CN1224447A - Liquid laundry detergent compositions comprising cotton soil release polymers - Google Patents
Liquid laundry detergent compositions comprising cotton soil release polymers Download PDFInfo
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- CN1224447A CN1224447A CN 97196085 CN97196085A CN1224447A CN 1224447 A CN1224447 A CN 1224447A CN 97196085 CN97196085 CN 97196085 CN 97196085 A CN97196085 A CN 97196085A CN 1224447 A CN1224447 A CN 1224447A
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Abstract
Liquid laundry detergent compositions comprising water soluble and/or dispersible, modified polyamines having functionalized backbone moieties which provide cotton soil release benefits in combination with selected non-cotton soil release agents.
Description
Invention field
The present invention relates to contain the liquid laundry detergent compositions of water-soluble and/or dispersible modified polyamine, said polyamine has with the non-cotton stain remover of selecting and combines the functionalization main chain with cotton soil-removing action.
Background technology of the present invention
At family and technical fabric treatment process, be known in the art as doing washing, in the warm air drier for clothes, extensively adopting stain remover among dry fabric or the like.Various stain removers are suitability for industrialized production, and is used in usually in detergent composition, fabric softener antistatic article and the composition.This class soil release polymer generally contains oligomer or polyester " main chain ".
When Tallow, beef, oil or similar hydrophobic stain expansion formation coherent film, and when therefore being not easy to remove in the water-based washing process, soil release polymer is very effective to polyester or other synthetic textiles usually.A lot of soil release polymers are to " mixings " fabric, that is to say that the fabric to the mixture that comprises cotton and synthetic materials does not have unusual effect, and cotton products are had very little or do not have effect.It is the mixture that the main chain of polyester soil release polymers generally contains terephthalate residue and inferior ethoxyl or inferior propoxy-polymer unit that many stain removers have the reason of affinity to synthetic textiles; They are the identical or close analogues that contain the Polyester Fibers of synthetic textiles.The analog structure of this stain remover and synthetic textiles produces inherent avidity between these compounds.
Big quantity research in this field has improved the polyester soil release agent greatly and has produced to have and enhance product performance and the efficient of the material of workability.Change main polymer chain and select suitable capping group to produce various polyester soil release polymers.For example, blocking modification, as adopting the sulphur aryl moiety, isethionic acid ester deutero-end-blocking unit has cheaply particularly improved the consistency of the binder component of the scope of solubleness and these polymkeric substance, and has not reduced clean effect.Many polyester soil release polymers can be mixed with liquid and solid (as particle) washing composition now.
Different with polyester soil release polymers, the oligopolymer or the polymer materials of preparation simulation cotton knot structure are not produced the polymkeric substance of removing cotton oil.Although cotton and polyester textile constitutes their chemical property difference by long chain polymer.Cotton contains the cellulosic fibre that the anhydroglucose unit that connected by 1～4 key constitutes.These join sugar chain, and to make gossypin be feature with the glycan, and polyester soil release polymers generally is the combination of terephthalate and oxygen ethylidene/oxygen propylidene residue.These difference in the composition cause cotton different with the textile properties of trevira.Cotton is hydrophilic with respect to polyester.Polyester is hydrophobic and adsorbed oil or Tallow, beef spot, " dry-cleaning " at an easy rate.Importantly the terephthalate of trevira and inferior ethoxyl/inferior propoxy-main chain does not have reflecting point, and as the hydroxylic moiety of cotton, it is had an effect with mode different with synthetic products and spot.Many cotton spots become " fixing " and can only solve by bleached woven fabric.
So far, the effective cotton stain remover that is used in the detergent for washing clothes of exploitation is inevitable.The convention that some attempt to adopt the structure of the structure that makes soil release polymer and fabric to match has produced decisive effect when the successful methods in polyester soil release polymers field still is being used for the cotton fabric stain remover.Proof adopts methylcellulose gum, and the cotton glycan of oligomer units that promptly has modification is more effective to polyester comparison cotton.
For example, disclosed UK1314897 disclosed a kind of Vltra tears material on April 26th, 1973, and it is used to prevent that wet spot from depositing once more and improve the removal effect of spot on the fabric that is washed.Though this material has certain effect to polyester and mixed goods, the disclosure points out that these materials can not produce required effect to cotton fabric.
Be used for aspect the stain remover of cotton fabric other to attempt general form that adopts be to make a kind of matrix and glycan main polymer chain react the chemical structure that forever changes cotton fabric itself in production.For example the Kearney US3897026 that obtains power discloses the fabric web material with improved decontamination and antifouling property, and it is to produce by the hydroxylic moiety reaction of ethylidene maleic anhydride copolymers and cotton polymkeric substance.A distinct disadvantage of this method is that the needed wetting ability of cotton fabric has been changed greatly by this technology.
Impermanent decontamination is handled or effort had just been done in arrangement in the past.It is protective layer used in the composition of cotton fabric that the US3912681 that Dickson obtains power provides a kind of impermanent decontamination that will contain the polycarboxylic acid ester polymer.But this material must use under less than 3 pH, be a kind of human consumer of being unsuitable for use and with general pH greater than the inconsistent method of 7.5 detergent for washing clothes.
The US3948838 that people such as Hinton obtain power has put down in writing high molecular (500,000 to 1,500, the 000) polyacrylate polymers that is used for decontamination.These materials can preferably use with the processing of other fabric, for example durable-press fabrics reagent, for example formaldehyde.This method also is not suitable for the human consumer and is used for general washing machine.
The US4559056 that people such as Leigh obtain power discloses a kind of method that adopts a kind of compositions-treated cotton goods or synthon, and said composition contains organopolysiloxane elastomerics, organopolysiloxane oxyalkylene copolymers linking agent and siloxanes vulcanization accelerator.The known organopolysiloxane oligopolymer of those skilled in the art can be used as suds suppressor.
Other stain remover of mixture that does not contain terephthalate and polyoxyethylene/propylene is by people such as Rupert disclosed ethylidene hexanolactam resin in US4579681 and 4614519.The effect of these disclosed ethylidene hexanolactam materials is confined to the mixture of polyester textile, cotton and polyester and the cotton fabric that becomes hydrophobic with finishing composition.
The example of oxyalkylated polyamine and quaternised alkoxylate polyamine is disclosed in the european patent application 206513, and they are applicable to as dirt dispersant, can not be used as cotton stain remover but disclose them.In addition, these materials do not contain nitrogen oxide, and this is the key improvements that the present invention carries out polyamine, and it is the component that improves the bleach stability that present disclosed compound had.
Found unexpectedly that now the effective stain remover that is used for cotton goods can be prepared by the polyamine of some modifications.In a single day this resultant composition that does not reckon with is used on just synthetic and the synthetic-cotton mixed goods, just can provide soil-removing action effectively.When cotton soil release polymers of the present invention is used in combination with non-cotton stain remover, all types of fabrics all there is clean effect.
The invention provides liquid laundry detergent compositions, it contains non-ionic and anionic tensio-active agent, together with non-cotton soil release polymers and cotton stain remover of the present invention.Such combination results liquid laundry detergent compositions, it all has clean effect to all fabrics.The viscosity of this liquid washing agent can have multiple and can comprise enriched material, dumpable " finished product " washing composition or light-duty fabric pretreating agent.
Background technology
Except above-mentioned document, following document discloses the polyamine of various soil release polymers or modification; Connor obtains the US4548744 of power on October 22nd, 1985; Vander Meer obtains the US4597898 of power on July 1st, 1986; Maldonado etc. obtain the US4877896 of power on October 31st, 1989; Vander Meer obtains the US4891160 of power in January 2 nineteen ninety; Maldonado etc. obtain the US4976879 of power in December 11 nineteen ninety; Gosselink obtains the US5415807 of power in May 16 nineteen ninety-five; Marco etc. obtain the US4235735 of power on November 25th, 1980; At disclosed UK1537288 on December 29th, 1978; At disclosed UK1498520 on January 18th, 1978; At disclosed WO95/32272 on November 30 nineteen ninety-five; Obtain the German patent DE 2829022 of power on January 10th, 1980; At disclosure JP06313271 in disclosed day of on April 27th, 1994.
The general introduction of invention
The present invention relates to have the liquid laundry detergent compositions of cotton clean effect, it contains:
A) at least about the anionic detergent tensio-active agent of 0.01% weight, it is selected from alkyl-sulphate, alkyl alkoxylated vitriol and their mixture;
B) at least about the non-cotton stain remover of 0.01% weight, it is selected from the multipolymer of terephthalate, and it contains:
ⅰ) main chain contains:
A) at least one has the part of following general formula:
B) at least one has the part of following general formula:
R wherein
9Be C
2-C
6Wire alkylidene group, C
3-C
6The alkylidene group of collateralization, C
5-C
7Cyclic alkylidene and their mixture; R
10Be independently selected from hydrogen or-L-SO
3 -M
+Wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group-poly-(oxyalkylene group) and their mixture; M is hydrogen or salt-forming cation; I is 0 or 1 number;
C) chain portion of the formed ester of at least one trifunctional;
D) at least one 1,2-oxyalkylene group oxygen part; With
ⅱ) one or several end-blocking unit, it contains:
A) general formula is (MO
3S) (CH
2)
m(R
11O)
n-ethoxylation or propenoxylated hydroxyethanesulfonic acid salt or ethoxylation or propenoxylated hydroxypropanesulfonic acid salt unit, wherein M is a salt-forming cation, R
11Be ethylidene or propylidene or their mixture, m is 0 or 1, and n is 1 to 20;
B) C (C of general formula-(O)
6H
4) (SO
3 -M
+) sulfo group aroyl unit, wherein M is a salt-forming cation;
C) poly-(oxyethylene group) oxygen monoalky lether unit of modification, general formula is R
12O (CH
2CH
2O)
k-, R wherein
12Contain 1 to 4 carbon atom, k from about 3 to about 100; With
D) ethoxylation or propenoxylated phenolsulfonate end-blocking unit, its general formula is MO
3S (C
6H
4) (OR
13)
nO-, wherein n is 1 to 20; M is a salt-forming cation; R
13Be ethylidene, propylidene and their mixture;
Sulfonated oligomer ester composition contains preformed sulfonated products, is the wire ester oligomer basically, and every mole of said wire ester oligomer contains:
ⅰ) 2 moles of terminal units, wherein about 1 mole to 2 moles said terminal units are to be produced by the unsaturated component of the olefinic that is selected from vinyl carbinol and methylallyl alcohol, and any remaining said terminal units other unit that is said wire ester oligomer;
ⅱ) about 1 mole to about 4 moles nonionic hydrophilic unit, said hydrophilic unit is to be produced by oxyalkylene, said oxyalkylene contains 50% to 100% the oxyethane of having an appointment;
ⅲ) about 1.1 moles are arrived about 20 moles repeating unit by the generation of aryl dicarbapentaborane component, wherein said aryl dicarbapentaborane component contains 50% to 100% the terephthalic acid dimethyl esters of having an appointment, and the repeating unit that is produced by said terephthalic acid dimethyl esters is a terephthaloyl; With
ⅳ) about 0.1 mole to about 19 moles by being selected from C
2-C
4The repeating unit that the diol component of alcohol produces;
The sulfonation degree of wherein said sulfonation oligomer ester component is that said terminal units is by ⅴ) chemical modification, wherein ⅴ) be about 1 mole to about 4 moles of terminal units substituting groups, its general formula is-SO
xM, wherein x is 2 or 3, said terminal units substituting group is by being selected from HSO
3M, wherein M is that the hydrosulphite component of the group of general water-soluble cationic produces;
End-blocking terephthalic acid ester copolymer has following general formula:
X[(OCH
2CH
2)
n(OR
5)
m][(A-R
1-A-R
2)
u(A-R
3-A-R
2)
v]-
A-R
4-A[(R
5O)
m(CH
2CH
2O)
n]X
Wherein each A partly is selected from:
With their combination, each R
1Part is selected from 1,4-phenylene and itself and 1, the combination of 3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2 '-biphenylene, 4,4 '-biphenylene, C
1-C
8Alkylidene group, C
1-C
8Alkenylene and their mixture, R
2Part is selected from the ethylidene part, contains C
1-C
4The ethylidene of the replacement of alkyl, alkoxy substituent and their mixture; R
3Part is the C that replaces
2-C
18The alkylene part, its have at least one-CO
2M ,-O[(R
5O)
m(CH
2CH
2O)
n] X or-A[(R
2-A-R
4-A)] w[(R
5O)
m(CH
2CH
2O)
n] the X substituting group; R
4Part is R
1Perhaps R
3Part or their mixture; A R
5Be C
1-C
4Alkylidene group or part-R
2-A-R
6, R wherein
6Be C
1-C
12Alkylidene group, alkenylene, arylidene or alkyl arylene part; M is hydrogen or water-soluble cationic; X is C
1-C
4Alkyl; The value of m and n will make part-(CH
2CH
2O)-contain at least about 50% weight of portions [(R
5O)
m(CH
2CH
2O)
n], as long as work as R
5Be part-R
6-A-R
6In-time, m is 1; N is at least about 10; The value of u and v will make u+v's and be about 3 to about 25; W is 0 or is at least 1; And when w was at least 1, the value of u, v and w will make u+v+w's and be about 3 to about 25; With their mixture;
C) at least about the cotton stain remover of the polyamine of the water-soluble or dispersible modification of 0.01% weight, this stain remover contains the polyamine main chain with following general formula:
Polyamine general formula V with modification
(n+1)W
mY
nThe polyamine main chain that Z or general formula are following:
Polyamine general formula V with modification
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and said polyamine main chain had before modification greater than about 200 daltonian molecular weight, wherein
ⅰ) the V unit is the end group unit with following general formula:
Or
Or
ⅱ) the W unit is the backbone units with following general formula:
Or
Or
ⅲ) the Y unit is the chain unit with following general formula:
Or
Or
With
ⅳ) the Z unit is the end group unit with following general formula:
Or
Or
Wherein main chain connection R unit is selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12Two alkyl arylenes ,-(R
1O)
xR
1,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
y-R
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-and their mixture; R wherein
1Be C
2-C
3Alkylidene group and their mixture; R
2Be hydrogen ,-(R
1O)
xB and their mixture; R
3Be C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and their mixture; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12Two alkyl arylenes ,-C (O)-,-C (O) NHR
6-NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-, CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1-OCH
2CH (OH) CH
2-and their mixture; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Arylalkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
p-CO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M)-CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3With their mixture; As long as when any E unit of a nitrogen is hydrogen, said nitrogen neither nitrogen oxide; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M and their mixture; M is hydrogen or the water-soluble cationic that is enough to satisfy charge balance; X is a water soluble anion; M is 4 to about 400 number; N is 0 to about 200 number; P is 1 to 6 number, and q is 0 to 6 number; R is 0 or 1; W is 0 or 1; X is 1 to 100 number; Y is 0 to 100 number; Z is 0 or 1; With
D) balance carrier and additive component; Wherein when with 10% determination of aqueous solution, the pH of said composition is about 7.2 to about 8.9.
All percentage ratio, ratio and share all are meant weight at this, unless other explanation is arranged.All temperature all be Celsius (℃), unless other explanation is arranged.The relevant portion of the file of all references can be in conjunction with as a reference.
Detailed description of the present invention
The present invention relates to be applicable to the liquid laundry detergent compositions of the mixture of cotton, non-cotton or cotton and non-cotton fabric.This liquid laundry detergent compositions can randomly contain albic material.
The preferred liquid laundry detergent compositions of the present invention contains some anion surfactants (preferably combining with nonionogenic tenside) and selected non-cotton stain remover, and when it was used in combination with cotton soil release polymers of the present invention, it provided improved cleaning and clean effect to all fabrics.The preferred liquid laundry detergent compositions of the present invention contains following component:
The anionic detergent tensio-active agent
Composition of the present invention preferably contains at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to 95%, the anionic detergent tensio-active agent of 1% to 80% weight most preferably from about, it is selected from alkyl-sulphate, alkyl-alkyl alkoxy sulfate and their mixture.Alkyl sulfate surfactant, uncle or secondary alkyl are the spendable important analog anion surfactants of the present invention.The general formula of alkyl-sulphate is ROSO
3M, wherein R C preferably
10-C
24Alkyl, preferred alkyl straight chain or side chain chain or have C
10-C
20The hydroxyalkyl of moieties, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is hydrogen or water-soluble cationic, as alkali metal cation (as sodium, potassium, lithium), replace or unsubstituted ammonium cation, as methyl-, dimethyl-and trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine, with by alkanolamine, positively charged ion that produces as thanomin, diethanolamine, trolamine and their mixture or the like.C
12-C
16Alkyl chain generally be preferred for lower wash temperature (as being lower than about 50 ℃) and C
16-C
18Alkyl chain is preferred for higher wash temperature (50 ℃ according to appointment).
Alkyl alkoxylated sulfate surfactant is another kind of preferred anionic surfactants tensio-active agent.These tensio-active agents are water miscible salt or acid, and general general formula is RO (A)
mSO
3M, wherein R is unsubstituted C
10-C
24Alkyl or have C
12-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A is oxyethyl group or propoxy-unit, m is the integer greater than 0, generally between about 0.5 and about 6, more preferably from about between 0.5 and 3, M is hydrogen or water-soluble cationic, and they can be the ammonium cations of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium ion or replacement for example.It is also conceivable that the vitriol and the propenoxylated vitriol of alkyl of alkyl ethoxylated.The object lesson of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium and quaternary ammonium cation, as tetramethyl-ammonium, lupetidine father-in-law with by alkanolamine, as Monoethanolamine MEA BASF, diethanolamine and trolamine and their mixture deutero-positively charged ion.Representational tensio-active agent is C
12-C
18Alkyl polyethoxylated (1.0) vitriol, C
12-C
18Alkyl polyethoxylated (2.25) vitriol, C
12-C
18Alkyl polyethoxylated (3.0) vitriol and C
12-C
18Alkyl polyethoxylated (4.0) vitriol, wherein M is selected from sodium and potassium usually.
The nonionic detergent surfactant
Composition of the present invention preferably also contains at least about 0.01%, and preferably at least 0.1%, more preferably from about 1% to 95%, the anionic detergent tensio-active agent of 1% to 80% weight most preferably from about.The preferred anionic surfactants tensio-active agent, as contain the C of so-called narrow peak alkylethoxylate
12-C
18Alkylethoxylate (" AE ") and C
6-C
12Alkylphenol alcoxylates (particularly ethoxylate and blended oxyethyl group/propoxy-), C
6To C
12The block oxyalkylene condenses of alkylphenol, C
8-C
22The oxyalkylene condenses of alkanol and oxyethane/propylene oxide block polymer (Pluronic
TM-BASF Corp.), and semi-polar nonionogenic tenside (as amine oxide and phosphine oxide) may be used to composition of the present invention.The tensio-active agent of these types is disclosed in Laughlin etc. in a large number and obtains among the US3929678 of power on December 30th, 1975, its at this in conjunction with as a reference.
Alkyl polysaccharide, this class material that for example is disclosed among the US4565647 (at this in conjunction with as a reference) of L1enado also can be a preferred nonionic in the composition of the present invention.
Further preferred nonionic is the polyhydroxy fatty acid amide with following general formula:
R wherein
7Be C
5-C
31Alkyl, preferred straight chain C
7-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl, most preferably straight chain C
11-C
15Alkyl or alkenyl or their mixture; R
8Be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, preferable methyl or ethyl, more preferably methyl.Q has to bring to few 3 the polyhydroxy alkyl parts that directly are connected the wire alkyl chain of the hydroxyl on the chain, perhaps its alkoxy derivatives; Preferred alkoxyl group is oxyethyl group or propoxy-and their mixture.Preferred Q is prepared in reductive amination process by reducing sugar.Preferred Q is sugar alcohol base section (glycityl).Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.The single sugar that can adopt high dextrose maize treacle, high sinistrose maize treacle and high malt sugar maize treacle and list above as raw material.These maize treacle can generate the mixture of the sugar component that is used for Q.Can think that this never gets rid of other proper raw material.Q more preferably is selected from-CH
2(CHOH)
nCH
2OH ,-CH (CH
2OH) (CHOH)
N-1CH
2OH ,-CH
2(CHOH)
2-(CHOR ') be CH (CHOH)
2OH and its oxyalkylated derivative, n is from 3 to 5 integer, comprises 3 and 5, R ' is hydrogen or ring-type or fatty monose.The most preferably substituting group of Q part is the sugar alcohol base, and wherein n is 4, particularly-and CH
2(CHOH)
4CH
2OH.
R
7CO-N＜can be is coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, tallow acid amides etc. for example.
R
8Can be for example methyl, ethyl, propyl group, sec.-propyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl.
Q can be 1-deoxidation glucityl, 2-deoxidation fructityl, 1-deoxidation maltityl, 1-deoxidation lactityl, 1-deoxidation galactityl, 1-deoxidation mannityl, 1-deoxidation maltotriotityl or the like.
Tensio-active agent to the special needs of this class of being used for composition of the present invention is alkyl-N-methyl glucose amide, the i.e. compound of above-mentioned general formula, wherein R
7Be alkyl (preferred C
11-C
13), R
8Be methyl, Q is 1-deoxidation glucityl.
Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, as C
10-C
18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low foamy.Can adopt C
10-C
20Conventional soap.High if desired foam can adopt collateralization C
10-C
16Soap.
Based on purpose of the present invention, other detergent surfactant described below also can be used in the liquid laundry detergent compositions.
Non-cotton soil release polymers
The non-cotton soil release polymers that can be used in the liquid laundry detergent compositions of the present invention is as follows.
Preferred non-cotton stain remover-A.The preferred non-cotton soil release polymers that is applicable to liquid laundry detergent compositions of the present invention contains:
A) main chain contains:
ⅰ) at least one has the part of following general formula:
ⅱ) at least one has the part of following general formula:
R wherein
9Be C
2-C
6Wire alkylidene group, C
3-C
6The alkylidene group of collateralization, C
5-C
7Cyclic alkylidene and their mixture; R
10Be independently selected from hydrogen or-L-SO
3 -M
+Wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group poly-(oxyalkylene group) and their mixture; M is hydrogen or salt-forming cation; I is 0 or 1 number;
A ⅲ) chain portion of the formed ester of at least one trifunctional;
ⅳ) at least one 1,2-oxyalkylene group oxygen part; With
B) one or several end-blocking unit, it contains:
ⅰ) general formula is (MO
3S) (CH
2)
m(R
11O)
n-ethoxylation or propenoxylated hydroxyethanesulfonic acid ester or ethoxylation or propenoxylated hydroxypropanesulfonic acid ester units, wherein M is a salt-forming cation, as sodium or tetra-allkylammonium, R
11Be ethylidene or propylidene or their mixture, m is 0 or 1, and n is 1 to 20;
ⅱ) C (the C of general formula-(O)
6H
4) (SO
3 -M
+) the sulfo group aroyl, wherein M is a salt-forming cation;
ⅲ) poly-(oxyethylene group) oxygen monoalky lether unit of modification, general formula is R
12O (CH
2CH
2O)
k-, R wherein
12Contain 1 to 4 carbon atom, k from about 3 to about 100; With
ⅳ) ethoxylation or propenoxylated phenolsulfonate end-blocking unit, its general formula is MO
3S (C
6H
4) (OR
13)
nO-, wherein n is 1 to 20; M is a salt-forming cation; R
13Be ethylidene, propylidene and their mixture.
The preferred non-cotton soil release polymers of this class of the present invention has following general formula:
[(end group) (R
4)
t] [(A-R
1-A-R
2)
u(A-R
1-A-R
3)
v(A-R
1-A-R
5)
w-A-R
1-A-] [(R
4)
t(end group)] wherein A be carboxyl connection portion with following general formula,
R
1Be arylidene, preferred 1, the 4-phenylen moiety, general formula is as follows:
Like this as A unit and R
1The unit is at general formula A-R
1When coupling together among-the A, they form has the terephthalate unit of following general formula:
R
2The unit is inferior ethoxyl or 1, the inferior propoxy-of 2-.R
2The unit combines the (A-R that formation has following general formula with the terephthalic acid ester moiety
1-A-R
2) unit:
Wherein R ' and R " be hydrogen or methyl, as long as R ' and R " not methyl simultaneously.
R
3The unit is a chain portion of the formation ester of trifunctional, and it has following general formula:
Preferred R
3The unit comprises the glycerine part, and it is positioned on the soil release polymer main chain so that the side chain position to be provided.Work as R
3The unit combines with the terephthalic acid ester moiety when forming the main polymer chain unit, for example (A-R
1-A-R
3)-A-R
1-A unit, these unit have following general formula:
Perhaps general formula:
One of them terephthalate residue becomes (A-R
1-A-R
3) a unitary part, the while, second terephthalate contained the part of another backbone units, for example (A-R
1-A-R
2) unit, (A-R
1-A-R
5) unit, A-R
1-A-[(R
4)
t(end group)] unit or second (A-R
1-A-R
3) unit.The 3rd functional group is the beginning of side chain, generally also be connected on the terephthalate residue, and also be (A-R
1-A-R
2) unit, (A-R
1-A-R
5) unit, A-R
1-A-[(R
4)
t(end group)] unit or another (A-R
1-A-R
3) a unitary part.
Contain glycerine unitary " chain portion of the formation ester of trifunctional " R
3The segmental example of unitary soil release polymer is to have following general formula:
R
4The unit is R
2, R
3Or R
5The unit.
R
5The unit has following general formula:
R wherein
9Be C
2-C
6Wire alkylidene group, C
3-C
6The alkylidene group of collateralization and their mixture; Preferred R
10Be selected from separately hydrogen or-L-SO
3 -M
+Wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group poly-(oxyalkylene group) and their mixture; M is hydrogen or salt-forming cation; I is 0 or 1 number;
R
9Unitary each carbon atom is by R
10The unit replaces, R
10Be selected from separately hydrogen or-L-SO
3 -M
+As long as no more than one-L-SO is arranged
3 -M
+The unit is connected R
9On the unit; L is the side chain connection portion that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group poly-(oxyalkylene group) and their mixture.
M is selected from lithium, sodium, potassium, calcium and magnesium, the cationic moiety of preferred sodium and potassium.
Preferred R
5Part mainly is R
10The C that replaces
2-C
6Alkylidene chain.R
5The unit comprises one by one or several R that selects separately
10(preferably) C of replacing partly
2-C
6Alkylidene chain, perhaps two C
2-C
6Alkylidene chain, said alkylidene chain is connected by ether oxygen, and each alkylidene chain is by one or several R that selects separately
10Part replaces, i.e. R
5Can contain two R that separate
9The unit, wherein each is by one or several R that selects separately
10Part replaces.Preferred each R
9Part has only a carbon atom quilt-L-SO
3 -M
+The unit replaces, residue R
10Substituting group contains hydrogen atom.(two R when symbol i equals 1
9The unit comprises R
5The unit), preferred general formula is:
Each R wherein
9Comprise a C
2Alkylene moiety.A preferred R
10Part is-L-SO
3 -M
+, preferred C
2Carbon atom quilt-L-SO
3 -M
+Partly replacement, and balance portion is a hydrogen atom, thereby has following general formula:
Wherein L is poly-inferior ethoxyl methyl substituents, and x is 0 to about 20.
Just as used herein, said " R
5Part mainly comprises the unit:
I equals 0, wherein R
10The unit is hydrogen and a R
10The unit is-L-SO
3 -M
+, wherein L is the side chain connection portion that is selected from alkylidene group, alkenylene, alcoxyl alkylidene group, oxyalkylene, arylidene, alkarylene, alkoxyl group arylidene and their mixture ", be meant preferred compound of the present invention, wherein R
10Part comprises one-L-SO
3 -M
+Part, R
10The other parts of part are hydrogen atoms, for example
It can be with one-A-R
5-A-main chain segment inserts the main polymer chain of soil release polymer of the present invention.The raw material that this unit is easy to have by employing following general formula is attached in oligopolymer or the main polymer chain:
Wherein in order to have L part of the present invention, x is 0 to 20.
Can be with R
5Other proper monomer that part is inserted in the main chain of the non-cotton soil release polymers of preferred category-A of the present invention comprises that alkylidene group gathers (oxyalkylene group) oxygen arylidene, and it contains the monomer with following general formula:
Wherein x is 0 to about 20.Produce the preferred R that i wherein equals 0
5Another example of unitary preferred monomers is to have the sodium of following general formula for poly-(inferior ethoxyl) methyl isophthalic acid of sulfo group, the 2-propylene glycol:
Wherein x is 0 to 20; Monomer more preferably:
Or
The preferred non-cotton stain remover of the present invention is except above-mentioned R
1, R
2, R
3, R
4And R
5Also comprise one or more end groups-(end group) outside the unit.It is (MO that this end group is selected from general formula separately
3S) (CH
2)
m(R
11O)
n-ethoxylation or propenoxylated hydroxyethanesulfonic acid ester and propane sulfonic acid ester units, wherein M is aforesaid salt-forming cation, as sodium or tetra-allkylammonium, R
11Be ethylidene or propylidene or their mixture, m is 0 or 1, and n is 1 to 20, and preferred n is 1 to about 4; General formula is-(O) C (C
6H
4) (SO
3 -M
+) sulphur aroyl unit, wherein M is aforesaid salt-forming cation; General formula is R
12O (CH
2CH
2O)
k-modification poly-(oxyethylene group) oxygen monoalky lether unit, wherein R
12Contain 1 to 4 carbon atom, R
12Preferable methyl, k is from about 3 to about 100, and is preferred about 3 to 50, more preferably 3 to about 30; With general formula be MO
3S (C
6H
4) (OR
13)
nThe ethoxylation of O-or propenoxylated phenolsulfonate end-blocking unit, wherein n is 1 to 20; M is a salt-forming cation; R
13Be ethylidene, propylidene and their mixture.
Most preferred end-blocking unit is the end-blocking unit of isethionic acid salt, and it is the hydroxyl ethane part, (MO
3S) (CH
2)
m(R
11O)
n-, preferred R
11Be ethyl, m equals 0, and n from 2 to 4.
The value of t is 0 or 1; The value of u is about 0 to about 60; The value of v is about 0 to about 35; The value of w is 0 to 35.
Have following general formula:
[(Cap)(R
4)
t][(A-R
1-A-R
2)
u(A-R
1-A-R
3)
v(A-R
1-A-R
5)
w
-A-R
1-A-][(R
4)
t(Cap)]
Of the present invention preferred non-cotton soil release polymers generally represent with following conventional structure formula easily:
Following structure is an example of preferred non-cotton soil release polymers of the present invention:
Above-mentioned preferred non-cotton stain remover all is documented in and obtains among the US08/545351 of power November 22 nineteen ninety-five, and it is the part continuation application that December 14 was obtained the US08/355938 of power in 1994, and they all in this combination as a reference.Other non-cotton soil release polymers that is applicable to the present composition is described below.
Preferred non-cotton SRA ' s can further describe into the oligopolymer ester, it comprises: (1) main chain comprises (a), and at least one is selected from dihydroxyl sulfonate, polyhydroxy sulfonate, one so as to the unit of the trifunctional at least of the oligopolymer main chain of formation ester bond generation collateralization and their bonded unit; (b) unit of at least one terephthaloyl part and (c) at least one is 1, the unsulfonated unit of 2-oxygen alkylene oxide group part; (2) one or several end-blocking unit; be selected from non-ionic end-blocking unit, negatively charged ion end-blocking unit; the isethionic acid ester of for example oxyalkylated, preferred ethoxylation; oxyalkylated propane sulfonic acid ester; oxyalkylated propane disulfonate; oxyalkylated sulfophenylate, sulphur aromatic acyl derivative and their mixture.The general formula of preferred ester is:
{(CAP)x(EG/PG)y’(DEG)y”(PEG)y(T)z(SIP)z′(SEG)q(B)m}
CAP wherein, EG/PG, PEG, T and SIP are meant terephthaloyl (T), sulfo group isophthaloyl base (SIP), oxidation inferior ethoxyl and oxygen-1,2-propylidene (EG/PG) unit, capping group (CAP), gather (ethylene glycol) (PEG), (DEG) expression two (ethylene oxide) oxygen unit, (SEG) expression is from the sulfonation ethyl ether and the deutero-unit, relevant portion unit of glycerine, (B) an expression chain unit, it is trifunctional at least, form the oligopolymer main chain that ester group produces a collateralization by it, x is about 1 to about 12, y ' is about 0.5 to about 25; y " from 0 to about 12, y from 0 to about 10, y '+y "+y summation is about 0.5 to about 25; z is about 1.5 to about 25, and z ' from 0 to about 12; Z+z ' summation is 1.5 to about 25, and q is about 0.05 to 12; M is about 0.01 to 10, x, y ', y ", y , z, z ', q and m represent the average mol of every mole of said ester corresponding units, the molecular weight of said ester is about 500 to 5000.
The preferred SEG and the CAP monomer that are used for above-mentioned ester comprise Na-2-(2-, 3-dihydroxyl propoxy-) ethane sulfonate (" SEG "), Na-2-{2-(2-hydroxyl-oxethyl) oxyethyl group } product of ethane sulfonate (" SE3 ") and its homologue and their mixture and ethoxylation and sulfonation allyl alcohol.In this class preferred SRA ester comprise adopt suitable Ti (IV) catalyzer to carry out transesterification and oligomeric 2-{2-(2-hydroxyl-oxethyl) oxyethyl group ethane sulfonic acid sodium and/or 2-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group-oxyethyl group] ethane sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) product of ethane sulfonic acid sodium, EG and PG gained, and can be expressed as (CAP) 2 (T) 5 (EG/PG) 1.4 (SEG) 2.5 (B) 0.13, wherein CAP is (Na+O
3S[CH
2CH
2O] 3.5)-and B be by glycerine deutero-unit, and the molar ratio of EG/PG is about 1.7: 1 by adopt conventional gas Chromatographic Determination after finishing hydrolysis.
Preferred non-cotton stain remover-B.Suitable SRA ' the s of second preferred kind comprises the sulfonated products of the ester oligomer that is wire basically, and this oligopolymer comprises multiple unitary oligopolymer ester main chain of terephthaloyl oxyalkylene oxygen basic weight and and covalently bound allyl group deutero-sulfonation terminal portions on main chain.This class ester oligomer can prepare by following method: (a) ethoxylation allyl alcohol; (b) with product and terephthalic acid dimethyl esters (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") reacts in two steps transesterify effect/oligomerization step; (c) product and the sodium metabisulfite with (b) reacts in water.
The preferred non-cotton soil release polymers that is applicable to laundry detergent composition of the present invention comprises:
A) one or two is selected from the terminal units of following group:
ⅰ)-(CH
2)
q(CHSO
3M)CH
2SO
3M，
ⅱ)-(CH
2)
q(CHSO
2M)CH
2SO
3M，
ⅲ)-CH
2CH
2SO
3M，
ⅳ) and their mixture; Wherein q is 1 to about 4 value, and M is a water-soluble cationic, preferred sodium;
B) main chain comprises:
ⅰ) arylene units preferably has the terephthalate unit of following general formula:
ⅱ) have the inferior ethoxyl unit of following general formula:
-O(CH
2CH
2O)
nCH
2CH
2O-
Wherein the value of n is about 1 to 20; With
ⅲ) have 1 of following general formula, the inferior propoxy-of 2-unit:
-O(CH
2CH(CH
3)O)
nCH
2CH(CH
3)O-
Wherein the value of n is about 1 to 20, and wherein the preferred main chain of this preferred non-cotton soil release polymers has and comprises and inferior ethoxyl and 1, the main chain of the arylene repeat units of the inferior propoxy-units alternately of 2-, inferior ethoxyl and 1 like this, the unitary molar ratio of the inferior propoxy-of 2-is 0: 1 to about 0.9: 0.1, preferred about 0: 1 to about 0.4: 0.6, more preferably arylene units be 1 mainly, 2-Asia propoxy-units alternately.
But other of said units is in conjunction with the non-cotton soil release polymers that can be used for forming the preparation present composition.These combinations are documented in Scheibel on the 6th in November nineteen ninety etc. in more detail and obtain among the US4968451 of power, its at this in conjunction with as a reference.
Preferred non-cotton stain remover-C.Be applicable to that laundry detergent composition of the present invention is the preferred non-cotton soil release polymers with following general formula:
(Cap)[(A-R
1-A-R
2)
u(A-R
3-A-R
2)v-A-R
4-A-](Cap)
Wherein A is the carboxyl connection portion, and preferred A is the carboxyl connection portion with following general formula:
Or
R
1Be the arylidene part, preferably have 1 of following general formula, the 4-phenylen moiety:
Wherein for R
1, by arylidene part rather than 1, the degree that the 4-phenylen moiety replaces will make the detergency ability of compound can not be subjected to very big influence.In general, the degree that the part that can bear replaces depends on the backbone length of compound.
R
2Part is the ethylidene part or has C
1-C
4The ethylidene part of the replacement of alkyl or alkoxy substituent.As what adopted herein, said " the R2 part mainly is the ethylidene part or has C
1-C
4The ethylidene part of the replacement of alkyl or alkoxy substituent " be meant and work as R
2Part all is that the ethylidene by ethylidene or replacement partly constitutes or the The compounds of this invention when partly being replaced by other adoptable part.The example of these other parts comprises trimethylene, tetramethylene, pentamethylene or hexamethylene, 1,2-hydroxy alkylidene and oxyalkylene group.
For R
2Part, the degree that is partly replaced by these other parts should make the decontamination character of this compound can not be subjected to very big disadvantageous effect.For example, for polyester prepared in accordance with the present invention, adopt Diethylene Glycol (CH
2CH
2OCH
2CH
2-) be just to have enough decontamination activity at 75: 25 with the molar ratio of ethylene glycol (ethylidene).
For R
3Part, the C of suitable replacement
2-C
18The alkylene part can comprise the C of replacement
2-C
12Parts such as alkylidene group, alkenylene, arylidene, alkarylene.Alkylidene group that replaces or alkenylene part can be wire, collateralization or cyclic.R
3Can also be identical (as the arylidene of whole replacements) or mixture (as the mixture of the alkylidene group of the arylidene that replaces and replacement).Preferred R
3Part is substituted 1,3-phenylene, preferred 5-sulfo group-1,3-phenylene.R
3Part or A-[(R
2-A-R
4)]-end-blocking, wherein R
4Be R
1, R
3With their mixture.
Preferably (end group) part comprises the unit with following general formula:
-[(R
5O)
m(CH
2CH
2O)
n]X
R wherein
5Be C
1-C
4Alkylidene group, perhaps part-R
2-A-R
6, R wherein
6Be C
2-C
12Alkylidene group, alkenylene, arylidene or alkarylene, X is C
1-C
4Alkyl, preferable methyl; Symbol m and n will make part-CH
2CH
2O-contains part shown in the following formula of at least 50% weight
-[(R
5O)
m(CH
2CH
2O)
n]X
As long as work as R
5Be part-R
2-A-R
6In-time, m is 1 at least; Each n is at least about 10, and it is about 3 to about 25 that symbol u and v will make the summation of u+v; Symbol w is O or at least 1; And when w was at least 1, it was about 3 to 25 that the value of symbol u, v and w will make the summation of u+v+w.
The example of the non-cotton decontamination block polyester of this class is to have following general formula:
R wherein
2Part mainly is ethylidene part, propylene part and their mixture; R
3Part all is potassium or preferred sodium 5-sulfo group-1, the 3-phenylen moiety; R
4Part is R
1Perhaps R
3Part, perhaps their mixture; Each X is ethyl, methyl, preferable methyl; Each n is about 12 to about 43; When w was 0, u+v was 3 to about 10; When w was at least 1, u+v+w was 3 to about 10.
Have general formula:
(Cap) [(A-R
1-A-R
2)
u(A-R
3-A-R
2)
v-A-R
4-A-] (Cap) above-mentioned non-cotton soil release polymers at length is documented in and authorized among the US4702857 of Gosselink on October 27th, 1987, and its at this in conjunction with as a reference.
Except above-mentioned non-cotton soil release polymers, other soil release polymer that is applicable to liquid laundry detergent compositions of the present invention is further described below.
Any other non-cotton stain remover of negatively charged ion is suitable for separately or in conjunction with being used for composition of the present invention, only the carboxymethyl cellulose that can not use separately (CMC) exception.If formulator is selected the anionic detergent of CMC as laundry detergent composition of the present invention, the amount of carboxymethyl cellulose must be greater than 0.2% of said composition.
Cotton soil release polymers
The cotton stain remover that can be used for liquid detergent composition of the present invention is water-soluble or dispersible modified polyamine.It can be wire or cyclic main chain that these polyamine contain.The polyamine main chain also can contain long or short polyamine side chain.In general, said here polyamine main chain is to come modification in unitary formal specification mode in the back with each nitrogen of polyamine chain wherein, and the unit is substituted, the combination of quaternized, oxidation or these reactions.
In order to reach purpose of the present invention, said " modification " is meant with the nitrogen (quaternized) of E replacement unit main chain-NH hydrogen atom (replacement), quaternized main chain or with main chain nitrogen and is oxidized to nitrogen oxide (oxidation).When being meant that when replacing the hydrogen atom be connected on the main chain nitrogen with the E unit, said " modification " and " replacement " can be used alternatingly.Quaternized or oxidation can be carried out under some situations that do not have to replace, but preferred replacement is accompanied by oxidation or quaternized at least one main chain nitrogen carries out.
The wire or the non-annularity polyamine main chain that contain cotton stain remover of the present invention have following general formula:
Said main chain before follow-up modification, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.The cyclic polyamines main chain that contains cotton stain remover of the present invention has following general formula:
Said main chain before follow-up modification, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.
In order to reach purpose of the present invention, just be defined as V or Z " end " unit in case contain the primary amine nitrogen modification of main chain or side chain.For example, when the structure that has that is positioned at a main polyamine main chain or a chain end:
H
2N-R]-primary amine part when carrying out modification according to the present invention, it just is meant V " end " unit afterwards, perhaps is exactly the V unit simply.But in order to reach purpose of the present invention, some or whole primary amine part can keep not modification according to other restriction that describes below.These unmodified primary amine parts are owing to their positions on main chain keep " end " unit.Equally, when having structure:
-NH
2The primary amine part that is positioned at main primary amine main chain end according to the present invention during modification, after this it is meant Z " end " unit, perhaps is the Z unit simply.This unit can keep not modification according to other restriction that the following describes.
Similarly, in case contain the secondary amine nitrogen modification of main chain or side chain, just be defined as W " main chain " unit.For example, when the secondary amine part, the major portion of main chain promptly of the present invention and side chain, it has following structure:
During modification, after this it just is defined as W " main chain " unit, or is called the W unit simply according to the present invention.But in order to reach purpose of the present invention, some or whole secondary amine part can keep not modification.These unmodified secondary amine parts are owing to their positions on main chain keep " main chain " unit.
Similarly, in case contain the tertiary amine nitrogen modification of main chain or side chain, just be defined as Y " side chain " unit.For example, when the tertiary amine part, it is the side chain point of the chain of polyamine main chain or other side chain or ring, has following structure:
When being modified according to the present invention, after this it just is defined as Y " side chain " unit, or is called the Y unit simply.But in order to reach purpose of the present invention, some or whole tertiary amine part can keep not modification.These unmodified tertiary amine parts are owing to their positions on main chain keep " side chain " unit.The R unit relevant with Y unit nitrogen with the V that is used to connect polyamine nitrogen, W is described below.
Therefore, the structure of the last modification of polyamine of the present invention can be used general formula:
V
(n+1)W
mY
nZ
Expression wire polyamine cotton soil release polymers and general formula:
V
(n-k+1)W
mY
nY’kZ
Expression cyclic polyamines cotton soil release polymers.Contain under the situation of ring general formula at polyamine:
Y ' unit play the effect of the side chain position of main chain or chain link.For each Y ' unit, have a Y unit to have following general formula:
It will form the tie point of ring and main polymer chain or side chain.At main chain is that this polyamine main chain has following general formula under the particular case of a domain:
Therefore do not have the Z terminal units and have following general formula:
V
n-kW
mY
nY’
k
Wherein k forms the unitary number of rings of side chain.Preferred polyamine main chain of the present invention does not contain ring.
Under the situation of acyclic polyamine, the ratio of symbol n and symbol m is relevant with the relative extent of side chain.Do not have the wire modified polyamine of collateralization to have following general formula fully according to of the present invention:
VW
mZ just n equals 0.The value of n big more (ratio of m and n is more little), the side chain degree in the molecule is big more.The general minimum of the value of m is 4 to about 400, still, and bigger m value is particularly very low or also be preferred near 0 the time when the value of symbol n.
Each polyamine nitrogen is no matter be primary, the nitrogen of the second month in a season or tertiary amine, in case the modification according to the present invention can be defined as one of them of three kinds of general types again: simply replace, quaternized or oxidation.These polyamine nitrogen unit that do not have a modification according to they whether be primary, the second month in a season or uncle's nitrogen is divided into V, W, Y or Z unit.In order to reach purpose of the present invention, unmodified primary amine nitrogen is V or Z unit, and unmodified secondary amine nitrogen is the W unit, and unmodified tertiary amine nitrogen is the Y unit.
The primary amine of modification partly is meant V " end " unit, and it has a kind of in following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternary ammonium unit of following structure:
Wherein X provides the suitable gegenion of charge balance; With
C) have the oxidized unit of following structure:
The secondary amine of modification partly is meant W " main chain " unit with one of following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternary ammonium unit of following structure:
Wherein X provides the suitable gegenion of charge balance; With
C) have the oxidized unit of following structure:
The tertiary amine of modification partly is meant Y " side chain " unit with one of following three kinds of forms:
A) have the unmodified unit of following structure:
B) have the quaternary ammonium unit of following structure:
Wherein X provides the suitable gegenion of charge balance; With
C) have the oxidized unit of following structure:
The primary amine of some modifications partly is meant Z " end group " unit with one of following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternary ammonium unit of following structure:
Wherein X provides the suitable gegenion of charge balance; With
C) have the oxidized unit of following structure:
Any position on nitrogen is not replace or unmodified, can think that hydrogen replaces E.For example, containing a form is that the hydroxyethyl unitary primary amine of E unit partly is to have general formula (HOCH
2CH
2) the V terminal units of HN-.
In order to reach purpose of the present invention, two class chain end unit are arranged, V and Z unit.Z " end " unit is by structure-NH
2The terminal primary amine moiety derive.Non-annularity polyamine main chain of the present invention only contains a Z unit, and cyclic polyamines can not conform to the Z unit is arranged.Z " end " unit can be replaced by any E unit of being described below, unless when the Z unit formation nitrogen oxide that is modified.Under the situation of the oxidized generation nitrogen oxide of Z unit nitrogen, nitrogen must be modified, and therefore E can not be a hydrogen.
Polyamine of the present invention contains main chain R " connection " unit, and it plays the effect that connects nitrogen-atoms on the main chain.R to contain the unit in order reaching and to the objective of the invention is to refer to " alkyl R " unit and " oxygen R " unitary unit." alkyl " R unit is C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, any position that hydroxylic moiety can be on the R cellular chain wherein is except directly being connected the carbon atom on the polyamine main chain nitrogen; C
4-C
12Alkyl sub-dihydroxy, wherein hydroxylic moiety can occupy any two carbon atoms of R cellular chain, except those directly are connected carbon atom on the polyamine main chain nitrogen; C
8-C
12Two alkarylene, it according to the invention ,the aim of the invention is to have the arylidene part of two alkyl substituents as the part of connection chain.For example, two alkarylene unit have following general formula:
Or
Although this unit needs not to be 1,4-replaces, but goes back 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and their mixture, more preferably ethylidene." oxygen " R unit comprises-(R
1O)
xR
5(OR
1)
x-,-CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-,-(R
1O)
xR
1-and their mixture, preferred R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12Two alkarylene ,-(R
1O)
xR
1-,-CH
2CH (OR
2) CH
2-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH) CH
2)
w-,-(R
1O)
xR
5(OR
1)
x-, more preferably the R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH) CH
2)
w-and their mixture, the R unit that is more preferably is C
2-C
12Alkylidene group, C
3Hydroxy alkylidene and their mixture, most preferably C
2-C
6Alkylidene group.The most preferred main chain of the present invention comprise at least 50% be the R unit of ethylidene.
R
1The unit is C
2-C
6Alkylidene group and their mixture, preferred ethylidene.R
2Be hydrogen and-(R
1O)
xB, preferred hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12 aryl alkylenes, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the unitary part of following said E.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
10Alkylidene group, C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group, most preferably ethylidene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12Two alkarylene ,-C (O)-,-C (O) NHR
6NHC (O)-,-C (O) (R
4)
rC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-, R
5Preferred ethylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably R can further be used in " oxygen " R unit
1, R
2And R
5The unit is represented.Preferably " oxygen " R unit contains preferred R
1, R
2And R
5The unit.The preferred cotton stain remover of the present invention contain at least 50% be the R of ethylidene
1The unit.Preferred R
1, R
2And R
5The unit combines in the following manner with " oxygen " R unit and generates preferred " oxygen " R unit.
ⅰ) with preferred R
5Substitute onto-(CH
2CH
2O)
xR
5(OCH
2CH
2)
x-generation-(CH
2CH
2O)
xCH
2CHOHCH
2(OCH
2CH
2)
x-.
ⅱ) with preferred R
1And R
2Substitute onto-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1O (CH
2CH-(OR
2) CH
2)
w-generation-(CH
2CH (OH) CH
2O)
z(CH
2CH
2O)
yCH
2CH
2O (CH
2CH (OH) CH
2)-,
ⅲ) with preferred R
2Substitute onto-CH
2CH (OR
2) CH
2-generation-CH
2CH (OH) CH
2-.
The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Arylalkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
mB ,-C (O) R
3, preferred hydrogen, C
2-C
22Hydroxy alkylidene, benzyl, C
1-C
22Alkylidene group ,-(R
1O)
mB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, most preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3When nitrogen not carried out modification or replacing, hydrogen atom will keep as the part of representing E so.
When V, W or Z unit were oxidized, the E unit did not comprise hydrogen atom, and promptly nitrogen is nitrogen oxide.For example, main chain or side chain do not comprise the unit with following structure:
Or
Or
In addition, when V, W or Z unit were oxidized, the E unit did not comprise directly and the carbonyl moiety of nitrogen-atoms Cheng Jian that promptly nitrogen is nitrogen oxide.According to the present invention, E unit-C (O) R
3Part not with nitrogen oxide in modification nitrogen Cheng Jian, promptly do not have the nitrogen oxide acid amides of following structure or their mixture:
Or
Or
B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, preferred hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M, more preferably hydrogen or-(CH
2)
qSO
3M.
M is hydrogen or the water-soluble cationic that is enough to satisfy the charge balance amount.For example sodium ion satisfies-(CH equivalently
2)
pCO
2M and-(CH
2)
qSO
3M, thereby generation-(CH
2)
pCO
2Na and-(CH
2)
qSO
3The Na part.More than a kind of monovalent cation (sodium, potassium etc.), can be in conjunction with satisfying required chemical charge balance.But, can come the electric charge of balance by two valency positively charged ions more than an anionic group, perhaps need an above monovalent cation to satisfy the electric charge needs of multivalent anions group.For example by sodium atom replace-(CH
2)
pPO
3M partly has general formula :-(CH
2)
pPO
3Na
3Divalent cation is as calcium ion (Ca
2+) or magnesium ion (Mg
2+) can replace other suitable monovalence water-soluble cationic or combine with it.Preferred cation is sodium ion and potassium ion, more preferably sodium ion.
X is a water soluble anion, as chlorion (Cl
-), bromide anion (Br
-) and iodide ion (I
-), perhaps X can be the group of any generation negative charge, as sulfate ion (SO
4 2-) and methyl sulfite ion (CH
3SO
3 -).
The symbol of general formula has following value: p and has 1 to 6 value, and q has 0 to 6 value; R has 0 or 1 value; W has 0 to 1 value, and x has 1 to 100 value; Y has 0 to 100 value; Z has 0 or 1 value; M has 4 to about 400 value, and n has 0 to about 200 value; M+n has at least 5 value.
The preferred cotton stain remover of the present invention contains the polyamine main chain, wherein contains " oxygen " R unit less than about 50% R group, preferably less than about 20%, is more preferably less than 5%, and most preferably the R unit does not contain " oxygen " R unit.
Do not contain the unitary most preferred cotton stain remover of " oxygen " R and contain the polyamine main chain, wherein contain carbon atom more than 3 less than 50% R group.For example, ethylidene, propylene and trimethylene contain 3 or carbon atom still less, and are preferred " alkyl " R unit.That is to say that working as main chain R unit is C
2-C
12During alkylidene group, C preferably
2-C
3Alkylidene group, most preferably ethylidene.
Cotton stain remover of the present invention contains the homogeneous phase or the heterogeneous polyamine main chain of modification, wherein 100% or less-NH unit be modified.In order to reach purpose of the present invention, said " homogeneous phase polyamine main chain " is meant the unitary polyamine main chain of R with identical (promptly all being ethylidene).But the less important unitary polyamine that contains other main polymer chain that comprises the artifact that exists owing to selected chemical synthesis process is not got rid of in this identical definition.For example, the known thanomin of those skilled in the art can be as the initiator of synthesizing polyethylene imines, therefore, the sample that contains a kind of polymine of the hydroxyethyl part that is produced by polyreaction " initiator " can be considered to contain the homogeneous phase polyamine main chain at the object of the invention place.Containing and not having the unitary polyamine main chain of the unitary inferior second R of side chain Y all is the homogeneous phase main chain.Containing all is that the unitary polyamine main chain of inferior second R is the homogeneous phase main chain, and no matter collateralization or ring-type side chain have a number.
In order to reach purpose of the present invention, said " heteropolymer main chain " is meant the polyamine main chain of the complex body of different R element lengths and R cell type.For example, to contain be the R unit of ethylidene and propylene unit mixture to heterogeneous main chain.In order to reach purpose of the present invention, the unitary mixture of " alkyl " and " oxygen " R is not to provide heterogeneous main chain necessary.The proper operation of these " length of R cellular chain " makes formulator can change the solubleness of cotton stain remover of the present invention and to the substantivity of fabric.
The preferred cotton soil release polymers of the present invention contains homogeneous phase polyamine main chain (they are partly replaced by poly-inferior ethoxyl in whole or in part), in whole or in part by quaternised amine, be oxidized to the nitrogen of oxide compound and their mixture in whole or in part.But, not the nitrogen modification in the same way of whole main chain amine, modification is selected according to the concrete needs of formulator.The degree of ethoxylation is also decided by the concrete needs of formulator.
The preferred polyamine that contains the The compounds of this invention main chain generally is polyalkylene amine (PAA ' s), polyalkyleneimine (PAI ' s), preferred poly-ethyleneamines (PEA ' s), polyethylene imine based (PEI ' s) are perhaps by having PEA ' s or the PEI ' s that the unitary part of the R longer than original PAA ' s, PAI ' s, PEA ' s or PEI ' s connects.General polyalkylene amine (PAA) is four butylidenes, five amine.PEA ' s is by comprising the reaction of ammonia and Ethylene Dichloride, then carries out the fractionation preparation.PEA ' the s of general preparation is four ethylidene tetramines (TETA) and tetren (TEPA).More than above-mentioned five amine, i.e. hexamine, seven amine, eight amine and may be nine amine, common deutero-mixture can not pass through fractionation by distillation, and can comprise other material, for example cyclic amine, particularly piperazine.Also can there be the cyclic amine that nitrogen-atoms is wherein arranged with side chain.Obtain the US2792372 of power referring to Dickinson in May 14 nineteen fifty-seven, it has put down in writing the preparation method of PEA ' s.
Preferred amine polymer main chain comprises the R unit, and it is C
2Alkylidene group (ethylidene) unit also is known as polyethylene imine based (PEI ' s).Preferred PEI ' s has medium side chain at least, and promptly the ratio of m and n is less than 4: 1, and still, it is most preferred that the ratio of m and n is about 2: 1 PEI ' s.General formula below preferred main chain had before modification:
Wherein m and n are same as described above.Preferred PEI ' s before modification molecular weight greater than about 200 dalton.
On the polyamine main chain under PEI ' the s situation particularly, the unitary relative proportion of primary amine, secondary amine and tertiary amine can change according to the preparation method.Be connected each hydrogen atom on each nitrogen-atoms of polyamine main chain represent one can replace subsequently, the position of quaternized or oxidation.
Can be by for example there be catalyzer in these polyamine, and the method for for example carrying out the polymerization ethylenimine under the situation of carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, spirit of salt, acetate etc. prepares.The concrete grammar for preparing these polyamine main chains is disclosed in Ulrich etc. and obtains among the US2182306 of power in 5 months December of nineteen thirty-nine; Mayle etc. obtained among the US3033746 of power on May 8th, 1962; Esselmann etc. obtain the US2208095 of power on July 16th, 1940; Crowther obtains the US2806839 of power in September 17 nineteen fifty-seven; Obtain among the US2553696 of power in May 21 nineteen fifty-one with Wilson; These documents all in this combination as a reference.
The example of the modification cotton soil release polymers of the PEI of containing ' s of the present invention illustrates with following formula I-V:
The formula I explanation contains the preferred cotton soil release polymers of PEI main chain, and wherein whole commutable nitrogen-atoms all pass through with polyoxyalkylene oxygen unit, promptly-and (CH
2CH
2O)
20H replaces hydrogen and carries out modification, and it has following general formula:
The formula I
The explanation of general formula II contains the cotton soil release polymers of PEI main chain, and wherein whole commutable nitrogen pass through with polyoxyalkylene oxygen unit, promptly-and (CH
2CH
2O)
7H replaces hydrogen and carries out modification, and it has following general formula:
The formula II
This is the example with the partially modified cotton soil release polymers of a class group.
The explanation of general formula III contains the cotton soil release polymers of PEI main chain, and wherein whole commutable amine nitrogen pass through with polyoxyalkylene oxygen unit, promptly-and (CH
2CH
2O)
7H replaces hydrogen and carries out modification, this molecule then by will whole oxidable primary nitrogen and secondary nitrogen be subsequently oxidized to nitrogen oxide and come modification, said cotton stain remover has following general formula:
The formula III
General formula IV explanation contains the cotton soil release polymers of PEI main chain, wherein all the main chain hydrogen atoms be substituted and part main chain amine unit by quaternized.Substituting group is polyoxyalkylene oxygen unit, promptly-and (CH
2CH
2O)
7H, perhaps methyl.The PEI cotton soil release polymers of modification has following general formula:
General formula V explanation contains the cotton soil release polymers of PEI main chain, and wherein main chain nitrogen is by being substituted (i.e. quilt-(CH
2CH
2O)
7H or methyl substituted), quaternized, be oxidized to nitrogen oxide or with their in conjunction with carrying out modification.The cotton soil release polymers that generates has following general formula:
The formula V
In above-mentioned example, not that the unitary whole nitrogen of a class have all carried out identical modification.The present invention allows formulator with the ethoxylation of a part of secondary amine nitrogen, simultaneously the nitrogen oxide that other secondary amine nitrogen is oxidized to.This also is applicable to primary amine nitrogen, wherein formulator can select with one or several substituting groups oxidation or quaternized before all or part of primary amine nitrogen of modification.Any possible combination of E group can replace on primary amine nitrogen and secondary amine nitrogen, have that above-mentioned strictness limits except.
Laundry detergent composition of the present invention contains binder component and carrier, said binder component is selected from auxiliary agent, white dyes, SYNTHETIC OPTICAL WHITNER, bleaching secondary accelerator, bleach activator, other non-cotton soil release polymers, dye transfer inhibitor, dispersion agent, enzyme, enzymic activity agent, suds suppressor, dyestuff, spices, pigment, filling salt, hydrotropic agent and their mixture, but listed here is not to get rid of or do not comprise the spendable suitable substance of any formulator.
Detergent surfactant
Except the preferred anionic and nonionic detergent surfactant of record here, other is suitable for detergent surfactant of the present invention is positively charged ion, negatively charged ion, nonionic, amphoteric, amphoteric tensio-active agent and their mixture, and this will further describe below.
The non-limiting example that the spendable concentration of other the present invention is generally the tensio-active agent of about 1% to 55% weight comprises conventional C
11-C
18Alkylbenzene sulfonate (" LAS "), C
10-C
18Secondary (2,3) alkyl-sulphate, general formula is CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3, wherein x and (y+1) be to be at least about 7 integer preferably is at least about 9, and M is a water-soluble cationic, sodium ion particularly, undersaturated vitriol for example is oleyl sulfate, C
10-C
18Alkyl alkoxy carboxylate salt (the particularly ethoxy carboxylate of E01-5), C
10-C
18Glyceryl ether, C
10-C
18The poly-glycosides of alkylpolyglycosides and their corresponding sulphatings, and C
12-C
18α-sulfonated fatty acid ester.If desired, conventional nonionic and zwitterionics, for example C
12-C
18Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C
6-C
12Alkylphenol alcoxylates (particularly ethoxylate and blended oxyethyl group/propoxy-), C
12-C
18Trimethyl-glycine and sultaine (" sultains "), C
10-C
18Amine oxides etc. also can be included in the above-mentioned composition.Also can use C
10-C
18N-alkyl polyhydroxy fatty acid amide.General example comprises C
12-C
18The N-methyl glucose amide.Referring to WO9206154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxy-propyl) glucamide.Also can adopt C
10-C
20Conventional soap.High if desired foamy can adopt side chain C
10-C
16Soap.The mixture of negatively charged ion and nonionogenic tenside is particularly preferred.Other tensio-active agent commonly used is listed in the standard article.
Other anion surfactant that can be used for washing purpose also can be included in herein the composition.They comprise soap salt (ammonium salt that for example comprises sodium salt, sylvite, ammonium salt and replacement, as one, two and triethanolamine salt), C
9-C
20Wire alkylbenzene sulfonate, C
8-C
22Primary-or secondary sulfonated alkane, C
8-C
24Olefin sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphonate, isethionate (isothionates) are as fatty acid amide, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (the particularly saturated and undersaturated C of acyl isethinate, N-acyl taurine salt, methyl tauryl amine (tauride)
12-C
18One ester), the diester of sulfo-succinic acid (particularly saturated and undersaturated C
6-C
14Diester), the vitriol of N-acyl group musculamine hydrochlorate, alkyl polysaccharide, for example primary alkyl sulphates of the vitriol of alkylpolyglycosides, collateralization, alkyl polyethoxye carboxylate salt, for example general formula is RO (CH
2CH
2O)
kCH
2COO
-M
+, wherein R is C
8-C
22Alkyl, k are from 0 to 10 integers, and M is the salt-forming cation of solubility, by the hydroxyl sulfoacid esterification with by sodium hydroxide neutral lipid acid.Other example provides in Surface Active Agents and Detergents (I of Schwartz, Perry and Berch and II volume).
Non-cotton stain remover
Known polymkeric substance stain remover is meant at this paper " SRA ", can optionally be used for the present composition.If adopt, SRA ' s is generally 0.01% to 10.0% of composition, is generally 0.1% to 5%, is preferably 0.2% to 3.0% weight.
Preferred SRA ' s generally contains hydrophilic segment makes hydrophobic fiber, adheres on it to be deposited on the hydrophobic fiber and by finishing the maintenance of washing and cleaning operation as the surface hydrophilic and the hydrophobic segment of polyester and nylon, so just plays the fixedly effect of hydrophilic segment.This can make the spot that adopts SRA to produce after handling be easy to remove in below the washing step.
SRA ' s can comprise various electric charges, as negatively charged ion or even positively charged ion, referring to the US4956447 that authorizes Gosselink September 11 nineteen ninety, and uncharged monomeric unit, and their structure can be wire, collateralization or or even starlike.They can comprise the end-blocking part, and they are being effective especially aspect control molecular weight or adjustment physical properties or the surfactivity.Structure can be adjusted to satisfy with charge distribution and be used for different fibers or fabric type and be used for various washing composition or detergent additives product.
Preferred SRA ' s comprises oligomeric terephthalate, generally is by comprising at least one transesterification reaction/oligomerization, adopt a kind of metal catalyst usually that for example the method for the alkoxide of titanium (IV) prepares.This class ester can adopt other can pass through one, two, three, four or a plurality of position, does not certainly form other monomer that intensive crosslinked one-piece construction is attached in the ester structure and prepares.
Other SRA ' s comprises that Gosselink etc. obtains nonionic end capped 1 among the US4711730 of power on December 8th, 1987,2-propylidene/polyoxyethylene terephthalic polyester, for example they are the transesterification reaction/oligomerization preparations by poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").The example of other SRA ' s comprises: Gosselink etc. obtained part and whole end capped oligomer esters of negatively charged ion among the US4721580 of power on January 26th, 1988, for example by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl sodium octyl preparation; With anionic; particularly Maldonado etc. obtained sulphur aroyl, end capped terephthalate among the US4877896 of power on October 31st, 1989; the latter is used for laundry and the typical SRA ' s of fabric adjustment product; an example is the ester composition that is prepared by a sulfosalicylic acid one sodium salt, PG and DMT; the PEG that randomly still preferably further contains adding is as PFG3400.
SRA ' s also comprises: the simple segmented copolymer of ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or polyoxytrimethylene terephthalate, referring to Hays at the US3959230 on May 25th, 1976 and Basadur US3893929 on July 8th, 1975; Derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the METHOCEL that provides as Dow; C1-C4 alkylcellulose and C
4Hydroxy alkyl cellulose is referring to the US4000093 on December 28th, 1976 such as Nicol; Be about 1.6 to 2.3 and be the methyl cellulose ether of about 80 to 120 centipoises with average replacement (methyl) degree of each anhydroglucose unit at 20 ℃ of soltion viscosities with 2% determination of aqueous solution.This class material can METOLOSE SM100 and METOLOSE SM200 title obtain, this is the trade(brand)name of the methyl cellulose ether produced by Shin-etsu Kagaku Kogyo KK..
SRA ' the s that is suitable for that is characterised in that poly-(vinyl ester) hydrophobic segment comprises the graft copolymer of poly-(vinyl ester), as C
1-C
6Vinyl ester, preferred poly-(vinyl-acetic ester), grafting on the polyalkylene oxide main chain.Referring to by Kud etc. at disclosed EP0219048 on April 22nd, 1987.Industry available example comprises SOKALAN SRA ' s, the SOKALAN HP-22 that provides as the BASF by Germany.Other SRA ' s is the polyester of the poly-terephthalic acid oxygen ethylidene ester that contains the ethylene terephthalate and 80～90% weight of 10～15% weight (is that 300～5000 polyoxyethylene glycol is derived by molecular-weight average) repeating unit.ZELCON5126 that is provided by Dupont and the MILEASE that is provided by ICI are provided industrial example.
Another kind of SRA is an oligopolymer, and its general formula is: (CAP)
2(EG/PG)
5(T)
5(SIP)
1It contains benzoyl group (SIP), oxidation inferior ethoxyl and oxygen-1 between benzoyl group (T), sulfo group; 2-propylidene (EG/PG) unit; and it is preferably by END CAPPED GROUP (CAP); the isethionic acid ester end-blocking of preferred modification; resemble and containing benzoyl group unit between a sulfo group, 5 oxidation inferior ethoxyl and oxidations-1 benzoyl group unit, qualification ratio; the same in the unitary oligopolymer of 2-propylidene oxygen; preferred 0.5: 1 to about 10: 1 ratio and two by 2-(2-hydroxyl-oxethyl) ethane sulfonic acid sodium deutero-end-blocking unit.Said SRA preferably further contains the minimizing crystallization-stable agent of 0.5% to 20% weight oligopolymer, anion surfactant for example, for example the wire Sodium dodecylbenzene sulfonate or be selected from dimethylbenzene-, cumene-and a kind of material of toluene-sulfonate or their mixture, these stablizers or properties-correcting agent can join in the synthesising container, and they all are documented in Gosselink, Pan, Kellett and Hall and obtain among the US5415807 of power in May 16 nineteen ninety-five.The proper monomer that is used for above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium, DMT, dimethyl isophthalate-5-sodium sulfonate, EG and PG.
Other type of SRA ' s comprises: (I) adopts the vulcabond coupler to connect the nonionic terephthalate of polyester structure, referring to the US4240918 of the US4201824 of Violland etc. and Lagasse etc.; (II) have by in known SRA ' s, add trimellitic acid 1,2-anhydride with the end hydroxyl be transformed into the trimellitate preparation the SRA ' s of carboxylicesters end group.Suitable selecting catalyst, the trimellitic acid acid anhydrides is by the ester of the independent carboxylic acid of trimellitic acid acid anhydrides rather than by opening the terminal Cheng Jian of anhydride bond and polymkeric substance.Non-ionic or negatively charged ion SRA ' s can be used as raw material, if they have can esterification hydroxyl.US4525524 referring to Tung etc.Other type comprises: the SRA ' s of the negatively charged ion terephthalic acid alkali of (III) urethane type of attachment, referring to the US4201824 of Violland etc.; (IV) poly-(caprolactam) and by monomer, for example the related copolymers of vinyl pyrrolidone and/or dimethyl amino ethyl methacrylate comprises nonionic and cationic polymkeric substance, referring to the US4579681 of Ruppert etc.; (V) graft copolymer, the SOKALAN class that provides except BASF also has by Acrylic Acid Monomer is grafted on to prepare on the sulfonated polyester.These SRA ' s should have the decontamination of the plain ether of the known fiber of being similar to and prevent sedimentary activity again: referring to the EP279134A of Rhone-Poulenc Chemie in 1988.Also have some types to comprise: (VI) vinyl monomer, for example vinylformic acid and vinylacetate are at albumen, and for example grafting on the casein is referring to the EP457205A of BASF (1991); (VII) can be used in particular for handling polyamide fabric by the polyester-polyamide SRA ' s of condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol preparation, referring to Bevan etc., the Unilever N.V. DE2335044 in 1974.Other effective SRA ' s is documented among the US4240918,4787989 and 4525524.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator
Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or several bleach activators.When containing SYNTHETIC OPTICAL WHITNER, its amount will be in particular for the detergent composition of fabric washing about 0.05% to about 30%, more preferably from about 1% to 30%, most preferably from about 5% to 20%.If contain bleach activator, its amount is generally and contains bleaching composition about 0.1% to 60% that SYNTHETIC OPTICAL WHITNER adds bleach activator, more generally is about 0.5% to 40%.
The SYNTHETIC OPTICAL WHITNER that the present invention adopts can be any can be used for the present known of clean fabric or will known detergent composition in SYNTHETIC OPTICAL WHITNER.They comprise oxygen bleaching agent, and other SYNTHETIC OPTICAL WHITNER.Can adopt perborate bleach, as Sodium peroxoborate (as one-or tetrahydrate).
Other kind indefiniteness SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprises Magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoic acid magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in Hartman obtains power on November 20th, 1984 US4483781, Burns etc. obtain the US740446 of power on June 3rd, 1985, Banks etc. are at disclosed EPO133354 on February 20th, 1985, and Chung etc. obtained among the US4412934 of power in November 1 nineteen eighty-three.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid, as what put down in writing in obtaining the US4634551 of power on January 6th, 1987 at Burns etc.
Also can adopt peroxygen bleach.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate and equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can adopt persulphate SYNTHETIC OPTICAL WHITNER (as the OXONE of the industrial production of DuPont).
Preferred percarbonate bleach contains dried particles, and its mean particle size arrives in about 1000 microns scope at about 500 microns, and the said particle that is not more than about 10% weight is less than about 200 microns, and the said particle that is not more than about 10% weight is greater than about 1250 microns.Randomly be that this percarbonate can be coated by silicate, borate or water soluble surfactant active.Percarbonate can be from various industrial raw material, for example FMC, Solvay and Tokai Denka.
Can also adopt the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach activator, and it can preparation (promptly in washing process) on the spot in corresponding to the peroxide aqueous acid of bleach activator.The non-limiting example of each of promoting agent is disclosed in Mao etc. and obtains among the US4915854 and US4412934 of power in April 10 nineteen ninety.Generally be nonanoyl oxygen benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) promoting agent, also can adopt their mixture.Referring to other type SYNTHETIC OPTICAL WHITNER and the promoting agent among the US4634551.
The general formula of acid amides deutero-bleach activator very preferably is:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L
R wherein
1Be the alkyl that contains 6 to 12 carbon atoms of having an appointment, R
2Be the alkylidene group that contains 1 to 6 carbon atom of having an appointment, R
5Be hydrogen or alkyl, aryl or the alkaryl that contains 1 to 10 carbon atom, L is the leavings group of any use.Leavings group be since cross the hydrolysis negatively charged ion to bleach activator carry out nucleation the result and from bleach activator by any group of metathetical.Preferred leavings group is the Phenylsulfonic acid root.
Preferred embodiment with bleach activator of above-mentioned general formula comprises (6-decoylamide-caproyl) oxygen benzene sulfonate, (6-pelargonamide caproyl) oxygen benzene sulfonate, (6-decanoyl-caproyl) oxygen benzene sulfonate and their mixture, and they are documented at this in conjunction with among the US4634551 as a reference.
Other kind of bleach activator is included in the promoting agent of disclosed benzo oxazinyl in the US4966723 of bulletin on October 30 nineteen ninety such as Hodge, its at this in conjunction with as a reference.Benzoxazine class promoting agent very preferably is:
Also have another kind of preferred bleach activator to comprise the acyl lactam promoting agent, particularly have the acyl caprolactam and the acyl group Valerolactim of following general formula:
R wherein
6Be hydrogen or contain 1 to alkyl, aryl, alkoxy aryl or the alkaryl of about 12 carbon atoms.Lactan promoting agent very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.Also can obtain the US4545784 of power on October 8th, 1985 referring to Sanderson, in conjunction with as a reference, it discloses the acyl caprolactam that is absorbed in the Sodium peroxoborate, comprises benzoyl caprolactam at this for it.
SYNTHETIC OPTICAL WHITNER outside the oxygen bleaching reagent also is known in the art and also can be used for the present invention.The particularly advantageous non-oxygen bleaching agent of one class comprises the photosensitization SYNTHETIC OPTICAL WHITNER, as the sulfonated zinc and/or the aluminium phthalein mountain valley with clumps of trees and bamboo.Obtain the US4033718 of power on July 5th, 1977 referring to Holcombe etc.If adopt, detergent composition generally contains 0.025% this class SYNTHETIC OPTICAL WHITNER, particularly the sulfonic acid zinc phthalein mountain valley with clumps of trees and bamboo to about 1.25% weight of having an appointment.
If desired, bleaching compounds can be by manganic compound catalysis.This compounds is known in the art and comprises for example manganese-based catalyst that it is disclosed in US5246621, US5244594, US5194416, US5114606 and EP549271A1,549272A1,544440A2 and 544490Al; The preferred example of these catalyzer comprises Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)
2-(ClO
4)
2, Mn
IV 4(u-O)
6(1,4,7-three azo-cycle nonanes)
4(ClO
4)
4, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)
2(ClO
4)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)-(OCH
3)
3(PF
6) and their mixture.Other metal matrix bleaching catalyst comprises and is disclosed among US4430243 and the US5114611 those.The manganese that use has various complex ligands promotes to bleach and also is disclosed in following US4728455,5284944,5246612,5256779,5280117,5274147,5153161 and 5227084.
In fact and not as limiting, can adjust the compositions and methods of the invention, make the active bleaching catalyst material that in the water-washing liquid body, has 1/10,000,000 concentration, and preferably contain the 0.1ppm that has an appointment to about 700ppm in laundry liquid, more preferably from about 1ppm is to the catalytic specie of about 500ppm.
Many other components that can be used for detergent composition can be included in the composition, comprise other active ingredient, carrier, hydrotropic agent, processing material, pigment or dyestuff, be used for liquid preparation solvent, be used for the solid packing of bar composition etc.High if desired foam can add profoamer, for example C in the said composition
10-C
16Alkylolamide is generally 1%-10%.C
10-C
14Simple ethanol and two alcohol amide illustrate the general classes of this class A foam A promotor.Employing contains high additive foam tensio-active agent, and for example this class A foam A promotor of amine oxide, trimethyl-glycine and above-mentioned sultaine also is favourable.If desired, the solubility magnesium salts is as MgCl
2, MgSO
4Deng can adding so that more foam to be provided, and promote to remove the smeary performance with the concentration of 0.1%-2%.
The various scrubbed component that are used for the present composition randomly can then apply said matrix further with hydrophobic coating and stablize by said component is absorbed porous hydrophobic matrix.Preferably washing component mixed with tensio-active agent before being absorbed into porous matrix.In use, cleaning composition is discharged into from matrix in the water-washing liquid body, and it plays its required cleaning function therein.
In order to illustrate in greater detail this technology, (trade mark SIPERNATD10 is DeGussa) with the C that contains 3%-5% for porous hydrophobic silicon-dioxide
13-C
15The protolysate enzyme solution of ethoxylated alcohol (E07) nonionogenic tenside mixes.In general, enzyme/surfactant soln is 2.5 times of silica weight.The powder that generates is dispersed under stirring state in the silicone oil and (can adopts the various silicone oil of viscosity at 500-12500).The silicone oil dispersion that generates is emulsified or join in the final washing composition matrix.By this method; component; for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, photosensitizers, pigment, white dyes, fabric adjust agent and the hydrolyzable tensio-active agent can be " protected ", and to be used for washing composition, comprises in the liquid laundry detergent compositions.
Liquid detergent composition contains water and other solvent as carrier.Low-molecular-weight primary alconol and secondary alcohol, representational is that methyl alcohol, ethanol, propyl alcohol and Virahol are to be suitable for.MHA is preferred for strengthening the dissolving tensio-active agent, still, also can adopt polyhydroxy-alcohol, as contains 2 to about 6 carbon atoms and 2 (as 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) to about 6 hydroxyls.Said composition can contain 5% to 90%, is generally 10% to 50% this carrier.
The detergent composition here preferably is mixed with and is being used for pH that the water-based washing operation makes washing water between about 6.5 and about 11, preferably between about 7.5 and 10.5.Laundry product is generally pH9～11.Be used for that pH is controlled at the technology of recommending use range and comprise use buffered soln, alkali, acid etc., this is well known by persons skilled in the art.
Enzyme
Detergent composition of the present invention can contain enzyme to be used for various uses, comprise from spot such as surface removal protein-based, carbohydrate-based or the triglyceride level base of fabric, preventing dye transfer (for example in laundry processes), and restore for fabric.Suitable enzyme comprises the mixture of proteolytic enzyme, amylase, lipase, cellulase, peroxidase and any applicable raw materials, for example vegetables, animal, bacterium, fungi and yeast source.Preferred select to be subjected to some factors, for example pH is active and/or stability, thermostability and to the stability influence of activated detergent, auxiliary agent etc.From this respect, preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.
Here " detersive enzyme " of Cai Yonging is meant any enzyme that has cleaning, decontamination or other beneficial effect in laundry, cleaning of hard surfaces or body care detergent composition.Preferred detersive enzyme is a lytic enzyme, for example proteolytic enzyme, amylase and lipase.The preferred enzyme that is used to wash purpose includes, but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.
Enzyme is generally to be enough to the providing amount of " washing significant quantity " to join in washing composition or the laundry additive composition.Said " washing significant quantity " is meant can be to matrix, and for example fabric produces cleaning, decontamination, de-sludging, brightens, any amount of deodorizing or bright-coloured improvement effect.In fact for present industrial production, general amount be every gram detergent composition up to 5 milligrams of weight, more generally be 0.01 to 3 milligram organized enzyme.Be noted that also composition of the present invention generally contains 0.001% to 5%, preferred 0.01% to 1% weight industrial enzyme preparation.Proteolytic enzyme exists with the activity that is enough to make every gram composition have 0.005 to 0.1 dalton unit (AU) in these industrial preparations usually.For some washing composition, the organized enzyme content that need to improve industrial preparation to be reducing the total amount of on-catalytic active substance, thereby is modified into a little/film forming or other net result.Higher active concentration also is that the high concentration detergent preparation is needed.
The example that proteolytic enzyme is suitable for is a subtilysin, and it is the specified genus preparation by Bacillus subtillis and lichenoid form bacillus.A kind of useful proteases be by the PH scope of maximum activity in 8～12 Bacillaceae preparation, this Bacillaceae by the Novo Industries A/S (this paper is " Novo ") of Denmark with ESPERASE
Exploitation and sale.The preparation of this kind of enzyme and similar enzyme is documented among the GB1243784 of Novo.The ALCALASE that is provided by Novo is provided other enzyme that is suitable for
And SAVINASE
With the International Bio-Synthetics by Holland, the MAXATASE that Inc. provides
And be disclosed in EP130756A, the protease A on January 9th, 1985 and be disclosed in EP303761A, on April 28th, 1987 and EP130756A, the proteolytic enzyme B on January 9th, 1985.Also can be referring to the high pH proteolytic enzyme of the WO9318140A that is documented in Novo from bacillus NCIMB40338.The enzyme washing composition that contains proteolytic enzyme, one or more other enzymes and reversible proteinase inhibitor is documented among the WO9203529A of Novo.Other preferred proteolytic enzyme comprises Procter﹠amp; Those of the WO9510591A record of Gamble.When needs, can adopt Procter﹠amp; The reduction of the WO9507791 record of Gamble absorbs and improves the proteolytic enzyme of hydrolysis.The proteolytic enzyme that is used for the recombinant chou Trypsin enzyme of washing composition of the present invention is documented in the WO9425583 of Novo.
The preferred liquid laundry detergent compositions of the present invention also contains the proteolytic enzyme of at least 0.001% weight.It is just enough that yet the proteolytic enzyme of significant quantity is used for the said liquid laundry detergent compositions of the present invention.Said " significant quantity " is meant can be to matrix, and for example fabric produces cleaning, scale removal, decontamination, brightens, any amount of deodorizing or bright-coloured improvement effect.In fact, with regard to existing industrial production, general amount is that every gram detergent composition is up to about 5 milligrams of weight, is generally 0.01 to 3 milligram organized enzyme.Also be noted that: composition of the present invention generally contains 0.001～5%, the industrial enzyme of preferred 0.01～1% weight.In such industrial production, proteolytic enzyme of the present invention generally exists to be enough to making every gram composition have the 0.005 active amount that arrives dalton (Anson) unit (AU) of 0.1A.
The proteolytic enzyme that preferred liquid laundry detergent composition of the present invention contains is meant " proteolytic enzyme D ", it is by being equal at said carbonylic hydrolase+position of 76 positions by the carbonylic hydrolase precursor, also preferred combination one or several be equal to be selected from according to the layout of bacillus amyloliquefaciens subtilysin sequence+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+274 amino acid residue position replaces a plurality of amino-acid residues to prepare according to the sequence of bacillus amylolyticus subtilysin with different amino acid, as Genencor International described in the April 20 nineteen ninety-five disclosed WO95/10615.
The effective protein proteins enzyme also be documented in following PCT open in: WO95/29979, November 9 nineteen ninety-five, The Procter﹠amp; Gamble Company; WO95/30010, November 9 nineteen ninety-five, The Procter﹠amp; Gamble Company and WO95/30011, November 9 nineteen ninety-five, The Procter﹠amp; Among the Gamble Company.
Preferred proteolytic enzyme still is the Pseudomonas proteolytic enzyme of modification, as be disclosed in EP87303761.8, on April 28th, 1987 (particularly at the 17th, 24 and 98 page), and it is referred to herein as " proteolytic enzyme B ", and EP199404, Venegas, on October 29th, 1986, it relates in this article the modification Pseudomonas proteolytic enzyme that is called as " protease A ", protease A is disclosed in EP130756A, and on January 9th, 1985, proteolytic enzyme B is disclosed in EP303761A, on April 28th, 1987 and EP130756A, on January 9th, 1985.
Being used for preferred protease of the present invention is bacterial serine proteolytic enzyme.For example be disclosed in EPA87.303761.8 (submission on April 28th, 1987), the particularly proteolytic enzyme on 17,24 and 98 pages and be called proteolytic enzyme B; Also referring to the EPA199404 of disclosed Venegas on the 29th October in 1986, the bacterial serine proteolytic ferment of indication modification, be called among the EPA130756A that protease A is disclosed on January 9th, 1985, proteolytic enzyme B is disclosed among EP303761A (on April 28th, 1987) and the EP130756A (on January 9th, 1985).
The amylase that the present invention is suitable for comprises, for example the described α-Dian Fenmei of the GB1296839 of Novo; International Bio-Synthetics, the RAPIDASE of Inc
TERMAMYL with Novo
, Novo FUNGAMYL
Be effective especially.Improve stability with enzyme, for example the technology of oxidative stability is known.Referring to, J.Biological Chem. for example, the 260th volume, the 11st, in June, 1985,6518-6521 page or leaf.The certain preferred embodiments of the present composition can adopt the amylase that improves stability in washing composition, particularly improves the TERMAMYL with respect to industrial employing in 1993
The oxidative stability measured of reference point.The preferred amylase of these the present invention has the diastatic feature of " improving stability ", it is characterized in that one or more aspect at least below produces bigger improvement: oxidative stability, as to hydrogen peroxide/tetra acetyl ethylene diamine in the buffered soln of pH9～10; Thermostability, as wash temperature under, 60 ℃ according to appointment; Perhaps alkaline stability as under about 8 to about 11 pH, is measured the enzyme contrast with above-mentioned reference point.Stability can adopt the disclosed engineering test in any this area to measure.Referring to for example with reference to WO9402597.The enzyme that improves stability can be obtained by Novo or Genencor International.One class the present invention enzyme very preferably has and adopts on the spot mutagenic compound from one or several bacillus amylases, the general character for preparing of bacillus α-Dian Fenmei particularly, and no matter whether a kind of, two kinds or more of amylase strains are instantaneous precursors.The enzyme that improves oxidative stability is compared with above-mentioned reference amylase and is preferred for particularly bleaching, more preferably with the detergent composition of the distinct oxygen bleaching of chlorine bleaching in.The preferred amylase of this class comprises (a) a kind of amylase that obtains the WO9402597 of power according to the Novo that puts down in writing previously on February 3rd, 1994, can further illustrate with a kind of mutant, wherein adopt L-Ala or Threonine, preferred Threonine replaces methionine residues, changes residue and is positioned at and is known as TERMAMYL
The position 197 of bacillus licheniformis alpha-amylase, perhaps similar parent amylase is as the variant of the correspondence position of bacillus amyloliquefaciens, subtilis or Bacillus licheniformis; (b) improve the amylase of stability, as the exercise question in the 207th American ChemicalSociety of 13-17 day in March, 1994 National Meeting, delivered by C.Mitchinson for described in the paper of " Oxidatively Resistant α-Amylases ".Should notice that wherein SYNTHETIC OPTICAL WHITNER makes the α-Dian Fenmei inactivation in automatic dishwashing detergent, but the amylase that improves oxidative stability is prepared from Bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) can be thought the residue that most possibly is modified.Met 8,15,197,256,304,366 and 438 replaces in the position sometimes, causes specific sudden change, particularly importantly M197L and M197T, and the M197T variant is the most stable variant.Stability is at CASCADE
And SUNLIGHT
Middle mensuration; (c) particularly preferred amylase is included in further improved amylase variant in the instantaneous parent, as described in the WO9510603A and applicant Novo with DURAMYL
Provide.The amylase of other particularly preferred raising oxidative stability is included in to be put down in writing among the WO9402597 of the WO9418314 of GenencorInternational and Novo.Can adopt any other to improve the amylase of oxidative stability, for example prepare by direct mutagenesis by spendable diastatic known mosaic, hybrid or simple mutant parent.Can carry out the improvement of other preferred enzyme.WO9509909 referring to Novo.
The adoptable cellulase of the present invention comprises bacterium class and Mycophyta, and preferred ideal pH is between 5 and 9.5.Barbesgoard etc. disclose by Humicola insolens or rotten fungal cellulase of planting mould genus DSM1800 preparation or cellulase 212-by fungi preparation that belongs to Aeromonas and the cellulase Dolabella Auricula Solander that extracted by the hepatopancreas of shipworm at the US4435307 on March 6th, 1984.Suitable cellulase also is disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832.CAREZYME
(Novo) be effective especially.WO9117243 referring to Novo.
The suitable lipase that is used to wash purposes comprises those by Rhodopseudomonas, and for example microorganism of Pseudomonas stutzeri ATCC19.154 preparation is disclosed as GB1372034.Lipase also can be referring at disclosed Japanese patent application 5320487 on February 24th, 1978.This lipase is by Amano Pharmaceutical Co.Lth., Nagoya, and Japan provides with trade name Lipase P " Amano " or " Amano-P ".Other suitable industrial lipase comprises Amano-CES, the lipase that is produced by Chromobacter viscosum, the Chromobacter viscosumvar.lipolyticumNRRLB3673 that provides as the ToyoJozo Co.Tagata by Japan; The Chromobacter viscosum lipase that provides by the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland, and by the lipase of gladiolus pseudomonas preparation.By Humicola lanuginosa deutero-and by the LIPOLASE of Novo industrial preparation
Enzyme referring to EP341947, here is preferred lipase.On the books in the WO9414951A of Novo by lipase and amylase variant that peroxidase is stable.Referring to WO9205249 and RD94359044.
Be applicable to that Cutinase enzyme of the present invention is documented among the WO8809367A of Genencor.
Peroxidase can with the oxygen raw material, as combinations such as percarbonate, perborate, oxyhydroxide, carry out " solution bleaching " or prevent in washing process dye transfer or pigment is transferred to other matrix that exists from matrix washing soln.Known superoxide comprises horseradish peroxidase, ligninase, halo peroxidase, as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in Novo and obtains among the WO8909813A of the WO89099813A of power and Novo on October 19th, 1989.
The scope of enzyme material and they are attached to method in the synthetic detergent composition are documented in the WO8908694A of the WO9307263A of Genencor International and WO9307260A, Novo and McCarty etc. obtain power on January 5th, 1971 US3553139.Enzyme also is disclosed in Place etc. and obtains the US4101457 of power and obtain the US4507219 of power at Hughes on March 26th, 1985 on July 18th, 1978.Can be effective to the enzyme of liquid detergent preparation and it is attached to method in this prescription be disclosed in Hora etc. and obtain among the US4261868 of power on April 14th, 1981.The enzyme that is used for washing composition can be stablized by various technology.The stabilization technique of enzyme is disclosed in and is to obtain the US3600319 of power at Gedge etc. on August 17th, 1971 typically, and Venegas is in the EP199405 and EP200586 on October 29th, 1986.The enzyme stabilising system is also on the books, for example at US3519570.A kind of effective subtilysin AC13 that produces proteolytic enzyme, zytase and cellulase is documented among the WO9401532A of Novo.
The enzyme stabilising system
The enzyme that contains of the present invention has an appointment 0.001% to about 10%, preferred about 0.005% to about 8% but the liquid composition that is not limited to this can contain, most preferably from about the enzyme stabilising system of 0.01% to 6% weight.This kind of enzyme stabilising system can be any stabilising system compatible with detersive enzyme.Such system was that the active substance by other preparation provides or added respectively by formulator or the manufacturers that is washed agent finished product enzyme and provides originally.This class stabilising system can for example contain calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and their mixture, and designs at different stable problems with physical condition according to the type of detergent composition.
A stable method is to adopt the water-soluble material of calcium ion and/or magnesium ion in final composition, so that enzyme contains this ion.Calcium ion is generally more effective than magnesium ion, and is that the present invention is preferred, if having only a kind ofly, can adopt calcium ion.General detergent composition, particularly liquid, every liter of finished product detergent composition contains has an appointment 1 to about 30, preferred about 2 to 20, and more preferably from about the calcium ion of 8 to 12 mmoles can change according to the concentration that comprises diversity, type and adding enzyme.Preferred water-soluble Ca salt and the magnesium salts of adopting comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; Usually can adopt calcium sulfate or corresponding to the magnesium salts of typical calcium salt.Yes for the concentration of further raising calcium and/or magnesium effectively, for example can promote the delipidation of some type list surface-active agent.
Another kind of stabilising method are to adopt borate.US4537706 referring to Severson.When using the borate stablizer, its concentration can up to composition 10% or more, and generally up to boric acid or other borate compound of about 3% weight, as the concentration of borax or ortho-borate purposes applicable to liquid washing agent.The boric acid that replaces as phenyl-boron dihydroxide, butane boric acid, can be used for substituted boracic acid to bromophenyl boric acid etc., and can be reduced in the total amount of boron in the detergent composition by the boron derivative that adopts this class to replace.
The stabilising system of some cleaning composition can further contain 0 to about 10%, and the preferred about 0.01% chlorine bleaching scavenging agent to about 6% weight works to enzyme and makes its inactivation with the chlorine bleaching material that prevents to exist in many water sources, particularly under alkaline condition.The concentration of chlorine hour in water, generally at about 0.5ppm in about 1.75ppm scope, the available chlorine in the cumulative volume of whole water of catalase, for example in the fabric washing process, can be quite big; Therefore enzyme has problems sometimes to the stability of the chlorine of use.Owing to can may be present in some instant compositions with isolating amount from stabilising system with the perborate or the percarbonate of chlorine bleach reaction, it may be not too important using other anti-chlorine stablizer, although use them can obtain improved result.Suitable chlorine scavenging agent negatively charged ion is known and is easy to use, if use, can be the salt that contains ammonium cation and sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Antioxidant, as carbamate, xitix etc., organic amine, as ethylene diaminetetraacetic acid (EDTA) or its an alkali metal salt, Monoethanolamine MEA BASF (MEA) and their mixture also can adopt.Equally, can add special enzyme inhibition system, so that various enzyme has maximum consistency.Other conventional scavenging agent, raw material as hydrosulfate, nitrate, muriate, hydrogen peroxide, as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, spissated phosphoric acid salt, acetate, benzoate, Citrate trianion, formate, lauroleate, malate, tartrate, salicylate etc. and their mixture also can adopt if desired.In general, because the effect of chlorine scavenging agent can be finished by being considered to the component (as the hydrogen peroxide raw material) that performance better lists respectively, need not to add independent chlorine scavenging agent, be not included in of the present invention containing in the enzyme embodiment unless have the compound of this required degree effect; Even adding scavenging agent only is for optimum.And formulator can avoid using any enzyme scavenging agent or stablizer according to chemist's universal experience, if adopt, they are extremely incompatible with other reactive component when preparation.As for adopting ammonium salt, this class salt can mix with detergent composition simply, but is easy to absorb water and/or discharges ammonia in storage process.Therefore, this material if present, need be protected in particle, is put down in writing among the US4652392 as Baginski etc.
Auxiliary agent
Detergent builder can randomly be included in the composition of the present invention, and this helps to control mineral substance hardness.Can adopt inorganic and organic additive.Auxiliary agent generally is used for fabric cleaning composition, to help removing particulate fouling.
The content of auxiliary agent can change in wide region according to end-use and its required physical form of composition.When containing sometimes, said composition generally contains the auxiliary agent at least about 1%.Liquid preparation generally contains 5% to about 50%, more generally about 5% detergent builder to about 30% weight of having an appointment.Granular preparation generally contains 10% to about 80%, more generally about 15% detergent builder to about 50% weight of having an appointment.But, and do not mean that the lower or more high-load auxiliary agent of eliminating.
Inorganic or phosphorus-containing detergent auxiliary agent comprises basic metal, ammonium and the alkanol ammonium salt (representational is three polyphosphonates, pyrophosphate salt and glassy polymeric metaphosphate) of (but being not limited to) polyphosphoric acid, phosphoric acid salt, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and aluminosilicate.And needing the nonphosphate auxiliary agent in some cases.Importantly the effect of the present composition is good unexpectedly, even exist under so-called " weak " auxiliary agent (comparing) situation with phosphoric acid salt, for example Citrate trianion is also like this during " bad auxiliary " of perhaps taking place under so-called employing zeolite or laminar silicic acid salt assitant situation.
The example of silicate auxiliary agent is an alkalimetal silicate, particularly those SiO
2: Na
2Silicate and the layered silicate of the ratio of O between 1.6: 1 to 3.2: 1, for example H.P.Rieck obtained the lamina sodium silicate of describing among the US4664839 of power on May 12nd, 1987.NaSKS-6 is the trade(brand)name (generally being abbreviated as " SKS-6 ") of the crystal layered silicate that provided by Hoechst.Different with zeolite builder, NaSKS-6 silicate auxiliary agent does not contain aluminium.NaSKS-6 is δ-Na
2SiO
5The layered silicate of form.It can be by the method preparation of for example putting down in writing in the DE-A-3417649 of Germany and DE-A-3742043.SKS-6 is used for silicate very preferably of the present invention, but other this class layered silicate is NaMSi as general formula
xO
2x+1YH
2Those of O, wherein M is sodium or hydrogen, and x is from 1.9 to 4 number, and is preferred 2, and y is from 0 to 20 number, and preferred 0 can be used for the present invention.Various other layered silicates from Hoechst comprise NaSKS-5, NaSKS-7 and NaSKS-11, as α, β and γ form.As mentioned above, δ-Na
2SiO
5(NaSKS-6 form) is that the present invention is most preferred.Other silicate also is effectively, Magnesium Silicate q-agent for example, and it plays crisp dose in granular preparation, as the stable reagent of oxygen bleaching agent and as the component of foam inhibition system.
The example of carbonate auxiliary agent is alkaline-earth metal and alkaline carbonate, for example is disclosed in the German Patent 2321001 on November 15th, 1973.
The aluminosilicate auxiliary agent is effective in the present invention.The aluminosilicate auxiliary agent is important in the at present commercially available high-efficient granule detergent composition of great majority, and also is important adjuvant component in liquid detergent composition.The aluminosilicate auxiliary agent comprises those with following general formula:
M
z(zAlO
2)
y·xH
2O
Wherein z and y are at least 6 integers, and the molar ratio of z and y is in 1.0 to 0.5 scope, and x is from about 15 to about 264 integer.
Effectively the aluminosilicate ion exchange material is industrial spendable.These aluminosilicates structurally can be crystal or unbodied, and can be natural aluminosilicate or synthetic.A kind of method for preparing the aluminosilicate ion exchange material is disclosed in Krummel etc. and obtains among the US3985669 of power on October 12nd, 1976.Can be used for preferred composite crystals aluminosilicate ion exchange material of the present invention and can adopt called after zeolite A, zeolite P (B), zeolite MAP and X zeolite.In particularly preferred embodiments, the crystalline aluminosilicate ion exchange material has following general formula:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
Wherein x is from about 20 to about 30 number, particularly about 27.This material is known as zeolite A.The present invention also can adopt dehydration zeolite (x=0～10).Preferably the particulate diameter is about 0.1～10 micron aluminosilicate.
The organic detergent auxiliary agent that is applicable to the object of the invention includes, but are not limited to various polycarboxylic acid salt compounds.The present invention adopts " polycarboxylate " to be meant to have a plurality of carboxylic acid root balls, the compound of preferred at least 3 carboxylate radicals.The polycarboxylate auxiliary agent generally can join in the composition with the form of acid, and can add with the form of its neutralized salt.When adopting salt form, preferred as alkali, for example sodium, potassium and lithium or pure ammonium salt.
Included in the polycarboxylate auxiliary agent is all kinds of effective substance.The important polycarboxylate auxiliary agent of one class comprises the ether polycarboxylate, comprises oxygen di-succinate, as Berg.Obtain among the US3128287 of power and Lamberri etc. obtains among the US3635830 of power disclosed on January 18th, 1972 on April 7th, 1964.Also can obtain " TMS/TDS " auxiliary agent of the US4663071 of power referring to Bush etc. on May 5th, 1987.Suitable ether polycarboxylate also comprises ring compound, particularly alicyclic compound, and is for example disclosed in US3923679,3835163,4158636,4120874 and 4102903.
Other effective detergent builder comprise the ether hydroxy-polycarboxylate, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxyl methyl oxygen Succinic Acid, poly-acetate, as the ammonium salt of various basic metal, ammonium and the replacement of ethylene diaminetetraacetic acid and nitrilotriacetic acid(NTA), and polycarboxylate, as mellitic acid, Succinic Acid, oxygen di-Succinic Acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxyl methyl oxygen Succinic Acid and its soluble salt.
The Citrate trianion auxiliary agent is the polycarboxylate auxiliary agent that is used for the particularly important of efficient liquid detergent formulations as citric acid and its soluble salt (particularly sodium salt), and this is because they are because be that renewable raw materials can utilize with its biodegradable.Citrate trianion also can be used in the particulate composition, particularly is used in combination with zeolite and/or laminar silicic acid salt assitant.Oxygen di-succinate also is effective especially in these compositions and combination.
What also be suitable in detergent composition of the present invention is, 3, and 3-dicarboxyl-4-oxa--1,6-adipate and related compound, they are disclosed in Bush and obtain among the US4566984 of power on January 28th, 1986.Effectively the Succinic Acid auxiliary agent comprises C
5-C
20Alkyl and alkenyl Succinic Acid and its salt.Particularly preferred this compounds is the dodecenyl succinic Succinic Acid.The specific examples of succinate comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.The lauryl succinate is a preferred auxiliary agent in this class, is documented in disclosed EP86200690.5/0200263 on November 5th, 1986.
Other polycarboxylate that is suitable for be disclosed in Crutchfield etc. on March 13rd, 1979 disclosed US4144226 and Diehl obtain among the US3308067 of power on March 7th, 1967.Also referring to the US3723322 of Diehl.
Lipid acid is as C
12-C
18Monocarboxylic acid also can join in the said composition separately or with above-mentioned auxiliary agent, particularly Citrate trianion and/or the combination of succinate auxiliary agent, makes it have additional auxiliary agent activity.Use lipid acid generally can reduce foam like this, this will depend on formulator.
Under the situation that adopts the phosphorus base auxiliary agent, and particularly at the bar-shaped preparation that is used for hand-washing operation, can use various alkali metal phosphates, for example known tripoly phosphate sodium STPP, trisodium phosphate and former sodium phosphate.Also can adopt the phosphonate auxiliary agent, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate (referring to, US3159581,3213030,3422021,3400148 and 3422137 for example).
Sequestrant
Detergent composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, the fragrant chelating agent of polyfunctional group replacement and their mixture, and they all describe in the back.Although do not want to be limited by theory, can think that the effect part of these materials is to remove the unexpected ability of iron and mn ion because they have by forming the soluble chelating thing from washing soln.
The aminocarboxylate of useful as selective sequestrant comprises ethylene diaminetetraacetic acid salt, N-hydroxyethyl ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylene diamine four propionic salts, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their ammonium salt of basic metal, ammonium and replacement and their mixture.
When allowing the total phosphorus of low levels at least in detergent composition, amino phosphonates do also is applicable in composition of the present invention as sequestrant, and comprises ethylene diamine four (methylene phosphonic acid salt), as DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.
The fragrant chelating agent that polyfunctional group replaces also is applicable to composition of the present invention.Obtain the US3812044 of power on May 21st, 1974 referring to Connor etc.The preferred compound of this class acid form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
The preferred biodegradable cheating agent that the present invention adopts is ethylene diamine two succinates (" EDDS "), and [S, S] isomer is particularly put down in writing in obtaining the US4704233 of power on November 3rd, 1987 as Hartman and Perkins.
If use, these sequestrants generally are that about 0.1% of detergent composition of the present invention arrives about 10% weight.If use, more preferably sequestrant is that about 0.1% of said composition arrives about 3.0% weight.
Remove the reagent of clay/antiredeposition
Composition of the present invention can also randomly contain the amine with the water-soluble ethoxylation of removing clay and antiredeposition character.The granular detergent composition that contains these compounds generally contains the 0.01% water-soluble ethoxylated amine to about 10.0% weight of having an appointment; Liquid detergent composition generally contains has an appointment 0.01% to about 5%.
Most preferred decontamination and antiredeposition reagent are the tetrens of ethoxylation.Representational ethoxylated amine obtains among the US4597898 of power on the books at VanderMeer on July 11st, 1986.The reagent of another kind of preferred removal clay-antiredeposition is cation compound, and it is disclosed in Oh and Gosselink is disclosed among the EP111965 on June 27th, 1984.Other operable removal clay/antiredeposition reagent comprises the amine polymer of the ethoxylation on June 27th, 1984 disclosed EP111984 that is disclosed in Gosseink; Be disclosed in the amphiphilic polymers on July 4th, 1984 disclosed EP112592 of Gosseink; With Connor disclosed amine oxide on October 22nd, 1985 disclosed US4548744.Other removal clay known in the art and/or antiredeposition reagent also can be used for composition of the present invention.Another kind of preferred antiredeposition reagent comprises carboxy methyl cellulose (CMC) material.These materials are known in the art.
Polymeric dispersant
It is favourable that polymeric dispersant uses to the amount of about 7% weight with 0.1% of the present composition, particularly exists under the situation of zeolite and/or laminar silicic acid salt assitant.The suitable polymers dispersion agent comprises polymer poly-carboxylate and polyoxyethylene glycol, although other known in the artly also can use.Although can be sure of not want to limit with theory, when being used in combination with other auxiliary agent, this polymeric dispersant improves whole detergent builder performance by suppressing crystal growth, discrete particles dirt and antiredeposition.
Polymeric polycarboxylate material can prepare by polymerization or the suitable unsaturated monomer of copolymerization, preferably its sour form.The unsaturated monomer acid that can polymerization generates suitable polymeric polycarboxylate comprises vinylformic acid, toxilic acid (perhaps maleic anhydride), fumaric acid, itaconicacid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Exist and do not contain carboxylate groups, for example the polymer poly-carboxylate or the monomer segment of vinyl methyl ether, vinylbenzene, ethene etc. are suitable for, as long as such segment is no more than about 40% weight.
The polymeric polycarboxylate of particularly suitable can be prepared by vinylformic acid.The present invention effectively polymkeric substance of this class acrylic is the acrylic acid water-soluble salt of polymeric.The molecular-weight average of the polymkeric substance of this class acid form is preferably 2000 to 10000, and more preferably 4000 to 7000, most preferably 4000 to 5000.The water-soluble salt of this class acrylate copolymer can comprise for example ammonium salt of basic metal, ammonium and replacement.This class soluble polymer is a known substances.This class polyacrylate is used for detergent composition and for example has been disclosed in that Diehl obtained among the US3308067 of power on March 7th, 1967.
The multipolymer of vinylformic acid/maleic also can be as the preferred component of dispersion/antiredeposition reagent.This class material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of the multipolymer of this class acid form is 2000 to 100000, more preferably from about 5000 to 75000, most preferably from about 7000 to 65000.Acrylate and maleic acid ester segmental ratio were generally 30: 1 to about 1: 1 in this polymkeric substance, more preferably from about 10: 1 to 2: 1.The aqueous solution salt of this class vinylformic acid/maleic acid comprises for example ammonium salt of an alkali metal salt, ammonium salt and replacement.The multipolymer of this class water-soluble acrylic ester/maleic acid ester is a known substances, and it is documented in the EP66915 that is disclosed in December 15 nineteen eighty-two and is disclosed among the EP193360 on September 23rd, 1986, and it has also described the polymkeric substance that contains the vinylformic acid hydroxy-propyl ester.Other effective dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol trimer.This class material also is disclosed among the EP193360, comprises for example trimer of toxilic acid/vinylformic acid of 45/45/10/vinyl alcohol.
The another kind of polymkeric substance that can contain is polyoxyethylene glycol (PEG).PEG has dissemination and can be used as removal clay-antiredeposition reagent.Their general molecular weight ranges are about 500 to about 100000 for this reason, and preferred about 1000 to about 50000, more preferably from about 1500 to 10000.
Also can adopt poly aspartic acid and polyglutamic acid dispersion agent, particularly use with zeolite builder.Dispersion agent, for example the preferred molecular weight of poly aspartic acid (on average) is about 10000.
Whitening agent
Any white dyes known in the art or other whitening agent can join in the detergent composition of the present invention to be generally 0.05% amount to about 1.2% weight.Can be used for commercially available white dyes of the present invention and can be divided into group, it includes, but are not limited to this De Shi, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophen-5,5-dioxide, pyrroles, 5 yuan and 6 yuan of heterocycles and other mix reagent.The example of these whitening agent is disclosed in the Wiley﹠amp by John; Sons is in the M.Zahradnik that New York (1982) publishes " The Production andApplication of Fluorescent Brightening Agents ".
The specific examples that can be used for the white dyes of the present composition illustrates in obtaining the US4790856 of power on December 13rd, 1988 at Wixon.The whitening agent of the PHORWHITE series that is provided by Verona is provided these whitening agent.Other whitening agent that is disclosed in these documents comprises: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Provide by Ciba-Geigy; By being positioned at Artic White CC and the Artic WhiteCWD that gondola Hilton-Davis provides; 2-(4-stryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (stryl) biphenyl; And aminocoumarin.The object lesson of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, two (venz imidazoles-2-yl) ethene of 2-; 1,3-phenylbenzene-phr azoles quinoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; The 2-stryl-naphtho--[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphthalene-[1,2-d] triazole.Obtain the US3646015 of power on February 29th, 1972 referring to Hamilton.Preferred anionic whitening agent of the present invention.
Suds suppressor
Can add in the composition of the present invention and be used to reduce or suppress the compound that foam forms.Suds suppressor as in the what is called described in US4489455 and 4489574 " high density cleaning procedure " and in the European washing machine of muzzle-loading, be particularly important.
Can be well known by persons skilled in the art as the various materials and the suds suppressor of suds suppressor.Referring to, Kirk Othmer Encyclopedia of Chemical Technology for example, the third edition, the 7th volume, the 430th～447 page of (John Wiley﹠amp; Sons., Inc., 1979).An effective especially class suds suppressor contains a carboxylic fatty acids and its soluble salt.Obtain the US2954347 of power in September 27 nineteen sixty referring to WayneSt.John.A carboxylic fatty acids and its salt as suds suppressor contain 10 to about 24, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium salt, and alkanol ammonium salt.
Detergent composition of the present invention also can contain the nonsurfactant suds suppressor.They for example comprise: high-molecular-weight hydrocarbons, for example paraffin, fatty acid ester (as fatty acid glyceryl ester), the fatty acid ester of monohydroxy-alcohol, fatty C
18-C
40Ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, as three-product two that generates to the primary amine that contains 1 to 24 carbon atom or the secondary amine of six-alkyl melamine or cyanuryl chloride and two or three moles-to four-alkyl diamine chlorotriazine, propylene oxide and a stearyl phosphoric acid salt, for example stearyl alcohol phosphoric acid ester and a stearyl two basic metal (as K, Na and Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbon, for example paraffin and halo paraffin can adopt with its liquid form.Liquid hydrocarbon at room temperature be liquid under the normal pressure, its pour point is approximately-40 ℃ to about 50 ℃, minimum boiling point is not less than about 110 ℃ (under normal pressures).The also known wax shape hydrocarbon that adopts, preferred fusing point is lower than about 100 ℃.Hydrocarbon is the suds suppressor of detergent composition preferred class.The hydrocarbon suds suppressor is documented in for example US4265779 that obtains power on May in 1981 5 of Gandolfo etc.Hydrocarbon comprise contain have an appointment 12 to the fat of about 70 carbon atoms, alicyclic ring, fragrance and heterocycle be saturated/or undersaturated hydrocarbon.In that this suds suppressor is discussed is that " paraffin " that is adopted is meant the real paraffin and the mixture of cyclic hydrocarbon.
Another kind of preferred nonsurfactant suds suppressor contains silicone suds suppressor.This class comprises uses poly organic silicon oil, the for example dispersion agent or the emulsifying agent of polydimethylsiloxane, organopolysiloxane oil or resin, the combination of organopolysiloxane and silica dioxide granule, wherein organopolysiloxane is chemisorption or dissolves on silicon-dioxide.Silicone suds suppressor is known in the art, for example is disclosed in Gandolfo etc. and obtains the US4265779 and the Starch of power on May 5th, 1981, and M.S. obtains the EP89307851.9 of power in February 7 nineteen ninety.
Other silicone suds suppressor is disclosed among the US3455839, and it relates to composition and by toward wherein adding the defoam method of the aqueous solution of a small amount of polydimethylsiloxane fluid preparation.
The mixture of the silicon-dioxide of siloxanes and silanization for example is documented among the German Patent DOS2124526.Disclosed siloxanes defoaming agents and suds suppressor are disclosed in the US3933672 of Bartolotta etc. and obtain among the US4652392 of power on March 24th, 1987 at Baginski etc. in granular detergent composition.
A kind of typical siloxanes of the suds suppressor that adopts based on the present invention is the suds suppressor of foam inhibition amount, and it is mainly formed and is:
(ⅰ) polydimethylsiloxane fluid, its viscosity arrives about 1500cs. at 25 ℃ for 20cs.;
(ⅱ) (ⅰ) about 5 of per 100 parts of weight to about 50 parts by (CH
3)
3SiO
1/2Unit and SiO
2The unit is with (CH
3)
3SiO
1/2Unit and SiO
2Unitary ratio is 0.6: 1 to about 12: 1 silicone resin that constitutes;
(ⅲ) (ⅰ) about 1 of per 100 parts of weight is to about 20 parts solid silicone.
In preferred silicone suds suppressor of the present invention, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably) or polypropylene glycol formation.Uncle's silicone suds suppressor be collateralization/crosslinked and be not wire preferably.
In order to further specify, the common liq laundry detergent composition that contains suds suppressor randomly contains has an appointment 0.001 to about 1, preferred about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight % silicone suds suppressor, it comprises the non-aqueous emulsifying agent of (1) basic antifoams, and antifoams is (a) organopolysiloxane, (b) polysiloxane compound of resin siloxanes or polyorganosiloxane resin preparation, (c) filler of good distribution and (d) promote constituents of a mixture (a) (b) and (c) reaction form the mixture of catalysts of silanol hydrochlorate (silanolates); (2) at least a nonionic siloxane tensio-active agent; (3) under polyoxyethylene glycol or the room temperature solubleness in water greater than the multipolymer of the polyethylene glycol-propylene glycol of about 2 weight %; And there is not polypropylene glycol.Similarly amount can be used for particulate composition, gel etc.Referring to Starch December 18 nineteen ninety obtain the US4978471 of power and Starch on January 8th, 1991 obtain power 4983316, Huber etc. obtains the 1st hurdle among the US4639489 and 4749740 of 5288431 and Aizawa etc. of power on February 22nd, 1994, the 46th row is to the 4th hurdle the 35th row.
Silicone suds suppressor of the present invention preferably contains the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and its molecular-weight average is all less than about 1000, preferably between 100 and 800.Polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol multipolymer solubleness at room temperature are preferably greater than about 5 weight % greater than about 2 weight %.
The preferred solvent of the present invention is a molecular-weight average less than about 1000, more preferably between 100 and 800, and the most preferably polyoxyethylene glycol between 200 and 400, and polyethylene/polypropylene glycol, the multipolymer of preferred PPG200/PEG300.Preferred polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene/polypropylene glycol is between about 1: 1 and 1: 10, more preferably between 1: 3 and 1: 6.
It is 4000 that preferred silicone suds suppressor that the present invention adopts does not contain polypropylene glycol, particularly molecular weight.They preferably do not conform to the segmented copolymer that oxyethane and propylene oxide are arranged yet, as PLURONIC L101.
Other suds suppressor of the present invention contains the mixture of secondary alcohol (as 2-alkyl alkanol) and this class alcohol and silicone oil, for example US4798679,4075118 and EP150872 in disclosed siloxanes.This secondary alcohol comprises and contains C
1-C
16The C of chain
6-C
16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it is provided with the trade(brand)name of ISOFOL12 by Condea.The mixture of secondary alcohol is provided with the trade(brand)name of ISALCHEM123 by Enichem.The blended suds suppressor generally contains the mixture that weight ratio is alcohol+siloxanes of 1: 5 to 5: 1.
For any detergent composition that can be used in the automatic washing machine, foam should not be formed into the degree that they overflow washing machine.When using suds suppressor, it preferably exists with the amount of foam inhibition amount.So-called " foam inhibition amount " is meant that the formulator of composition selects the amount of this suds suppressor to make it be enough to control foam, generates the low foam detergent for washing clothes that is used for automatic washing machine.
Composition of the present invention generally contains 0% to about 5% suds suppressor.When the suds suppressor, the general content of a carboxylic fatty acids and its salt is to about 5% weight up to detergent composition.Preferably adopt about 0.5% to about 3% fatty monocarboxylic acid salt suds suppressor.The consumption that silicone suds suppressor is general is up to 2.0% weight of detergent composition, also can adopt higher amount.Because mainly take into account the more a spot of validity that reduces cost with effective control foam, it is feasible that the upper limit is actually.Preferred adopt about 0.01%, more preferably from about 0.25% to about 0.5% silicone suds suppressor to about 1%.As of the present invention, the numerical value of these weight percentage comprises be useful on and organopolysiloxane bonded silicon-dioxide, and all additive materials that can adopt.The consumption of one stearyl phosphoric acid salt suds suppressor generally is about 0.1% to 2% weight of composition.The consumption of hydrocarbon suds suppressor is generally about 0.01% to about 5.0%, also can adopt higher amount.The alcohol suds suppressor generally is 0.2%～3% weight of final product composition having.
Fabric softener
The fabric softener that various washings are general, particularly Storm and Nirschl obtained the US4062647 of power on December 13rd, 1977, and other tenderizer clay known in the art can provide the effect of fabric softener randomly with the 0.5% amount use to about 10% weight of the present composition in laundering of textile fabrics.The clay softening agent can be used in combination with amine and cationic softening agent, and for example be disclosed among the US4375416 in March 1 nineteen eighty-three of Crisp etc. and Harris etc. obtained among the US4291071 of power on September 22nd, 1981.
Dye transfer inhibitor
Composition of the present invention also can contain one or more and can suppress dyestuff transfer to material on another fabric from a kind of fabric in washing process.In general, this class dye transfer inhibitor comprises multipolymer, the manganese phthalein mountain valley with clumps of trees and bamboo, peroxidase and their mixture of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If adopt these reagent, its amount generally be composition about 0.01% to about 10% weight, preferred about 0.01% to about 5%, more preferably from about 0.05% to about 2%.
More particularly, be preferred for polyamine N-oxide pllymers of the present invention and contain the unit with following general structure: R-A
x-P; Wherein P is a polymerizable unit, and it can be connected with the N-O group or the N-O group can form polymerizable unit a part or N-O group can be connected on two unit; A have one of them of a following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; And R is fat, fat, fragrance, heterocycle or the alicyclic group of ethoxylation or their any combination, and the nitrogen or the N-O group that can connect on it in N-O group are the parts of these groups.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example those of pyridine, pyrroles, imidazoles, pyrrolidone, piperidines and their derivative.
The N-O group can be represented with following structural formula:
R wherein
1, R
2, R
3Be fat, fragrance, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; And the nitrogen of N-O group can be connected or form the part of any above-mentioned group with above-mentioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, most preferably pKa＜6.
Can adopt any main polymer chain, as long as formed amine oxide polymers is water miscible and has the performance that suppresses dye transfer.The example of the main polymer chain that is suitable for is polyvinyls, polyolefine, polyester, polyethers, polymeric amide, pi, polyacrylic ester and their mixture.These polymkeric substance comprise unregulated polymer or segmented copolymer, and one of them monomer type is an amine n-oxide, and another monomer type is the N-oxide compound.The amine of amine n-oxide polymkeric substance and the ratio of amine n-oxide were generally 10: 1 to 1: 1000000.But the amine oxide group number that exists in the polyamine oxide polymer can change according to suitable copolymerization or according to the suitable degree of N-oxidation.Polyoxygenated amine can be almost being that the polyreaction of any degree prepares.In general, molecular-weight average is 500 to 1000000; More preferably 1000 to 500000; Most preferably 5000 to 100000.The preferred material of this class can be represented with " PVNO ".
Most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in detergent composition of the present invention, and its molecular-weight average is about 50000, and the ratio of amine and amine n-oxide is about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being meant a class that resembles " PVPVI ") also is that the present invention preferably adopts.Preferably the molecular-weight average of PVPVI is 5000 to 1000000, more preferably 5000 to 200000, most preferably 10000 to 20000.(scope of molecular-weight average is by descriptions in Chemical Annlysis the 113rd volume " Modern Methods of Polymer Characterization " such as Barth, and it is disclosed in this combination as a reference.) molar ratio of PVPVI multipolymer General N-vinyl imidazole and N-vinyl pyrrolidone is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1.These multipolymers can be wire or collateralization.
Composition of the present invention also can adopt Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is about 5000 to 400000, and preferred about 5000 to about 200000, and most preferably from about 5000 to about 50000.PVP ' s is the known to the skilled of detergent applications; Referring to for example EP-A-262897 and EP-A-256696, they in this combination as a reference.The composition that contains PVP also can contain polyoxyethylene glycol (" PEG "), and its molecular-weight average is about 500 to about 100000, preferred about 1000 to about 10000.Preferably PEG and PVP are about 2: 1 to about 50: 1 in the ratio of ppm in washing soln, more preferably 3: 1 to about 10: 1.
Detergent composition of the present invention also can randomly contain the wetting ability white dyes of some types of 0.005% to 5% weight of having an appointment, and it also has the effect that suppresses dye transfer.If adopt this whitening agent, composition of the present invention will preferably contain this fluorescent bleaches of 0.01% to 1% weight of having an appointment.
Can be used for wetting ability white dyes of the present invention and have following general structure:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; And M is salifiable positively charged ion, as sodium ion or potassium ion.
When in above-mentioned general formula, R
1Be anilino, R
2Be N-2-two-hydroxyethyl, M is a positively charged ion, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-family name disulfonic acid and its disodium salt.This specific brightener species is to be sold with the trade(brand)name of Tinopal-UNPA-GX by Ciba-Geigy Corporation.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that is used for detergent composition of the present invention.
When in above-mentioned general formula, R
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino, M is a positively charged ion, and during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-family name disulfonic acid disodium salt.The special whitening agent of this class is to be sold with the trade(brand)name of Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in above-mentioned general formula, R
1Be anilino, R
2Be morpholino, M is a positively charged ion, and during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-family name disulfonic acid, its sodium salt.The special whitening agent of this class is to be sold with the trade(brand)name of Tinopal AMS-GX by Ciba-GeigyCorporation.
Be used for concrete white dyes of the present invention and when being used in combination, have especially effectively dye transfer inhibition effect with selected above-mentioned polymeric dye transfer inhibitor.Like this polymkeric substance of Xuan Zeing (as PVNO and/or PVPVI) with the white dyes (as Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) selected a kind of significant more dye transfer that can provide in the water-based washing soln than in these two kinds of detergent composition components of independent employing be provided suppress effect.Be not subjected to theoretic restriction, can be sure of this class whitening agent, and therefore be deposited on the fabric faster owing to they play such effect to the strong affinity of fabric in washing soln.The degree that whitening agent is deposited in washing soln on the fabric can be determined by so-called parameter " consumption coefficient ".Consumption coefficient generally is that (a) is deposited on the whitening agent and (b) ratio of the original concentration of whitening agent in washing liq on the fabric.Consumption coefficient is suitable for inhibition dye-transfer of the present invention most than higher whitening agent.
Certainly, can think that the compound of other conventional white dyes class can randomly be used for composition of the present invention, so that fabrics in general produces " brightening " effect, rather than real dye transfer suppresses effect.This purposes is conventional to detergent formulations and is known.
The preparation of cotton soil release polymers
Embodiment 1
PEI1700E
7Preparation
Carry out ethoxylation being equipped with thermometric and temperature control, pressure measurement, vacuum and inert gas purge, sampling unit and having added in 2 gallons of stirring-type stainless steel cauldrons of liquid epoxy ethane.The netted tube of one～20 pounds oxyethane (ARC) is set to be come by pump liquid epoxy ethane to be transported to and has in the reactor that is positioned over the tube on the pan of a steelyard, with the changes in weight of monitoring tube.
In reactor, add 750 gram part polyethylene imine based (PEI) (NipponShokubai, Epomin SP-018, listed molecular-weight average 1800 equal about 0.417 mole polymkeric substance and 17.4 mole of nitrogen functional groups).The then sealed reactor and the air of draining (vacuum tightness is reduced to 28 " Hg, then feed nitrogen to 250psia, become normal pressure again).The content of reactor is heated to 130 ℃ under vacuum condition.After about 1 hour, reactor is filled to 250 psia with nitrogen, general formula is cooled to about 105 ℃ with reactor.Then accurately again oxyethane is being added in the reactor gradually in assaying reaction still pressure, temperature and the ethylene oxide flow rate.Close the temperature rising that ethylene oxide pump and cooling cause owing to exothermic heat of reaction with restriction.Temperature is remained between 100 and 110 ℃, in reaction process, stagnation pressure is raise gradually simultaneously.With (being about as much as every PEI nitrogen functional group 1 moles of ethylene oxide) after the oxyethane of 750 grams join reactor altogether, temperature is brought up to 110 ℃, and again reactor was stirred 1 hour.At this moment, adopt vacuum to remove all remaining unreacted ethylene oxide.
Below, continue to adopt vacuum simultaneously reactor to be cooled to about 50 ℃, add the methanol solution (1.74 moles) of the sodium methylate of 376 grams 25% simultaneously with the PEI nitrogen functional group's that obtains 10% load catalyzer.Methanol solution is inhaled into reactor under vacuum condition, then the set point with the temperature of reaction kettle controller is elevated to 130 ℃.Adopt a kind of device to measure the pressure of agitator.Measure the pressure of agitator with temperature and pressure.When methyl alcohol was removed from reactor, the pressure and temperature value of agitator raise gradually, and the viscosity of mixture raises and stablizes and illustrated that most methyl alcohol removed in about 1 hour.With mixture further heating and under vacuum restir 30 minutes.
Remove vacuum and reactor is cooled to 105 ℃, feed nitrogen simultaneously and reach 250psia, become normal pressure again.Reactor is full of nitrogen reaches 200psia.As above again oxyethane is joined in the reactor gradually, simultaneously the flow velocity of pressure, temperature and the oxyethane of accurate assaying reaction still in the process that any temperature that maintains the temperature between 100 and 110 ℃ and control causes owing to exothermic heat of reaction raises.Add in the several hrs process (every mole of PEI nitrogen functional group of result is 7 moles of ethylene oxide altogether) after the 4500 gram oxyethane, temperature is elevated to 110 ℃ and with mixture restir 1 hour.
Then reaction mixture is collected in the container of nitrogen purge, and finally transfers in 22 liters of three mouthfuls of round-bottomed flasks that assembled heating and whipping appts.Add in the 167 gram methane sulfuric acid (1.74 moles) and strong alkali catalyst.Then when stirring, feed 100 cubic feet of rare gas elementes (argon gas or nitrogen) deodorizing by the gas dispersion plate and by reaction mixture, and with mixture heating up to 130 ℃.
Slowly cool off final reaction product and be collected in and use in the Glass Containers of nitrogen purge.
In another preparation, neutralization and deodorizing were finished in reactor before taking out product.
Embodiment 2
PEI1800E
7Quaternized
Add molecular-weight average in 500 milliliters of erlenmeyer flasks that assembled the mechanical stirring rod and be 1800 polymine, it by by ethoxylation to each nitrogen nearly 7 ethylidene oxygen residues (PEI1800, E
7) degree come modification (207.3 grams, 0.590 mole of nitrogen, prepared), and acetonitrile (120 gram) as embodiment 1.Methyl-sulfate (28.3 gram, 0.224 mole) is once joined in the solution of quick stirring, then stop and at room temperature stirring diel.Remove acetonitrile by rotary evaporation at about 60 ℃, then adopt Kugelrohr equipment, until obtaining the required quaternised chocolate thick liquid nano of the part material of 220 grams at about 80 ℃ of further stripping solvents.On the sample of reaction product, obtain
13C-NMR (D
2O) spectrum explanation corresponding to methyl-sulfate～58ppm do not have carbon resonance.
1H-NMR (D
2O) spectrum shows that the methylene radical that is connected on the not quaternised nitrogen shifts in the part of the resonance of about 2.5ppm and has transferred to about 3.0ppm.This is quaternized consistent with required about 38% nitrogen.
Embodiment 3
PEI1800E
7The generation of amine oxide
Add molecular-weight average in 500 milliliters of erlenmeyer flasks of a make-up machinery stirring rod and be 1800 and by polymine (PEI1800, the E of ethoxylation to nearly 7 inferior ethoxyls of each nitrogen group
7) (209 grams, 0.595 mole of nitrogen, prepared as embodiment 1) and hydrogen peroxide (120 grams are 30% solution in water, 1.06 moles).Cover this Erlenmeyer flask, after the initial heat release, at room temperature stir a whole night.On the sample of reaction mixture, obtain
1H-NMR (D
2O) show that conversion fully.The resonance of the methene proton that links to each other with unoxidized nitrogen is transferred to～3.5ppm from the original position at～2.5ppm.Add about 5 grams, 0.5% alumina wafer in the reaction soln and carry Pd, and this solution was placed under the room temperature about 3 days.Test this solution and find no superoxide by test paper.The material that obtains is suitable for the living solution storage to be 51.1% in water.
Other the preparation in, adopts more a spot of hydrogen peroxide and in product be excessive or randomly by the adding reductive agent, for example S-WAT decomposes.
Embodiment 4
Quaternized PEI1800E
7The formation of amine oxide
Add molecular-weight average in 500 milliliters of erlenmeyer flasks of a make-up machinery stirring rod and be 1800 polymine, its by ethoxylation to each nitrogen nearly 7 inferior ethoxyl groups (PEI1800, E
7) degree come modification, and then by adopting methyl-sulfate quaternized to about 38% further modification (130 grams,～0.2 mole of oxidable nitrogen), also add hydrogen peroxide (48 grams are the solution of 30% weight, 0.423 mole) and water (～50 gram) in water.Cover this Erlenmeyer flask, after the initial heat release, at room temperature stir a whole night.On the sample of reaction mixture, obtain
1H-NMR (D
2O) show that the resonance relevant with the methylene peak of observed 2.5～3.0ppm in front is transformed into the material that the chemical shift that contains methylene radical is approximately 3.7ppm fully.Add about 5 grams, 0.5% alumina wafer in the reaction soln and carry Pd, and this solution was placed under the room temperature about 3 days.Test this solution and find that by test paper no superoxide exists.The material that obtains is suitable for the living solution storage to be 51.1% in water.
Embodiment 5
PEI1200E
7Preparation
Carry out ethoxylation being equipped with thermometric and temperature control, pressure measurement, vacuum and inert gas purge, sampling unit and having added in 2 gallons of stirring-type stainless steel cauldrons of liquid epoxy ethane.The netted tube of one～20 pounds oxyethane (ARC) is set to be come by pump liquid epoxy ethane to be transported to and has in the reactor that is positioned over the tube on the pan of a steelyard, with the changes in weight of monitoring tube.
In reactor, add 750 gram part polymines (PEI) (listed molecular-weight average 1200 equals about 0.625 mole polymkeric substance and 17.4 mole of nitrogen functional groups).The then sealed reactor and the air of draining (vacuum tightness is reduced to 28 " Hg, then feed nitrogen to 250psia, become normal pressure again).The content of reactor is heated to 130 ℃ under vacuum condition.After about 1 hour, reactor is filled to 250psia with nitrogen, general formula is cooled to about 105 ℃ with reactor.Then accurately again oxyethane is being added in the reactor gradually in assaying reaction still pressure, temperature and the ethylene oxide flow rate.Close the temperature rising that ethylene oxide pump and cooling cause owing to exothermic heat of reaction with restriction.Temperature is remained between 100 and 110 ℃, in reaction process, stagnation pressure is raise gradually simultaneously.With (being about as much as every PEI nitrogen functional group 1 moles of ethylene oxide) after the oxyethane of 750 grams join reactor altogether, temperature is brought up to 110 ℃, and again reactor was stirred 1 hour.At this moment, adopt vacuum to remove all remaining unreacted ethylene oxide.
Below, continue to adopt vacuum simultaneously reactor to be cooled to about 50 ℃, add the methanol solution (1.74 moles) of the sodium methylate of 376 grams 25% simultaneously with the PEI nitrogen functional group's that obtains 10% load catalyzer.Methanol solution is inhaled into reactor under vacuum condition, then the set point with the temperature of reaction kettle controller is elevated to 130 ℃.Adopt a kind of device to measure the pressure of agitator.Measure the pressure of agitator with temperature and pressure.When methyl alcohol was removed from reactor, the pressure and temperature value of agitator raise gradually, and the viscosity of mixture raises and stablizes and illustrated that most methyl alcohol removed in about 1 hour.With mixture further heating and under vacuum restir 30 minutes.
Remove vacuum and reactor is cooled to 105 ℃, feed nitrogen simultaneously and reach 250psia, become normal pressure again.Reactor is full of nitrogen reaches 200psia.As above again oxyethane is joined in the reactor gradually, simultaneously the flow velocity of pressure, temperature and the oxyethane of accurate assaying reaction still in the process that any temperature that maintains the temperature between 100 and 110 ℃ and control causes owing to exothermic heat of reaction raises.Add in the several hrs process (every mole of PEI nitrogen functional group of result is 7 moles of ethylene oxide altogether) after the 4500 gram oxyethane, temperature is elevated to 110 ℃ and with mixture restir 1 hour.
Then reaction mixture is collected in the container of nitrogen purge, and finally transfers in 22 liters of three mouthfuls of round-bottomed flasks that assembled heating and whipping appts.Add in the 167 gram methane sulfuric acid (1.74 moles) and strong alkali catalyst.Then when stirring, feed 100 cubic feet of rare gas elementes (argon gas or nitrogen) deodorizing by the gas dispersion plate and by reaction mixture, and with mixture heating up to 130 ℃.
Slowly cool off final reaction product and be collected in and use in the Glass Containers of nitrogen purge.
In another preparation, neutralization and deodorizing were finished in reactor before taking out product.
Another preferred examples can prepare by the oxyethane relative quantity of adjusting the reaction times and be used to react by top method as PEI 1200 E 15 and PEI 1200 E20.
Embodiment 6
PEI 1200 E7's is 9.7% quaternized
The ethoxylation degree that adds MW1200 in 500 milliliters of erlenmeyer flasks of a make-up machinery stirring rod is 7 polymine (248.4 grams, 0.707 mole of nitrogen is as preparation in embodiment 5) and acetonitrile (Baker, 200 milliliters).Immediately methyl-sulfate (Aldrich, 8.48 grams, 0.067 mole) is joined in the solution of quick stirring, then it is covered and at room temperature stirs a whole night.In～60 ℃ rotatory evaporator, then in～80 ℃ Kugelroho device (Aldrich), evaporate the second eyeball, obtain～the required chocolate thick liquid nano material of 220 grams.
13C-NMR (D
2O) spectrum does not show not corresponding to the peak of methyl-sulfate at～58ppm.
1H-NMR (D
2O) spectrum shows in the peak part of 2.5ppm (being connected the methylene radical on the not quaternized nitrogen) and transfers to～3.0ppm.
Embodiment 7
PEI 600 E
20Preparation
In 2 gallons of stirring-type stainless steel cauldrons that are equipped with thermometric and temperature control, pressure measurement, vacuum and inert gas purge, sampling and the required device of adding liquid epoxy ethane, carry out ethoxylation.The netted tube (ARC) that one～20 pounds of oxyethane are set comes by pump liquid epoxy ethane to be transported to and has in the reactor that is positioned over the tube on the pan of a steelyard, with the changes in weight of monitoring tube.
In reactor, add 250 gram part polymines (PEI) (Nippon Shokubai, listed molecular-weight average 600 equal about 0.417 mole polymkeric substance and 6.25 mole of nitrogen functional groups).The then sealed reactor and the air of draining (vacuum tightness is reduced 28 " Hg, then feed nitrogen to 250psia, become normal pressure again).The content of reactor is heated to 130 ℃ under vacuum condition.After about 1 hour, reactor is filled to 250psia with nitrogen, general formula is cooled to about 105 ℃ with reactor.Then accurately again oxyethane is being added in the reactor gradually in assaying reaction still pressure, temperature and the ethylene oxide flow rate.Close the temperature rising that ethylene oxide pump and cooling cause owing to exothermic heat of reaction with restriction.Temperature is remained between 100 and 110 ℃, in reaction process, stagnation pressure is raise gradually simultaneously.With (every PEI nitrogen functional group is about as much as 1 moles of ethylene oxide) after 275 gram oxyethane join reactor altogether, temperature is brought up to 110 ℃, and again reactor was stirred 1 hour.At this moment, adopt vacuum to remove all remaining unreacted ethylene oxide.
Below, continue to adopt vacuum simultaneously reactor to be cooled to about 50 ℃, add the methanol solution (0.625 mole reaches the catalyzer of 10% carrying capacity based on the PEI nitrogen functional group) of the sodium methylate of 135 grams 25% simultaneously.Methanol solution is inhaled into reactor under vacuum condition, then the set point with the temperature of reaction kettle controller is elevated to 130 ℃.Adopt a kind of device to measure the power that agitator consumes.Measure the power of agitator with temperature and pressure.When methyl alcohol was removed from reactor, the power and the temperature value of agitator raise gradually, and the viscosity of mixture raises and stablizes and illustrated that most methyl alcohol removed in about 1 hour.With mixture further heating and under vacuum restir 30 minutes.
Remove vacuum and reactor is cooled to 105 ℃, feed nitrogen simultaneously and reach 250psia, become normal pressure again.Reactor is full of nitrogen reaches 200psia.As above again oxyethane is joined in the reactor gradually, simultaneously the flow velocity of pressure, temperature and the oxyethane of accurate assaying reaction still in the process that any temperature that maintains the temperature between 100 and 110 ℃ and control causes owing to exothermic heat of reaction raises.Add in the several hrs process (every mole of PEI nitrogen functional group of result is 20 moles of ethylene oxide altogether) after about 5225 gram oxyethane, temperature is elevated to 110 ℃ and with mixture restir 1 hour.
Then reaction mixture is collected in the container of nitrogen purge, and finally transfers in 22 liters of three mouthfuls of round-bottomed flasks that assembled heating and whipping appts.Add in the 60 gram methylsulfonic acids (0.625 mole) and strong alkali catalyst.Then when stirring, feed 100 cubic feet of rare gas elementes (argon gas or nitrogen) deodorizing by the gas dispersion plate and by reaction mixture, and with mixture heating up to 130 ℃.
Slowly cool off final reaction product and be collected in and use in the Glass Containers of nitrogen purge.
In another preparation, neutralization and deodorizing were finished in reactor before taking out product.
The preparation of non-cotton soil release polymers
Embodiment 8
Synthetic 2-(2,3-two propoxyls) ethane sulfonic acid sodium monomer
Be equipped with mechanical stirrer, improved claisen head, condenser (for distillation is provided with), thermometer and temperature regulator (Therm-O-Watch toward one 500 milliliters
TM, I
2R) add isethionic acid, sodium salt (Aldrich, 50.0 grams, 0.338 mole), sodium hydroxide (2.7 grams, 0.0675 mole) and glycerine (Baker, 310.9 grams, 3.38 moles) in three mouthfuls of round-bottomed flasks.Solution is heated a whole night to distill out moisture from reaction mixture at 190 ℃ under argon gas atmosphere.
13C-NMR (DMSO-d
6) in fact disappeared～53.5ppm and～the isethionic acid peak of 57.4ppm, illustrate that this reaction finishes.～51.4ppm (CH
2SO
3Na) and～67.5ppm (CH
2CH
2SO
3Na) the product peak has appearred.This solution is cooled to-100 ℃, and with methanesulfonic (Aldrich) pH7 that neutralizes.Potassiumphosphate by adding 0.8 mole of %, obtain required pure raw material as an alkali valency thing of buffered soln, and Kugelrohr device (Aldrich) 200 ℃ ,～1mmHg heating～3 hours, generate the yellow waxy solid of 77 grams.As selection, before being used to prepare oligopolymer, remove a part of glycerine.The glycerine solution of employing SEG can be so that handle sulfonated monomers.
Embodiment 9
Synthetic 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] ethane sulfonic acid sodium monomer
Be equipped with mechanical stirrer, improved claisen head, condenser (for distillation is provided with), thermometer and temperature regulator (Therm-O-Watch toward one 1 liter
TM, I
2R) add isethionic acid, sodium salt (Aldrich, 100.0 grams, 0.675 mole) and distilled water (90 milliliters) in three mouthfuls of round-bottomed flasks.After the dissolving, add the hydrosulphite that a hydrogen peroxide (Aldrich is 30% weight) comes the oxidation trace in water.With solution stirring 1 hour.The demonstration of superoxide bar is the very weak positive.Add sodium hydroxide (MCB, 2.5 grams, 0.0625 mole), then add Diethylene Glycol (Fisher, 303.3 grams, 2.86 moles).Solution is heated a whole night so that distill out moisture from solution mixture at 190 ℃ under argon gas atmosphere.
13C-NMR (DMSO-d
6) be by in fact disappear in～53.5ppm and～the isethionic acid peak of 57.4ppm illustrates that this reaction finishes.With this solution cool to room temperature, and with 16.4% the solution of 57.4 gram tosic acid monohydrates in the Diethylene Glycol pH7 that neutralizes.(randomly can adopt methanesulfonic.) product
13C-NMR spectrum shows that remaining 4 methylene radical are at～51ppm (CH
2SO
3Na) ,～60ppm (CH
2OH) and～69ppm ,～72ppm and～77ppm has resonance.Owing in N-process, generate paratoluenesulfonic acid sodium salt, also can see its a small amount of resonance.Reaction produces 451 gram 35.3%2-[2-(2-hydroxyl-oxethyl) oxyethyl groups] solution of ethane sulfonic acid sodium in Diethylene Glycol.Remove unnecessary Diethylene Glycol by an alkali valency potassiumphosphate (Aldrich) that adds 0.8 mole of % as buffered soln, and Kugelrohr device (Aldrich) 150 ℃ ,～1mmHg heating～3 hours, generate suitable heavy-gravity oil or glass required " SE3 " (as mentioned above).
Embodiment 10 Synthetic 2s-and 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oxyethyl group } ethane sulfonic acid sodium monomer
Toward one 1 liter be equipped with mechanical stirring rod, improved claisen head, condenser (for distillation is provided with), thermometer and temperature regulator (Therm-O-Watch
TM, I
2R) add isethionic acid, sodium salt (Aldrich, 205.0 grams, 1.38 moles) and distilled water (～200 milliliters) in three mouthfuls of round-bottomed flasks.After the dissolving, add the hydrosulphite that a hydrogen peroxide (Aldrich is 30% weight) comes the oxidation trace in water.With solution stirring 1 hour.The superoxide bar is the very weak positive.Add sodium hydroxide (MCB, 5.5 grams, 0.138 mole), then add Diethylene Glycol (Aldrich, 448.7 grams, 3.0 moles).Randomly be that for example NaOH heats the triethylene glycol of purifying until colour stable, then distills out pure alcohol and is used to synthesize by employing highly basic.Solution is heated a whole night so that distill out moisture from solution mixture at 190 ℃ under argon gas atmosphere.
13C-NMR (DMSO-d
6) be by in fact disappear in～53.5ppm and～the isethionic acid peak of 57.4ppm, appear at～51ppm (CH
2SO
3Na) ,～60ppm (CH
2OH) and～67ppm ,～69ppm and～the product peak of the residue methylene radical of 72ppm illustrates that this reaction finishes.With this solution cool to room temperature, and with methanesulfonic (Aldrich) pH7 that neutralizes.Reaction produces 650 gram 59.5%2-{2-[2-(2-hydroxyl-oxethyl) oxyethyl groups] oxyethyl group } solution of ethane sulfonic acid sodium in triethylene glycol.Remove unnecessary triethylene glycol by what add 0.8 mole of % as an alkali valency potassiumphosphate (Aldrich) of buffered soln, and Kugelrohr device (Aldrich) 180 ℃ ,～1mmHg heating～5.5 hours, generate brown solid shape desired substance.Find that more diffluent buffered soln can more effectively control pH in removing the process of excessive triethylene glycol.The example of the more diffluent buffered soln of this class is the salt that methanesulfonic is become with N-methylmorpholine.Randomly be that pH can be by frequent or adding acid continuously, for example methanesulfonic is controlled near neutrality to keep pH in removing the process of unnecessary alcohol.
Can believe that this material contains on a small quantity from the two ends of triethylene glycol and the stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate of isethionic acid reactant salt generation.But coarse raw materials can further not purified just with the negatively charged ion capping group that acts on polymer manufacture.
A large amount of triethylene glycols is adopted in other preparation, is 5 to 10 moles as every mole of isethionic acid.
Embodiment 11
2-[2-(2-hydroxyl-oxethyl) oxyethyl group] ethane sulfonic acid sodium, dimethyl terephthalate, 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium, glycerine, ethylene glycol and propylene glycol
Oligopolymer synthetic
Be equipped with mechanical stirring rod, improved claisen head, condenser (being used for distillation), thermometer and temperature regulator (Therm-O-Watch toward one 250 milliliters
TM, I
2R) add 2-[2-(2-hydroxyl-oxethyl) oxyethyl group in three mouthfuls of round-bottomed flasks] ethane sulfonic acid sodium (7.0 grams, 0.030 terephthalic acid dimethyl esters (14.4 grams mole),, 0.074 2-(2 mole),, 3-dihydroxyl propoxy-) ethane sulfonic acid sodium (3.3 grams, 0.015 glycerine (Baker mole),, 1.4 gram, 0.015 ethylene glycol (Baker mole),, 14.0 gram, 0.225 mole) and propylene glycol (Fisher, 17.5 gram, 0.230 mole) and titanium propanolate (IV) (0.01 restrains, total reactant weight 0.02%).With this mixture heating up to 180 ℃ and under this temperature, keeping a whole night under the argon gas atmosphere, from reaction vessel, to distill out the first alcohol and water.Material is transferred in 500 milliliters of single necked round bottom flask, in Kugelelrohr device (Aldrich), be heated to 240 ℃ gradually in about 20 minutes, and kept 1.5 hours at about 2mmHg.Reaction flask is carried out air cooling, be cooled fast in a vacuum near room temperature (～30 minutes).Reaction produces the required oligopolymer of 21.3 gram amber glass shapes.
13C-NMR (DMSO-d
6) show at～63.2ppm (diester) have-C (O) OCH
2CH
2The resonance of O (O) C has-C (O) OCH at～59.4ppm (monoesters)
2CH
2The resonance of OH.The ratio of the peak height of the peak height of diester resonance and monoesters resonance is about 10.Representative sulfo group oxyethyl group (CH has also appearred
2SO
3Na)～51.5ppm and～resonance of 51.6ppm.
1H-NMR (DMSO-d
6) be illustrated in～7.9ppm has the resonance of representing terephthalate fragrance hydrogen.Molar ratio by unconjugated ethylene glycol of the analysis revealed of hydrolysis gas-chromatography and unconjugated propylene glycol is 1.7: 1.It represents that also about 0.9% final polymkeric substance is a glycerine.If all the glycerine monomer is with the form combination of glyceryl ester, it is about 4% weight of final oligopolymer.Add in the phial by a spot of material of weighing, add enough distilled water and make the solution and the vigorous stirring phial of 35% weight and test solubleness.Material is easy to dissolving under these conditions.
Embodiment 12
2-[2-(2-hydroxyl-oxethyl) oxyethyl group] ethane sulfonic acid sodium, terephthalic acid dimethyl esters, 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium, ethylene glycol and propylene glycol oligomeric
Synthesizing of thing
Be equipped with mechanical stirring rod, improved claisen head, condenser (being used for distillation), thermometer and temperature regulator (Therm-O-Watch toward one 250 milliliters
, I
2R) add 2-[2-(2-hydroxyl-oxethyl) oxyethyl group in three mouthfuls of round-bottomed flasks] ethane sulfonic acid sodium (7.0 grams, 0.030 terephthalic acid dimethyl esters (14.4 grams mole),, 0.074 2-(2 mole),, 3-dihydroxyl propoxy-) ethane sulfonic acid sodium (6.6 grams, 0.030 mole), ethylene glycol (Baker, 14.0 grams, 0.225 mole) and propylene glycol (Fisher, 18.3 gram, 0.240 mole) and titanium propanolate (IV) (0.01 restrains, gross weight 0.02%).With this mixture heating up to 180 ℃ and under this temperature, keep a whole night, from reaction vessel, to distill out the first alcohol and water.Material is transferred in 500 milliliters of single necked round bottom flask, in Kugelelrohr device (Aldrich), under about 0.1mmHg, be heated to 240 ℃ gradually in about 20 minutes, and kept 110 minutes.Reaction flask is carried out air cooling in a vacuum, be cooled fast near room temperature (～30 minutes).Reaction produces the required oligopolymer of 24.4 gram amber glass shapes.
13C-NMR (DMSO-d
6) show at～63.2ppm (diester) have-C (O) OCH
2CH
2O (O) C-resonance has-C (O) OCH at～59.4ppm (monoesters)
2CH
2OH resonance.The ratio measuring at diester peak and monoesters peak is about 8.Representative sulfo group oxyethyl group (CH has also appearred
2SO
3Na)～51.5ppm and～resonance of 51.6ppm.
1H-NMR (DMSO-d
6) be illustrated in～7.9ppm has the resonance of expression terephthalate fragrance hydrogen.Molar ratio by unconjugated ethylene glycol of the analysis revealed of hydrolysis gas-chromatography and unconjugated propylene glycol is 1.6: 1.Add in the phial by a spot of material of weighing, add enough distilled water and make the solution and the vigorous stirring phial of 35% weight and test solubleness.Material is easy to dissolving under these conditions.
Embodiment 13
2-[2-(2-hydroxyl-oxethyl) oxyethyl group] ethane sulfonic acid sodium, terephthalic acid dimethyl esters, 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium, glycerine, ethylene glycol and propylene glycol
Oligopolymer synthetic
Be equipped with mechanical stirring rod, improved claisen head, condenser (being used for distillation), thermometer and temperature regulator (Therm-O-Watch toward one 250 milliliters
, I
2R) add 2-[2-(2-hydroxyl-oxethyl) oxyethyl group in three mouthfuls of round-bottomed flasks] ethane sulfonic acid sodium (7.0 grams, 0.030 mole), terephthalic acid dimethyl esters (9.6 grams, 0.049 mole), 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium (2.2 grams, 0.010 glycerine (Baker mole),, 1.8 the gram, 0.020 mole), ethylene glycol (Baker, 6.1 the gram, 0.100 mole) and propylene glycol (Fisher, 7.5 gram, 0.100 mole) and titanium propanolate (IV) (0.01 restrains, gross weight 0.02%).With this mixture heating up to 180 ℃ and under hydrogen atmosphere this temperature keep a whole night, from reaction vessel, to distill out the first alcohol and water.Material is transferred in 250 milliliters of single necked round bottom flask, in Kugelelrohr device (Aldrich), under about 3mmHg, be heated to 240 ℃ gradually in about 20 minutes, and kept 1.5 hours.Reaction flask is carried out air cooling in a vacuum to be cooled fast near room temperature (～30 minutes).Reaction produces the required oligopolymer of 18.1 gram amber glass shapes.
13C-NMR (DMSO-d
6) show at～63.2ppm have-C (O) OCH
2CH
2O (O) C-(diester) resonance.～59.4ppm-C (O) OCH
2CH
2OH (monoesters) resonance can not detect and is littler 12 times than diester peak.Representative sulfo group oxyethyl group (CH has also appearred
2SO
3Na)～51.5ppm and～resonance of 51.6ppm.
1H-NMR (DMSO-d
6) show the resonance that expression terephthalate fragrance hydrogen is arranged at～7.9ppm.Molar ratio by unconjugated ethylene glycol of the analysis revealed of hydrolysis gas-chromatography and unconjugated propylene glycol is 1.6: 1.The final polymkeric substance of also finding 0.45% weight is a glycerine.Add in the phial by a spot of material of weighing, add enough distilled water and make the solution and the vigorous stirring phial of 35% weight and test solubleness.Material is easy to dissolving under these conditions.
Embodiment 14
2-[2-(2-hydroxyl-oxethyl) oxyethyl group] ethane sulfonic acid sodium, terephthalic acid dimethyl esters, 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium, glycerine, ethylene glycol and propylene glycol
Oligopolymer synthetic
Be equipped with mechanical stirring rod, improved claisen head, condenser (being used for distillation), thermometer and temperature regulator (Therm-O-Watch toward one 250 milliliters
, I
2R) add 2-[2-(2-hydroxyl-oxethyl) oxyethyl group in three mouthfuls of round-bottomed flasks] ethane sulfonic acid sodium (2.7 grams, 0.011 mole, as embodiment 2), the terephthalic acid dimethyl esters (12.0 the gram, 0.062 mole, Aldrich), 2-(2,3-dihydroxyl propoxy-) ethane sulfonic acid sodium (5.0 grams, 0.022 the mole, as embodiment 1), glycerine (Baker, 0.50 the gram, 0.0055 ethylene glycol (Baker mole),, 6.8 gram, 0.110 mole) and propylene glycol (Fisher, 8.5 grams, 0.112 mole) and titanium propanolate (IV) (0.01 restrains, gross weight 0.02%).With this mixture heating up to 180 ℃ and under argon gas atmosphere this temperature keep a whole night, from reaction vessel, to distill out the first alcohol and water.Material is transferred in 500 milliliters of single necked round bottom flask, in Kugelelrohr device (Aldrich), under about 0.5mmHg, be heated to 240 ℃ gradually in about 20 minutes, and kept 150 minutes.Reaction flask is carried out air cooling in a vacuum to be cooled fast near room temperature (～30 minutes).Reaction produces the required oligopolymer of 16.7 gram amber glass shapes.
13C-NMR (DMSO-d
6) show at～63.2ppm have-C (O) OCH
2CH
2The resonance of O (O) C-(diester) has-C (O) OCH at～59.4ppm
2CH
2The resonance of OH (monoesters).The ratio of the peak height of the peak height of diester resonance and monoesters resonance is about 6.1.Representative sulfo group oxyethyl group (CH has also appearred
2SO
3Na)～51.5ppm and-peak of 51.6ppm.
1H-NMR (DMSO-d
6) be illustrated in～7.9ppm has the resonance of expression terephthalate fragrance hydrogen.Molar ratio by unconjugated ethylene glycol of the analysis revealed of hydrolysis gas-chromatography and unconjugated propylene glycol is 1.42: 1.Add in the phial by a spot of material of weighing, add enough distilled water and make the solution and the vigorous stirring phial of 35% weight and test solubleness.Material is easy to dissolving under these conditions.With one～9 gram samples of this material again in the Kugelelrohr device at 0.5mmHg 240 ℃ of heating, and kept 80 minutes.
13C-NMR (DMSO-d
6) be illustrated in 59.4ppm and do not have the monoesters peak that can monitor.Diester peak at～63.2ppm is bigger 11 times than monoesters peak at least.The solvability of this material is as above tested, and also finds its dissolving easily under these conditions.
High density liquid detergent composition of the present invention is described below.
The table I
| Component | Weight % | |||
| ????15 | ????16 | ????17 | ????18 | |
| Poly-hydroxy coconut fatty acid acid amides | ????3.65 | ????3.50 | ????- | ????- |
| ????C 12-C 13Alcohol ethoxylate E 9 | ????3.65 | ????0.80 | ????- | ????- |
| ????C 12-C 15Alcohol sodium sulfate | ????6.03 | ????2.50 | ????- | ????- |
| ????C 12-C 15Alcohol ethoxylate E 2.5Sodium sulfate | ????9.29 | ????15.10 | ????- | ????- |
| ????C 14-C 15Alcohol ethoxylate E 2.25Sodium sulfate | ????- | ????- | ????18.00 | ????18.00 |
| Alkyl N-methyl glucose amide | ????- | ????- | ????4.50 | ????4.50 |
| ????C 10Amido propyl amine | ????- | ????1.30 | ????- | ????- |
| Citric acid | ????2.44 | ????3.00 | ????3.00 | ????3.00 |
| Lipid acid (C 12-C 14) | ????4.23 | ????2.00 | ????2.00 | ????2.00 |
| ????NEODOL?23-9 1 | ????- | ????- | ????2.00 | ????2.00 |
| Ethanol | ????3.00 | ????2.81 | ????3.40 | ????3.40 |
| Monoethanolamine MEA BASF | ????1.50 | ????0.75 | ????1.00 | ????1.00 |
| Propylene glycol | ????8.00 | ????7.50 | ????7.50 | ????7.00 |
| Boric acid | ????3.50 | ????3.50 | ????3.50 | ????3.50 |
| Tetren | ?????- | ????1.18 | ????- | ????- |
| Toluenesulfonic acid sodium salt | ????2.50 | ????2.25 | ????2.50 | ????2.50 |
| ????NaOH | ????2.08 | ????2.43 | ????2.62 | ????2.62 |
| Other component 2 | ????1.60 | ????1.30 | ????0.27 | ????0.27 |
| Cotton soil release polymers 3 | ????0.50 | ????0.50 | ????- | ????- |
| Cotton soil release polymers 4 | ????- | ????- | ????2.00 | ????1.00 |
| Non-cotton soil release polymers 5 | ????0.33 | ????0.22 | ????- | ????- |
| Non-cotton soil release polymers 6 | ????- | ????- | ????1.00 | ????- |
| Non-cotton soil release polymers 7 | ????- | ????- | ????- | ????1.00 |
| Water 8 | Balance | Balance | Balance | Balance |
1. the E that sells by Shell Oil Co.
9Ethoxylated alcohol.
2. other component-comprise white dyes and enzyme (proteolytic enzyme, lipase, cellulase and amylase).
3. the cotton soil release polymers of embodiment 7.
4. the cotton soil release polymers of embodiment 1.
5.Scheibel Deng obtain the non-cotton soil release polymers of the US4968451 of power in November 6 nineteen ninety.
6. the non-cotton soil release polymers of embodiment 11.
7.Gosselink Deng the non-cotton soil release polymers that obtains the US4702857 of power on October 27th, 1987.
8. equilibrate to 100% water and the filler that can for example contain a spot of white dyes, spices, suds suppressor, stain remover, sequestrant, dye transfer inhibitor, interpolation, comprise lime carbonate, talcum, silicate etc.
The table II
| Component | Weight % | |||
| ????19 | ????20 | ????21 | ????22 | |
| Poly-hydroxy coconut fatty acid acid amides | ????2.50 | ????2.50 | ????- | ????- |
| ????C 12-C 13Alcohol ethoxylate E 9 | ????- | ????- | ????3.65 | ????0.80 |
| ????C 12-C 15Alcohol sodium sulfate | ????- | ????- | ????6.03 | ????2.50 |
| ????C 12-C 15Alcohol ethoxylate E 1.8Sodium sulfate | ????20.15 | ????20.15 | ????- | ????- |
| ????C 14-C 15Alcohol ethoxylate E 2.25Sodium sulfate | ????- | ????- | ????18.00 | ????18.00 |
| Alkyl N-methyl glucose amide | ????- | ????- | ????4.50 | ????4.50 |
| ????C 10Amido propyl amine | ????0.50 | ????0.50 | ????- | ????- |
| Citric acid | ????2.44 | ????3.00 | ????3.00 | ????3.00 |
| Lipid acid (C 12-C 14) | ????- | ????- | ????2.00 | ????2.00 |
| ????NEODOL?23-9 1 | ????0.63 | ????0.63 | ????- | ????- |
| Ethanol | ????3.00 | ????2.81 | ????3.40 | ????3.40 |
| Monoethanolamine MEA BASF | ????1.50 | ????0.75 | ????1.00 | ????1.00 |
| Propylene glycol | ????8.00 | ????7.50 | ????7.50 | ????7.00 |
| Boric acid | ????3.50 | ????3.50 | ????3.50 | ????3.50 |
| The ethoxylation tetren 2 | ????0.50 | ????- | ????- | ????0.50 |
| Tetren | ????- | ????1.18 | ????- | ????- |
| Toluenesulfonic acid sodium salt | ????2.50 | ????2.25 | ????2.50 | ????2.50 |
| ????NaOH | ????2.08 | ????2.43 | ????2.62 | ????2.62 |
| Other component 3 | ????1.60 | ????1.30 | ????0.27 | ????0.27 |
| Cotton soil release polymers 4 | ????0.50 | ????0.50 | ????- | ????- |
| Cotton soil release polymers 5 | ????- | ????- | ????2.00 | ????1.00 |
| Non-cotton soil release polymers 6 | ????0.33 | ????- | ????- | ????0.55 |
| Non-cotton soil release polymers 7 | ????- | ????0.50 | ????1.00 | ????- |
| Non-cotton soil release polymers 8 | ????- | ????- | ????- | ????1.00 |
| Water 9 | Balance | Balance | Balance | Balance |
1. the E that sells by Shell Oil Co.
9The alcohol of ethoxylation.
2. obtain the tetren (PEI189E of ethoxylation of the US4597898 of power on July 1st, 1986 according to Vander Meer etc.
15-E
18).
3. other component-comprise white dyes and enzyme (proteolytic enzyme, lipase, cellulase and amylase).
4. the cotton soil release polymers of embodiment 7.
5. the cotton soil release polymers of embodiment 4.
6.Scheibel Deng obtain the non-cotton soil release polymers of the US4968451 of power in November 6 nineteen ninety.
7. the non-cotton soil release polymers of embodiment 11.
8.Gosselink Deng the non-cotton soil release polymers that obtains the US4702857 of power on October 27th, 1987.
9. equilibrate to 100% water and the filler that can for example contain a spot of white dyes, spices, suds suppressor, stain remover, sequestrant, dye transfer inhibitor, interpolation, comprise lime carbonate, talcum, silicate etc.
The table III
| Component | Weight % | |||
| 23 | 24 | 25 | 26 | |
| C 14-C 15Alcohol ethoxylate E 2.25Sodium sulfate | 13.00 | - | - | 8.43 |
| C 12-C 15Alcohol ethoxylate E 2.5Sodium sulfate | - | 18.00 | 13.00 | - |
| C 12-C 13Wire benzene sulfonamide acid esters | 9.86 | - | - | 8.43 |
| Lipid acid (C 12-C 14) | - | 2.00 | 2.00 | 2.95 |
| C 12-C 13Alcohol ethoxylate E 9 | - | - | - | 3.37 |
| C 10Amido propyl amine | - | - | 0.80 | - |
| NEODOL?23-9 1 | 2.22 | 2.00 | 1.60 | - |
| Alkyl N-methyl glucose amide | - | 5.00 | 2.50 | - |
| Citric acid | 7.10 | 3.00 | 3.00 | 3.37 |
| Ethanol | 1.92 | 3.52 | 3.41 | 1.47 |
| Monoethanolamine MEA BASF | 0.71 | 1.09 | 1.00 | 1.05 |
| Propylene glycol | 4.86 | 8.00 | 6.51 | 6.00 |
| Boric acid | 2.22 | 3.30 | 2.50 | - |
| The tetren of ethoxylation | 1.18 | 1.18 | - | 1.48 |
| Cumene sodium sulfonate | 1.80 | 3.00 | - | 3.00 |
| Toluenesulfonic acid sodium salt | - | - | 2.50 | - |
| NaOH | 6.60 | 2.82 | 2.90 | 2.10 |
| Dodecyl trimethyl ammonium chloride | - | - | - | 0.51 |
| Sodium tartrate one and two Succinic Acid | - | - | - | 3.37 |
| Sodium formiate | - | - | - | 0.32 |
| Other component 2 | 1.60 | 1.80 | 2.00 | 1.60 |
| Cotton soil release polymers 3 | 0.50 | 2.00 | - | - |
| Cotton soil release polymers 4 | 1.50 | - | 2.00 | 3.00 |
| Non-cotton soil release polymers 5 | 1.50 | - | 2.00 | - |
| Non-cotton soil release polymers 6 | - | 1.15 | - | 1.50 |
| Water 7 | Balance | Balance | Balance | Balance |
1. the E that sells by Shell Oil Co.
9The alcohol of ethoxylation.
2. other component-comprise white dyes and enzyme (proteolytic enzyme, lipase, cellulase and amylase).
3. the cotton soil release polymers of embodiment 4.
4. the cotton soil release polymers of embodiment 7.
5. the non-cotton soil release polymers of embodiment 10.
6. the non-cotton soil release polymers of embodiment 11.
7. equilibrate to 100% water and the filler that can for example contain a spot of white dyes, spices, suds suppressor, stain remover, sequestrant, dye transfer inhibitor, interpolation, comprise lime carbonate, talcum, silicate etc.
The table IV
| Component | Weight % | |||
| 27 | 28 | 29 | 30 | |
| C 14-C 15Alcohol ethoxylate E 2.25Sodium sulfate | 13.00 | - | - | 8.43 |
| C 12-C 15Alcohol ethoxylate E 2.5Sodium sulfate | - | 18.00 | 13.00 | - |
| C 12-C 13The wire sodium alkyl benzene sulfonate | 9.86 | - | - | 8.43 |
| Lipid acid (C 12-C 14) | - | 2.00 | 2.00 | 2.95 |
| C 12-C 13Alcohol ethoxylate E 9 | - | - | - | 3.37 |
| C 10Amido propyl amine | - | - | 0.80 | - |
| NEODOL?23-9 1 | 2.22 | 2.00 | 1.60 | - |
| Alkyl N-methyl glucose amide | - | 5.00 | 2.50 | - |
| Citric acid | 7.10 | 3.00 | 3.00 | 3.37 |
| Ethanol | 1.92 | 3.52 | 3.41 | 1.47 |
| Monoethanolamine MEA BASF | 0.71 | 1.09 | 1.00 | 1.05 |
| Propylene glycol | 4.86 | 8.00 | 6.51 | 6.00 |
| Boric acid | 2.22 | 3.30 | 2.50 | - |
| The tetren of ethoxylation | 1.18 | 1.18 | - | 1.48 |
| Cumene sodium sulfonate | 1.80 | 3.00 | - | 3.00 |
| Toluenesulfonic acid sodium salt | - | - | 2.50 | - |
| NaOH | 6.60 | 2.82 | 2.90 | 2.10 |
| Dodecyl trimethyl ammonium chloride | - | - | - | 0.51 |
| Sodium tartrate one and two Succinic Acid | - | - | - | 3.37 |
| Sodium formiate | - | - | - | 0.32 |
| Other component 2 | 1.60 | 1.80 | 2.00 | 1.60 |
| Cotton soil release polymers 3 | 0.50 | 2.00 | - | - |
| Cotton soil release polymers 4 | 1.50 | - | 2.00 | 3.00 |
| Non-cotton soil release polymers 5 | 1.50 | - | 2.00 | - |
| Non-cotton soil release polymers 6 | - | 1.15 | - | 1.50 |
| Water 7 | Balance | Balance | Balance | Balance |
1. the E that sells by Shell Oil Co.
9The alcohol of ethoxylation.
2. other component-comprise white dyes and enzyme (proteolytic enzyme, lipase, cellulase and amylase).
3. the cotton soil release polymers of embodiment 4.
4. the cotton soil release polymers of embodiment 7.
5. the non-cotton soil release polymers of embodiment 10.
6. the non-cotton soil release polymers of embodiment 11.
7. equilibrate to 100% water and the filler that can for example contain a spot of white dyes, spices, suds suppressor, stain remover, sequestrant, dye transfer inhibitor, interpolation, comprise lime carbonate, talcum, silicate etc.
The table V
| Component | 31 | ?32 | ?33 | ?34 | ?35 |
| Poly-hydroxy coconut fatty acid acid amides | 3.50 | ?3.50 | ?3.15 | ?3.50 | ?3.00 |
| NEODOL?23-9 1 | 2.00 | ?0.60 | ?2.00 | ?0.60 | ?0.60 |
| C 25The vitriol of alkyl ethoxylated | 19.00 | ?19.40 | ?19.00 | ?17.40 | ?14.00 |
| C 25Alkyl-sulphate | - | ?- | ?- | ?2.85 | ?2.30 |
| C 10-aminopropyl acid amides | - | ?- | ?- | ?0.75 | ?0.50 |
| Citric acid | 3.00 | ?3.00 | ?3.00 | ?3.00 | ?3.00 |
| Tallow fatty acids | 2.00 | ?2.00 | ?2.00 | ?2.00 | ?2.00 |
| Ethanol | 3.41 | ?3.47 | ?3.34 | ?3.59 | ?2.93 |
| Propylene glycol | 6.22 | ?6.35 | ?6.21 | ?6.56 | ?5.75 |
| One carbinolamine | 1.00 | ?0.50 | ?0.50 | ?0.50 | ?0.50 |
| Sodium hydroxide | 3.05 | ?2.40 | ?2.40 | ?2.40 | ?2.40 |
| Paratoluenesulfonic acid sodium salt | 2.50 | ?2.25 | ?2.25 | ?2.25 | ?2.25 |
| Borax | 2.50 | ?2.50 | ?2.50 | ?2.50 | ?2.50 |
| Proteolytic enzyme 2 | 0.88 | ?0.88 | ?0.88 | ?0.88 | ?0.88 |
| Lipolytic enzyme 3 | 0.04 | ?0.12 | ?0.12 | ?0.12 | ?0.12 |
| Duramyl 4 | 0.10 | ?0.10 | ?0.10 | ?0.10 | ?0.40 |
| CAREZYME | 0.053 | ?0.053 | ?0.053 | ?0.053 | ?0.053 |
| White dyes | 0.15 | ?0.15 | ?0.15 | ?0.15 | ?0.15 |
| Cotton stain remover 5 | 1.18 | ?1.18 | ?1.18 | ?1.18 | ?1.75 |
| Non-cotton stain remover 6 | 0.22 | ?0.15 | ?0.15 | ?0.15 | ?0.15 |
| Fumed | 0.119 | ?0.119 | ?0.119 | ?0.119 | ?0.119 |
| Aesthetic feeling articles for use, water on a small quantity, | Balance | Balance | Balance | Balance | Balance |
1.C
12-C
13Alkyl E9 ethoxylate is provided by Shell Oi1 Co..
2. be documented in the bacillus amyloliquefaciens subtilysin among the WO95/10615 of the Genencor International that is disclosed in April 20 nineteen ninety-five.
3. by Humicola lanuginosa preparation and commercially available by Novo.
4. be disclosed among the WO9510603A and commercially available by Novo.
5. according to the soil release polymer of embodiment 7.
6. be disclosed in Scheibel etc. and obtain the terephthalic acid ester copolymer of the US4968451 of power in November 6 nineteen ninety.
Claims (5)
1. liquid laundry detergent compositions, contain:
A) the anionic detergent tensio-active agent of at least 0.01% weight, it is selected from alkyl-sulphate, alkyl alkoxylated vitriol and their mixture;
B) the non-cotton stain remover of at least 0.01% weight, it is selected from the multipolymer of terephthalate, and it contains:
ⅰ) main chain contains:
A) at least one has the part of following general formula:
B) at least one has the part of following general formula:
R wherein
9Be C
2-C
6Wire alkylidene group, C
3-C
6The alkylidene group of collateralization, C
5-C
7Cyclic alkylidene and their mixture; R
10Be independently selected from hydrogen or-L-SO
3 -M
+Wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group-poly-(oxyalkylene group) and their mixture; M is hydrogen or salt-forming cation; I is 0 or 1 number;
C) chain portion of the formed ester of at least one trifunctional;
D) at least one 1,2-oxyalkylene group oxygen part; With
ⅱ) one or several end-blocking unit, it contains:
A) general formula is (MO
3S) (CH
2)
m(R
11O)
n-ethoxylation or propenoxylated hydroxyethanesulfonic acid salt or ethoxylation or propenoxylated hydroxypropanesulfonic acid salt unit, wherein M is a salt-forming cation, R
11Be ethylidene or propylidene or their mixture, m is 0 or 1, and n is 1 to 20;
B) C (C of general formula-(O)
6H
4) (SO
3 -M
+) sulfo group aroyl unit, wherein M is a salt-forming cation;
C) poly-(oxyethylene group) oxygen monoalky lether unit of modification, general formula is R
12O (CH
2CH
2O)
k -, R wherein
12Contain 1 to 4 carbon atom, k from about 3 to about 100; With
D) ethoxylation or propenoxylated phenolsulfonate end-blocking unit, its general formula is MO
3S (C
6H
4) (OR
13)
nO-, wherein n is 1 to 20; M is a salt-forming cation; R
13Be ethylidene, propylidene and their mixture;
Sulfonated oligomer ester composition, contain preformed, be the sulfonated products of wire ester oligomer basically, every mole of said wire ester oligomer contains:
ⅰ) 2 moles of terminal units, wherein about 1 mole to 2 moles said terminal units are to be produced by the unsaturated component of the olefinic that is selected from vinyl carbinol and methylallyl alcohol, and any remaining said terminal units other unit that is said wire ester oligomer;
ⅱ) about 1 mole to about 4 moles nonionic hydrophilic unit, said hydrophilic unit is to be produced by oxyalkylene, said oxyalkylene contains 50% to 100% the oxyethane of having an appointment;
ⅲ) about 1.1 moles are arrived about 20 moles repeating unit by the generation of aryl dicarbapentaborane component, wherein said aryl dicarbapentaborane component contains 50% to 100% the terephthalic acid dimethyl esters of having an appointment, and the repeating unit that is produced by said terephthalic acid dimethyl esters is a terephthaloyl; With
ⅳ) about 0.1 mole to about 19 moles by being selected from C
2-C
4The repeating unit that the diol component of glycol produces;
The sulfonation degree of wherein said sulfonation oligomer ester composition is that said terminal units is by ⅴ) chemical modification, wherein ⅴ) be 1 mole to 4 moles terminal units substituting group, its general formula is-SO
xM, wherein x is 2 or 3, said terminal units substituting group is by being selected from HSO
3M, wherein M is that the hydrosulphite component of general water-soluble cationic produces;
End-blocking terephthalic acid ester copolymer has following general formula:
X[(OCH
2CH
2)
n(OR
5)
m][(A-R
1-A-R
2)
u(A-R
3-A-R
2)
v]-
A-R
4-A[(R
5O)
m(CH
2CH
2O)
n]X
Wherein each A partly is selected from:
With their combination, each R
1Part is selected from 1,4-phenylene and itself and 1,3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2 '-biphenylene, 4,4 '-biphenylene, C
1-C
8Alkylidene group, C
1-C
8The combination of alkenylene and their mixture, R
2Part is selected from the ethylidene part, contains C
1-C
4The ethylidene of the replacement of alkyl, alkoxy substituent and their mixture; R
3Part is the C that replaces
2-C
18The alkylene part, its have at least one-CO
2M ,-O[(R
5O)
m(CH
2CH
2O)
n] X or-A[(R
2-A-R
4-A)] w[(R
5O)
m(CH
2CH
2O)
n] the X substituting group; R
4Part is R
1Perhaps R
3Part or their mixture; Each R
5Be C
1-C
4Alkylidene group or part-R
2-A-R
6, R wherein
6Be C
1-C
12Alkylidene group, alkenylene, arylidene or alkyl arylene part; M is hydrogen or water-soluble cationic; X is C
1-C
4Alkyl; The value of m and n will make part-(CH
2CH
2O)-contain at least about 50% weight of portions [(R
5O)
m(CH
2CH
2O)
n], as long as work as R
5Be part-R
2-A-R
6In-time, m is 1; N is at least 10; The value of u and v will make u+v's and be 3 to 25; W is 0 or is at least 1; And when w was at least 1, the value of u, v and w will make u+v+w's and be 3 to 25; With their mixture;
C) the cotton stain remover of the polyamine of the water-soluble or dispersible modification of at least 0.01% weight, this stain remover contains the polyamine main chain with following general formula:
Polyamine general formula with modification is V
(n+1)W
mY
nThe polyamine main chain that Z or general formula are following:
Polyamine general formula with modification is V
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and said polyamine main chain had before modification greater than 200 daltonian molecular weight, wherein
ⅰ) the V unit is the end group unit with following general formula:
Or
Or
ⅱ) the W unit is the backbone units with following general formula:
Or
Or
ⅲ) the Y unit is the chain unit with following general formula:
Or
Or
With
ⅳ) the Z unit is the end group unit with following general formula:
Or
Or
Wherein main chain connection R unit is selected from C2-C
12Alkylidene, C4-C
12Alkenylene, C3-C
12Hydroxy alkylidene, C4-C
12Alkyl sub-dihydroxy, C8-C
12Two alkyl arylenes ,-(R1O)
xR
1-、
-(R
1O)
xR
5(OR
1)
x-、-(CH
2CH(OR
2)CH
2O)
z(R
1O)
y-R
1(OCH
2CH(OR
2)CH
2)
w-、
-C(O)(R
4)
rC(O)-、-CH
2CH(OR
2)CH
2-and their mixture, preferred C2-C
12Alkylidene, C3-C
12Hydroxy alkylidene, C4-C
12Alkyl sub-dihydroxy, C8-C
12Two alkyl arylenes ,-(R1O)
zR
1、-(R
1O)
xR
5(OR
1)
x-、-(CH
2CH(OH)CH
2O)
z(R
1O)
y-R
1(OCH
2CH(OH)CH
2)
w-、
-CH
2CH(OR
2)CH
2-and their mixture, more preferably C2-C
12Alkylidene, C3-C
12Hydroxy alkylidene, C4-C
12Alkyl sub-dihydroxy ,-(R1O)
xR
1、-(R
1O)
xR
5(OR
1)
x -、-(CH
2CH(OH)CH
2O)
z(R
1O)
y-R
1(OCH
2CH(OH)CH
2)
w-and their mixture; C most preferably2-C
12Alkylidene and their mixture; R wherein1C2-C
6Alkylidene, preferred ethylidene, and their mixture, preferred hydrogen; R2Be hydrogen ,-(R1O)
xB and their mixture, preferred hydrogen; R3C1-C
18Alkyl, C7-C
12Aryl alkyl, C7-C
12Aryl, C that alkyl replaces6-C
12Aryl and their mixture, C1-C
6Alkyl and their mixture, more preferably methyl; R4C1-C
12Alkylidene, C4-C
12Alkenylene, C8-C
12Aryl alkylene, C6-C
10Arlydene and their mixture, preferred C2-C
12Alkylidene, C8-C
12Arylmethylene alkyl, and their mixture, more preferably ethylidene, butylidene and their mixture; R5C1-C
12Alkylidene, C3-C
12Hydroxy alkylidene, C4-C
12Alkyl sub-dihydroxy, C8-C
12Two alkyl arylenes ,-C (O)-,-C (O) NHR6-NHC(O)-、-R
1(OR
1)-、
-C(O)(R
4)
rC(O)-、CH
2CH(OH)CH
2-、
-CH
2CH(OH)CH
2O(R
1O)
yR
1-OCH
2CH(OH)CH
2-and their mixture, preferred ethylidene ,-C (O)-,-C (O) NHR6NHC(O)-、-R
1(OR
1)
y-、
-(CH
2CH(OH)CH
2O)
z(R
1O)
yR
1-(OCH
2CH(OH)CH
2)
w-、-CH
2CH(OH)CH
2-and their mixture, more preferably-CH2CH(OH)CH
2-；R
6C2-C
12Alkylidene or C6-C
12Arlydene; The E unit is selected from hydrogen, C1-C
22Alkyl, C3-C
22Alkenyl, C7-C
22Aryl alkyl, C2-C
22The hydroxyl alkyl ,-(CH2)
p-CO
2M、-(CH
2)
qSO
3M、-CH(CH
2CO
2M)-CO
2M、
-(CH
2)
pPO
3M、-(R
1O)
xB、-C(O)R
3With their mixture, preferred hydrogen, C3-C
22Hydroxyalkyl, benzyl, C1-C
22Alkyl ,-(R1O)
xB、、-C(O)R
3、
-(CH
2)
pCO
2 -M
+、-(CH
2)
qSO
3 -M
+、-CH(CH
2CO
2M)-CO
2M and their mixture, more preferably hydrogen C1-C
22Alkyl ,-(R1O)
xB、-C(O)R
3With their mixture, most preferably-(R1O)
xB； As long as when any one E unit of nitrogen is hydrogen, said nitrogen neither nitrogen oxide; B is hydrogen, C1-C
6Alkyl ,-(CH2)
qSO
3M、
-(CH
2)
pCO
2M、-(CH
2)
q(CHSO
3M)CH
2SO
3M、-(CH
2)
q(CHSO
2M)CH
2SO
3M、
-(CH
2)
pPO
3M、-PO
3M and their mixture, preferred hydrogen, C1-C
6Alkyl ,-(CH2)
qSO
3M、-(CH
2)
q(CHSO
3M)CH
2SO
3M、-(CH
2)
q(CHSO
2M)CH
2SO
3The mixture of M and they, more preferably hydrogen ,-(CH2)
qSO
3M and their mixture, most preferably hydrogen; M is hydrogen or the water-soluble cation that presents in an amount at least sufficient to meet charge balance; X is water soluble anion; M is 4 to 400 number; N is 0 to 200 number; P is 1 to 6 number, and q is 0 to 6 number; R is 0 or 1; W is 0 or 1; X is 1 to 100 number; Y is 0 to 100 number; Z is 0 or 1; With
D) balance carrier and additive component; Wherein when with 10% determination of aqueous solution, the pH of said composition is 7.2 to 8.9.
2. the composition of claim 1, further contain: nonionogenic tenside is selected from alkyl alkoxylates, the following fatty acid amide of general formula:
R wherein
7Be C
7-C
22Alkyl, R
8Be independently to be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl ,-(C
2H
4O)
jH and their mixture; Wherein j is from 1 to 3; With said surfactant mixtures; Preferred alkyl alcoxylates, the following fatty acid amide of general formula:
R wherein
7Be C
7-C
22Alkyl, R
8Be independently to be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl ,-(C
2H
4O)
jH and their mixture; Wherein j is from 1 to 3; With said surfactant mixtures.
3. claim 1 or 2 composition, wherein non-cotton soil release polymers is selected from:
I) non-cotton stain remover, contain:
A) main chain contains:
ⅰ) at least one has the part of following general formula:
ⅱ) at least one has the part of following general formula:
R wherein
9Be C
2-C
6Wire alkylidene group, C
3-C
6The alkylidene group of collateralization, C
5-C
7Cyclic alkylidene and their mixture; R
10Be independently selected from hydrogen or-L-SO
3 -M
+Wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene group, alkylidene group oxyalkylene group, arylidene, oxygen arylidene, alkylidene group oxygen arylidene, poly-(oxyalkylene group), oxyalkylene group oxygen arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group-poly-(oxyalkylene group) and their mixture; M is hydrogen or salt-forming cation; I is 0 or 1 number;
A ⅲ) chain portion of the formed ester of at least one trifunctional;
ⅳ) at least one 1,2-oxyalkylene oxygen part; With
B) one or several end-blocking unit, it contains:
ⅰ) general formula is (MO
3S) (CH
2)
m(R
11O)
n-ethoxylation or propenoxylated hydroxyethanesulfonic acid salt or ethoxylation or propenoxylated hydroxypropanesulfonic acid salt unit, wherein M is a salt-forming cation, R
11Be ethylidene or propylidene or their mixture, m is 0 or 1, and n is 1 to 20;
ⅱ) C (the C of general formula-(O)
6H
4) (SO
3 -M
+) sulfo group aroyl unit, wherein M is a salt-forming cation;
ⅲ) poly-(oxyethylene group) oxygen monoalky lether unit of modification, general formula is R
12O (CH
2CH
2O)
k -, R wherein
12Contain 1 to 4 carbon atom, k from 3 to 100; With
ⅳ) ethoxylation or propenoxylated phenolsulfonate end-blocking unit, its general formula is MO
3S (C
6H
4) (OR
13)
nO-, wherein n is 1 to 20; M is a salt-forming cation; R
13Be ethylidene, propylidene and their mixture;
II) sulfonated oligomer ester composition contains and is pre-formed, and is the sulfonated products of wire ester oligomer basically, and every mole of said wire ester oligomer contains:
A) 2 moles of terminal units, wherein 1 mole to 2 moles said terminal units is to be produced by the unsaturated component of the olefinic that is selected from vinyl carbinol and methylallyl alcohol, and any remaining said terminal units other unit that is said wire ester oligomer;
B) 1 mole to 4 moles nonionic hydrophilic unit, said hydrophilic unit are to be produced by oxyalkylene, and said oxyalkylene contains 50% to 100% oxyethane;
C) 1.1 moles to 20 moles repeating unit by the generation of aryl dicarbapentaborane component, wherein said aryl dicarbapentaborane component contains 50% to 100% terephthalic acid dimethyl esters, and the repeating unit that is produced by said terephthalic acid dimethyl esters is a terephthaloyl; With
D) 0.1 mole to 19 moles by being selected from C
2-C
4The repeating unit that the diol component of glycol produces;
The sulfonation degree of wherein said sulfonation oligomer ester composition is that said terminal units is by e) chemical modification, wherein e) be 1 mole to 4 moles terminal units substituting group, its general formula is-SO
xM, wherein x is 2 or 3, said terminal units substituting group is by being selected from HSO
3The hydrosulphite component of M produces, and wherein M is general water-soluble cationic;
III) have the non-cotton stain remover of following general formula:
X[(OCH
2CH
2)
n(OR
5)
m][A-R
1-A-R
2)
u(A-R
3-A-R
2)
v]-
A-R
4-A[R
5O)
m(CH
2CH
2O)
n]X
Wherein each A partly is selected from:
With their combination, each R
1Part is selected from 1,4-phenylene and itself and 1,3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2 '-biphenylene, 4,4 '-biphenylene, C
1-C
8Alkylidene group, C
1-C
8The combination of alkenylene and their mixture, R
2Part is selected from the ethylidene part, contains C
1-C
4The ethylidene of the replacement of alkyl, alkoxy substituent and their mixture; R
3Part is the C that replaces
2-C
18The alkylene part, its have at least one-CO
2M ,-O[(R
5O)
m(CH
2CH
2O)
n] X or-A[(R
2-A-R
4-A)] w[(R
5O)
m(CH
2CH
2O)
n] the X substituting group; R
4Part is R
1Perhaps R
3Part or their mixture; Each R
5Be C
1-C
4Alkylidene group or part-R
2-A-R
6, R wherein
6Be C
1-C
12Alkylidene group, alkenylene, arylidene or alkyl arylene part; M is hydrogen or water-soluble cationic; Each X is C
1-C
4Alkyl; The value of m and n will make part-(CH
2CH
2O)-contain at least 50% weight of portions [(R
5O)
m(CH
2CH
2O)
n], as long as work as R
5Be part-R
2-A-R
6In-time, m is 1; N is at least 10; The value of u and v will make u+v's and be 3 to 25; W is 0 or is at least 1; And when w was at least 1, the value of u, v and w will make u+v+w's and be 3 to 25; Mixture with described non-cotton stain remover.
4. any one composition of claim 1～3, wherein said binder component is selected from auxiliary agent, enzyme, enzyme stabilizers, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleach activator, dye transfer inhibitor, dispersion agent, enzyme activator, suds suppressor, dyestuff, spices, pigment, filling salt, hydrotropic agent and their mixture.
5. the liquid laundry detergent compositions of one of claim 1～4 further contains proteolytic enzyme.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97196085 CN1224447A (en) | 1996-05-03 | 1997-04-25 | Liquid laundry detergent compositions comprising cotton soil release polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/016,525 | 1996-05-03 | ||
| CN 97196085 CN1224447A (en) | 1996-05-03 | 1997-04-25 | Liquid laundry detergent compositions comprising cotton soil release polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1224447A true CN1224447A (en) | 1999-07-28 |
Family
ID=5179558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97196085 Pending CN1224447A (en) | 1996-05-03 | 1997-04-25 | Liquid laundry detergent compositions comprising cotton soil release polymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1224447A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111868222A (en) * | 2018-03-02 | 2020-10-30 | 荷兰联合利华有限公司 | Laundry compositions |
| US11814607B2 (en) | 2018-03-02 | 2023-11-14 | Conopco, Inc. | Laundry additive composition comprising a soil release polymer/silicone mixture |
-
1997
- 1997-04-25 CN CN 97196085 patent/CN1224447A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111868222A (en) * | 2018-03-02 | 2020-10-30 | 荷兰联合利华有限公司 | Laundry compositions |
| US11814607B2 (en) | 2018-03-02 | 2023-11-14 | Conopco, Inc. | Laundry additive composition comprising a soil release polymer/silicone mixture |
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