabOratOry,
11 Cellulase 36 (ROhmandHaas), Miles Cellulase 4,000 (MllesCeI)
luIase4, OOO) Miles,
G2OR&H Cellulase 35, 36, 38 Conc (R&H
HCellulase35,36,38CONC)PhilipMorris,Q
1. COm-Bizym Nysco Laboratory, Inc., Cellulase Manufacturer Chemicals, Inc., 2. 25) Cellulase (
Cell, 8e) Gist Procades (Gist-
BrOcades) The present invention is achieved by using these cellulases in combination with known detergent compositions. The content of cellulase is such that the enzymatic activity of cellulase is 0.0.
01 unit/M9 solid content (1 unit/M9 solid content =
1.0 from cellulose in 1 hour at 37°C and pH 5
Produces micromoles (μMOle) of glucose. ) or more is preferably contained in the composition in an amount of 0.01 to 70% by weight, more preferably 0.1 to 10% by weight. Alternatively, the content of cellulase is preferably such that the enzymatic activity of cellulase in the bath is 0.1 to 1000 units/l, more preferably 1 to 100 units/l. That is, the present invention comprises 0.01 to 70% by weight of a cellulase having a maximum enzyme activity of 0.001 unit/Mg solid content or more, 10% by weight or more of one or more surfactants, and an alkaline agent or an inorganic electrolyte. ~50% by weight,
This relates to a low phosphorus powder detergent composition for clothing containing a phosphate builder, which is characterized by containing other detergent ingredients, and has detergency against slimy stains on clothing due to the combination of cellulase. A low-phosphorus powder detergent for clothing with significantly improved properties is obtained. The various components other than cellulase will be explained below. [1] Surfactant 1) Straight chain or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 2) Straight chain or branched chain alkyl group or alkenyl group having an average carbon number of 10 to 20 with an average of 0.5 in one molecule
~8 moles of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide/propylene oxide = 0.1/9.9-9
．． Alkyl or alkenyl ether sulfate added in a ratio of 9/0.1 or in a ratio of ethylene oxide/butylene oxide = 0.1/9.9/0.1 3) Alkyl group or alkenyl having an average carbon number of 10 to 20 Alkyl or alkenyl sulfates having groups 4) Olefin sulfonates having an average of 10 to 20 carbon atoms in one molecule 5)
Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule 6) Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule 7) Average carbon number of 10 to
It has 20 alkyl or alkenyl groups, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, or butylene oxide in one molecule, or ethylene oxide/propylene oxide = 0.1/
At a ratio of 9.9 to 9.9/0.1 or ethylene oxide/butylene oxide = 0.1/9.9 to 9.9/
Alkyl or alkenyl ether carboxylic acid salt added at a ratio of 0.1 8) α-sulfo fatty acid salt or ester represented by the following formula [wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z is a counter ion] It is an ion. R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ] Here, the counter ions of the anionic surfactant include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium,
Examples include ammonium ions and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (eg, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). 9) Amino acid type surfactant represented by the following general formula (where R1 is an alkyl or alkenyl group having 8 to 24 carbon atoms, R2 is hydrogen or an alkyl group having 1 to 2 carbon atoms, R3 is
represents an amino acid residue, and X represents an alkali metal or alkaline earth metal ion. ) (Rl, R2 and R4 represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.)↓T2↓B3 (R2, R3 and X are as described above. R5 is β-hydroxyalkyl having 6 to 28 carbon atoms or β
- represents a hydroxyalkenyl group. ) (R3, R5 and '+m'=3, n'=1~2) Waterfall 2 Alkyl (
or alkyl phosphate ester (R' is as described above,
n″+m″=3, n″=1~3) Waterfall 3 Alkyl (or alkenyl) phosphoric acid styrene salt (R′, n″, m″ are as described above, M is Na, K, Ca)
2011) A sulfonic acid type amphoteric surfactant represented by the following general formula (where R, , is a carbon number of 8 to 24
an alkyl or alkenyl group, R,2 is an alkyl group having 1 to 4 carbon atoms, Rl is an alkyl group having 1 to 5 carbon atoms, R,
4 represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. ) (Here, Rll and Rl4 are as described above, Rl5,
R and 6 represent an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms. ) (Here, Rll and Rl4 are as described above. n1 represents an integer of 1 to 20.) 12) A petaine type amphoteric activator represented by the following general formula (here, R2l is a carbon number of 8
~24 alkyl or alkenyl or β-hydroxyalkyl or β-hydroxyalkenyl group, R22 represents an alkyl group having 1 to 4 carbon atoms, and R23 represents an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms. ) (Here, R2l and R2, are as described above. N2 represents an integer of 1 to 20.) (Here, R2l and R23 are as described above. R24 represents a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms. )13) Average carbon number 10-20
Polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group of 1 to 20 moles of ethylene oxide 14) Average carbon number 6 to 12
polyoxyethylene alkyl phenyl ether anole having an alkyl group of 1 to 20 moles of ethylene oxide 15) having an alkyl group or alkenyl group having an average carbon number of 10 to 20, and 1 to 20 moles of propylene oxide 16) Polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having an average of 1 to 20 moles of butylene oxide added 17) An average carbon number of 10 A nonionic surfactant having ~20 alkyl or alkenyl groups and adding a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (ratio of ethylene oxide and propylene oxide or butylene oxide) is 0.1/9.9~9.9
/0.1) 18) Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following general formula [wherein R'11 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R'12 is H or CH3, N3 is an integer of 1 to 3, and M3 is an integer of O to 3. [19] Sucrose fatty acid ester consisting of a fatty acid with an average carbon number of 10 to 20 and sucrose 20) Fatty acid glycerin monoester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin 21) Alkylamine oxide represented by the following general formula [In the formula, R'13 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R'14, R', and 5 are alkyl groups having 1 to 3 carbon atoms. [22) A cationic surfactant represented by the following general formula (wherein at least one of R'1, R'2, R'3, and R'4 is an alkyl or alkenyl group having 8 to 24 carbon atoms,
Others represent an alkyl group having 1 to 5 carbon atoms. X' indicates halogen. ) (where R'1, R'2, R
'3 and X' are as described above. ) (Here, R'1, R/2, and X' are as described above. R'5 is an alkylene group having 2 to 3 carbon atoms, and N4 is an alkylene group having 1 to 20 carbon atoms.
indicates an integer. ) The composition contains at least 10% by weight of one or more of the above surfactants. Preferred surfactants include 1), 2), 3), 4)
, 5), 6), 11) A2, 12) Waterfall 1, 13),
14), 15), 17), and 18). [2] Divalent metal ion scavenger 1 of the following various alkali metal salts and alkanolamine salts
It is also possible to contain O to 50% by weight of a species or two or more builder components. 1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc. 2) Ethane-1,1 diphosphonic acid, ethane-1,2 triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethane-1,1,
2-totophosphonic acid, ethane-1,2 dicarboxy-1
, 2-diphosphonic acid, methanehydroxyphosphonic acid and the like. 3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Phosphonocarboxylic acid salts such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid. 4) Amino acid salts such as aspartic acid and glutamic acid. 5) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, and diethylenetriaminepentaacetate. 6) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-di Isobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-decanoic acid monoethylene crosslink copolymer, monomaleic anhydride Vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, maleic anhydride and poly-β-ketocarboxylic acid derived from carbon monoxide, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, Malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone monovinyl acetate copolymer, 1-butene-2,3,4-trigger 25 rubonic acid- Itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid with quaternary ammonium groups, Cie monoisomer of epoxysuccinic acid, poly[N,N-bis(carboxymethyl)acrylamide], poly(O3)
Polymer electrolytes such as starch succinic acid or maleic acid or terephthalic acid ester, starch phosphate ester, dicarboxy starch, dicarboxymethyl starch, cellulose succinate ester, etc. 357) Non-dissociable polymers such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, cold water soluble urethanized polyvinyl alcohol. 8) Diglycolic acid, oxydisuccinic acid, Cal-40-boxymethyloxysuccinic acid, cyclopentane-1,2,3
, 4-tetracarboxylic acid, tetrahydrofuran-1,2
, 3,4-tetracarboxylic acid, tetrahydrofuran-2
, 2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, carboxymethylated products such as raffinose, carboxymethylated pentaerythritol, carboxymethylated gluconic acid, polyhydric alcohols or sugars. Condensates of maleic anhydride or succinic anhydride, condensates of oxycarboxylic acids and maleic anhydride or succinic anhydride, benzene polycarboxylic acids represented by mellitic acid, ethane-1,1,2,2
-tetracarboxylic acid, ethene-1,1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-
1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid,
Organic acid salts such as gluconic acid and CMOSl builder. 9) Aluminosilicate waterfall A crystalline aluminosilicate represented by the linear formula (in the formula,
M' is an alkali metal atom, M'' is an alkaline earth metal atom exchangeable with calcium, x', y', and w' are the number of moles of each component, and are generally 0.74x'41. 5
, 0.8oty′? 6. 冫 is any positive number. ) As the cleaning agent builder, those represented by the following general formula are particularly preferred. (Here, n represents a number from 1.8 to 3.0, and w represents a number from 1 to 6.) An amorphous aluminosilicate represented by a reduced cubic formula (wherein M represents a sodium and/or potassium atom) Hail,
X, y, w represent the number of moles of each component within the following microvalue range) , Z, and ω represent the number of moles of each component within the following numerical range. [3] Alkaline agent or inorganic electrolyte Furthermore, one or two of various alkali metal salts of the following as an alkaline agent or inorganic electrolyte. The composition can contain 1 to 50% by weight, preferably 5 to 30% by weight of silicates, carbonates, sulfates, and organic alkali agents such as triethanolamine, diethanolamine, and monoethanol. amines, triisopropanolamine, etc.
[4] Anti-restaining agent Furthermore, one or more of the following compounds can be contained in the composition in an amount of 0.1 to 5% as an anti-staining agent. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.
Among these, the combination of carboxymethyl cellulose or polyethylene glycol with the cellulase of the present invention has a synergistic effect in removing mud stains. In order to avoid decomposition of carboxymethylcellulose by cellulase in detergents, it is desirable to blend carboxymethylcellulose in the form of granulation or coating. [5] Bleach agents such as sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, and/or bleaching agents such as sulfonated phthalocyanine zinc salt, aluminum salt, etc. The combined use of sensitive bleaching dyes and the like with the cellulase of the present invention further improves the cleaning effect. [6] Enzymes (Enzymes that perform their original enzymatic action during the cleaning process.) Classified based on enzyme reactivity, they are hydrolases, hydrolases, oxidoreductases, desmolases,
Examples include transferases and isomerases, both of which are applicable to the present invention. Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases. Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, BPNlpapain, promelin, carboxypeptidase A and B1 aminopeptidase, aspergylopeptidase A and B. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases. Carbohydrases other than cellulases include maltase, satucarase, amylase, pectinase, lysozyme, α-glycosidase, and β-glycosidase. [7] Blurring agents and fluorescent dyes Various blurring agents and fluorescent dyes can be added as necessary. For example, the following structure is recommended: [8] Anti-caking agent In the case of a powder detergent, the following anti-caking agent may also be blended. para-toluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, calcium-silicate (e.g. TOhnsMan
vill's microcell, etc.), calcium carbonate, magnesium oxide, etc.

[9] Inhibitors of factors that inhibit cellulase activity Cellulase activity may be inactivated by the presence of ions and compounds such as copper, zinc, chromium, mercury, lead, manganese, and silver. Various metal chelating agents and metal precipitating agents are effective against these inhibitory factors. Examples thereof include the divalent metal ion scavenger mentioned in optional component [2], magnesium silicate, magnesium sulfate, and the like. Cerbiose,
Glucose and gluconolactone are also sometimes inhibitors. It is necessary to avoid the coexistence of these types of saccharides and cellulases as much as possible, or, if their coexistence cannot be avoided, to avoid direct contact between these saccharides and cellulases, such as a method of coating each of them. Strong chelating agents such as ethylenediaminetetraacetate, anionic surfactants, and cationic surfactants can also be inhibitors in some cases. The coexistence of these substances and cellulase is also possible by devising manufacturing techniques such as tableting and coating methods. The above-mentioned anti-inflammatory agents or methods can be combined or applied depending on the case. [10] Senolyse activator Depending on the type of cellulase, protein, cobalt and its salts, calcium and its salts, potassium and its salts, sodium and its salts, mannose, monosaccharides such as xylose are allowed to coexist. This activates cellulase and dramatically improves the cleaning effect. [10 Antioxidant tertiary-butylhydroxytoluene 4,4'-butylidenepis-(61-tert-butyl-3-methylphenol), 2
, 2'-butylidene bis-(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis-(4-hydroxyphenyl) ) Antioxidants such as cyclohexane. Next, the present invention will be specifically explained with reference to Examples. Note that the percentages in the examples are based on weight unless otherwise specified. Example 1 It is shown that among various enzymes, only cellulase is effective against artificially contaminated cotton cloth contaminated with mud. 2) Muddy contaminated cloth (artificially contaminated cloth) Kanuma gardening Akadama soil was dried at 120°C ± 5°C for 4 hours, then ground, and passed through 150 mesh (100 ttm).
After drying for 2 hours at ±5°C, ±1509 is dispersed in 10001 perculane, and a #2023 gold cloth is brought into contact with the liquid and brushed to remove the dispersion liquid and remove excess dirt (Japanese Patent Laid-Open No. 55-26473). . A test piece of 10CTIL×10CTfL was prepared and used for the experiment. 3) Cleaning conditions, cleaning method, and evaluation method 4) Dissolve detergent in DH hard water to prepare 0.133% detergent aqueous solution 11. Add 5 muddy cotton artificially contaminated cloths to a detergent solution,
After standing at 0° C. for 2 hours, the detergent solution and the artificially contaminated cloth were transferred as they were to a stainless steel beaker for Tergotometer 1, and washed with stirring at 100 rpm at 20° C. for 10 minutes in Tergotometer 1. After rinsing under running water, it was iron pressed and subjected to reflectance measurement. The cleaning rate was calculated according to the following formula; the reflectance at 460 mμ of the original cloth before cleaning and the contaminated cloth before and after cleaning was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (support) was calculated using the following formula. ) was calculated. Note that the pH of the detergent aqueous solution before washing was 10.6.

Claims (1)

[Claims] 1 0.01 to 70% by weight of cellulase with a maximum enzyme activity of 0.001 unit mg solid content or more, 10% by weight or more of one or more surfactants, and 1 to 50% by weight of an alkaline agent or inorganic electrolyte. 1. A low-phosphorus powder detergent composition for clothing containing a phosphate builder, comprising: and other detergent ingredients.