CN1085599A - Mix can be in washing lotion the detergent composition of the polyimide biopolymer of hydrolysis - Google Patents
Mix can be in washing lotion the detergent composition of the polyimide biopolymer of hydrolysis Download PDFInfo
- Publication number
- CN1085599A CN1085599A CN 93118644 CN93118644A CN1085599A CN 1085599 A CN1085599 A CN 1085599A CN 93118644 CN93118644 CN 93118644 CN 93118644 A CN93118644 A CN 93118644A CN 1085599 A CN1085599 A CN 1085599A
- Authority
- CN
- China
- Prior art keywords
- detergent composition
- polyimide
- polyimide biopolymer
- weight
- biopolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the detergent composition that contains at least a polyimide biopolymer or derivatives thereof, it is characterized in that, this polymer has and is higher than 5 * 10
-10The COO of mol/g
-Ionic concn, and can increase COO in the washing lotion
-Ionic concn.
The present invention also relates to the application of the defined polyimide biopolymer in front in powder detergent composition.
Description
The invention relates to a kind of detergent composition that contains a kind of polyimide biopolymer, and its application in detergent applications, wherein polymer can produce the polypeptide washing assistant of partially biodegradable at least by hydrolysis in washing lotion.
Among the present invention, washing assistant can be regarded as all compositions that can strengthen the Action of Surfactant of detergent composition.
The activity of washing assistant in washing medium shows the following aspects:
-it can remove interfering ion, particularly alkaline-earth metal ions (calcium, magnesium) by chelating and precipitation, stoping the precipitation of anion surfactant,
-it can keep alkalescence and ionic strength,
-it can make the dirt that extracts keep suspending,
-it can stop the inorganic sclerosis of clothing in washing process.
For a long time, tri-polyphosphate is often used as the washing assistant in detergent composition and the cleaning product.But because ecological the limit, people are seeking its substitute always.
Therefore, zeolite and vinylformic acid/copolymer-maleic anhydride have been proposed.
Regrettably, zeolite can not be used for separately needing other additive to strengthen its effect for tri-polyphosphate.
Concerning vinylformic acid/copolymer-maleic anhydride (or its alkali metal salts or ammonium salt), mainly as sclerosis inhibitor (European patent No.25,551), it has non-biodegradable shortcoming in physical environment for it.
Recently, the applicant has proposed to have simultaneously good elementary and secondary scourability, can produce the detergent composition of the washing assistant of partially biodegradable (patent application EP92400875.8) at least by hydrolysis in washing lotion.
The characteristics of this composition are that the employing of one of its component has 0-5 * 10
-4The COO of mol/g
-Ionic concn also can obtain to equal 10 at least in washing lotion
-3The COO of mol/g polymkeric substance
-The polyimide biopolymer of ionic concn.
The present invention is especially in regard to the detergent composition that contains at least a polyimide biopolymer or derivatives thereof, and its characteristics are that polymer has and are higher than 5 * 10
-4The COO of mol/g
-Ionic concn also can increase COO in the washing lotion
-Ionic concn.
Can be as this detergent composition of theme of the present invention by the hydrolysis and produce the washing assistant of partially biodegradable at least effectively in washing lotion of polyimide biopolymer.
According to the preferred embodiment of the invention, the COO of polyimide biopolymer or derivatives thereof
-The ion initial concentration is less than or equal to 2 * 10
-3The mol/g polymer.
According to the present invention, detergent composition refers to other family expenses cleaning product of laundry detergent, bowl dish washing composition or all.
" washing lotion " or " washing medium " is understood to be in the aqueous solution of the cleaning product (detergent composition) that exists in the washing process of washing machine; The washing composition consumption is recommended by manufacturers; And generally be less than 20g/L; The pH value of this solution is greater than or equal to 9.
Illustrate, have COO of the present invention
-The practical polyimide biopolymer of ionic concn is the polyimide that dibasic aminoacid (the particularly precursor of aspartic acid and L-glutamic acid or said dibasic aminoacid) polycondensation produces, and these polymer dissolution are just formed free COO in the water of alkaline PH
-Functional group.
This polymkeric substance can be aspartic acid or L-glutamic acid homopolymer, it equally also can be aspartic acid and L-glutamic acid multipolymer with any ratio, or aspartic acid and/or the acid of paddy institute and other amino acid whose multipolymer (for example other amino acid accounts for 15%W/W, preferably is less than 5%).
But copolymerization amino acid has glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, phenylalanine.Methionine(Met), tryptophane, Histidine, proline(Pro), Methionin, arginine, Serine, Threonine.Halfcystine etc.
Said polyimide biopolymer or derivatives thereof weight-average molecular weight is 300 to 10
7, be generally 500-60,000.
The biopolymers such as polyimide of aspartic acid or L-glutamic acid can be by J.A.C.S.80,3361(1958), J.Med.Chem.16,893(1973), Polymer23, the method of describing 1237(1982) or in the U.S. Patent No. 3,052,655 allows said amino acid make by adding thermal condensation in essentially no water medium.
COO required for the present invention
-Ionic concn also can reach with the partial hydrolysis of polyimide biopolymer.These compounds, promptly the polyimide derivative can be by at least one the imide ring open loop that particularly controlledly allows in the initial polyimide chain, and forms carboxylate salt simultaneously and obtain.
The polyimide biopolymerization scale of construction (constituting theme of the present invention) is counted 0.2% to 80% of detergent composition by weight in the detergent composition, is preferably 2-5%.
Except polyimide biopolymer or its thing that spreads out, in detergent composition, amount of surfactant is the 2-50% of detergent composition by weight percentage, is preferably 6-30%.
Tensio-active agent in the detergent composition of formation theme of the present invention has:
-anion surfactant comprises basic metal and soap (C
8-C
24Fatty acid alkali metal salt), alkali metal sulfonate (C
8-C
13Alkylbenzene sulfonate, C
12-C
16Alkylsulfonate, oxyethylation and sulfation C
6-C
16Fatty Alcohol(C12-C14 and C12-C18), oxyethylation and sulfation C
8-C
13Alkylphenol).Sulfo-succsinic acid an alkali metal salt (C
12-C
16Alkyl-thio-succinate) or the like.
-nonionogenic tenside comprises polyoxyethylene C
6-C
12Alkylphenol, oxyethylation C
8-C
22Fatty Alcohol(C12-C14 and C12-C18), ethylene oxide-propylene oxide block copolymer, the carboxylic acid amides of polyoxyethyleneization in case of necessity.
-alkyl dimethyl betaines amphoterics,
-cats product such as alkyltrimethylammonium, alkyl-dimethyl ammonium muriate or bromide.
Other multiple component also can be arranged, to form powdered detergent or cleaning product in the detergent composition of the present invention.
Other component that also may occur in detergent composition is as described below:
-washing assistant comprises:
The phosphoric acid salt of Football Association's formulation weight 25% not,
Zeolite can reach about 40% of total formulation weight,
Yellow soda ash can reach about 80% of total formulation weight,
Itrile group acetate can reach about 10% of total formulation weight,
Citric acid, tartrate can reach total prescription and weigh about 20%,
Washing assistant (polyimide precursor+other active factor) total amount is equivalent to the 0.2-80% of detergent composition gross weight, is preferably 20-45%.
-sanitas such as silicate can reach about 25% of cleaning composition gross weight,
-SYNTHETIC OPTICAL WHITNER such as perborate, chlorine isocyanate, N, N, N ', N '-tetraacetyl ethylene diamine (TAED) can reach about 30% of detergent composition gross weight at most.
-anti-redeposition agent such as carboxymethyl cellulose, methylcellulose gum class, its amount can reach about 5% of detergent composition gross weight at most.
-anti-setting agent such as vinylformic acid/copolymer-maleic anhydride, its amount can reach about 10% of detergent composition gross weight at most.
The filler of-powdered detergent such as sodium sulfate, its amount can reach 50% of washing composition gross weight at most.
The present invention also is related to the application of previous defined polyimide biopolymer in powder detergent composition.
The detergent composition that constitutes theme of the present invention washs with all there is good effectiveness the washing stage subsequently first.In addition, only use in washings just the polyimide of hydrolysis guaranteed this detergent composition between the shelf lives than the composition stable that directly contains biodegradable polypeptide.
The following examples and unique accompanying drawing are indicative explanations, can not think the restriction to scope of the present invention and design.
Only accompanying drawing is represented the variation along with the variation lime carbonate level of sedimentation of polymer concentration.
Embodiment 1:
The preparation of lower molecular weight polysuccinimide
It is 95cm that the Maleic Acid, Anhydrous ammonium salt of 45g intersperses among area
2About rectangle have no chance in the Stainless Steel Disc.Dish is put into THERMOSI SR 2000
RIn the no air draft stove, be preheated to 230 ℃.React after two hours, the amount of extractable content is 1.64%W/W after measured.Obtaining a kind of meal is polysuccinimide (infrared spectra), and its number-average molecular weight Mn equals 900(at 0.5N NaOH medium viscosity method of masurement).
Embodiment 2:
Utilize the laundry detergent composition prescription of the polysuccinimide of embodiment 1
Various additives join in the meal of embodiment 1 preparation, dry mixed, to obtain following detergent composition (cleaning product):
The composition % weight of washing composition
Linear hydrocarbon phenyl sulfonate 7.5
CEMUSOL LA 90
R(polyoxyethylene lauric acid, S.F.O.S. sells) 4
Zeolite 4A 24
Water glass (SiO
2/ Na
2O=2) 1.5
Yellow soda ash 10
TAED 2
Sodium peroxoborate 15
Ethylenediamine tetraacetic acid (EDTA) 0.1
The polysuccinimide 3 of above-mentioned preparation
Tinopal DMSX
R0.1
Tinopal SOP(fluorescent bleaches, CIBAGEIGY sells) 0.1
Polysiloxane defoamers 0.2
Alcalaze 0.15
The Savinaze(enzyme) 0.15
Sodium sulfate qs 100%
" contrast cleaning product " is meant that above cleaning product does not contain polysuccinimide in forming.
The effect characteristics of this washing composition are tested and describe in the following example.
Embodiment 3:
Polysuccinimide among this example explanation embodiment 1 is the on-the-spot sequestering action that is hydrolyzed to behind the poly aspartic acid calcium ion in alkaline medium.
The calcium ion sequestering action utilizes a kind ofly to have the electrode that the selectivity calcium ion sees through film and measures.
In the 100ml pH10.5 solution that contains 3g/L sodium-chlor, add 10
-5To 3 * 10
-3The mol/L calcium ion, earlier with this solution working curve that draws, the voltage curve that draws and show by electrode is as Free Ca
2+The function of concentration.
With the strong caustic hydrolysis of the polysuccinimide among the embodiment 1, contain 20%(weight up to obtaining PH10.5) the poly aspartic acid sodium solution.Gained solution is called " hydrolyzed solution ".
With this solution dilution,, transfer PH to 10.5 with strong caustic up to obtaining the aqueous solution that 100g contains the 10g/L poly (sodium aspartate).Add 0.3g powdery sodium-chlor again.Calcium ion is also with from 10
-5To 3 * 10
-3The amount of mol/L adds, and makes a free (Ca of expression
2+)/in conjunction with (Ca
2+)=f((the Ca that dissociates
2+)) straight line.
According to this straight line, can determine following:
The calcium ion complexation constant of-polymkeric substance, K,
The coordination of-polymkeric substance the S that counts
0, be defined as follows:
(free ［ Ca
2+])/(in conjunction with ［ Ca
2+])=1/ (KS
0)+1/ (S
0) free ［ Ca
2+]
Calculate according to this method and can find that the poly aspartic acid that the hydrolysis of polysuccinimide by embodiment 1 obtains has 2.6 * 10
-3Individual site/g polymkeric substance, affinity constant logK=3.6.
Embodiment 4:
The poly-succinimide of this example explanation embodiment 1 is the on-the-spot dispersive ability that is hydrolyzed to behind the poly aspartic acid lime carbonate in alkaline medium.
(high 26cm in the 100ml graduated cylinder; Diameter 3cm), 2 gram precipitated chalks are dispersed in 100ml pH10.5(NaOH) contain the NaCl, 3 * 10 of 3g/L
-3The CaCl of mol/L
2And in the aqueous solution of the hydrolyzed solution of different concns.
Measure the level of sedimentation after 10 minutes, with cm
3Be unit, make the curve of level of sedimentation as the polymer concentration function, concentration is represented (for dry-matter) with ppm.
Curve representation has flocculation phenomenon (polymkeric substance is too thin to the particulate tectum) then to be stabilization again earlier in unique accompanying drawing.
This stabilization to inorganic particle is beneficial especially because inorganic particle on cotton system thing deposition and collection tired be the hardened root.
Embodiment 5:
Polysuccinimide among this example explanation embodiment 1 is the on-the-spot restraining effect that is hydrolyzed to behind the poly aspartic acid calcium carbonate crystal in alkaline medium.
This product can be with Z.AMJAD at LANG-MUIR 1987,3 to the rejection characteristic of calcium carbonate crystal, and the method for describing among the 224-228 illustrates.
Containing 10
-3Mol/l sodium bicarbonate and 2 * 10
-3In the thermally-stabilised airtight pond of the supersaturated solution of mol/L calcium chloride (pH=8.6), add synthetic calcium carbonate (specific surface area=80m of 5g/L
2/ g theoretical diameter=20nm); Add 500ppm(to dry-matter) the hydrolyzed solution of embodiment 3 preparations after, measure the drop-out value of calcium carbonate crystal speed.
The result is as follows:
No polymkeric substance has polymkeric substance
Crystallization velocity 5 * 10
-710
-7
mol/L.S
Embodiment 6:
The effect of sclerosis inhibitor
This effect is when not having stained fabrics to exist, and following no dirty test piece is washed after 20 times measure:
Cotton fabric Testfabric 405(4)
Cotton Krefeld 12A(8)
Inorganic sclerosis is to calculate according to washing, the ash content (with the per-cent of cotton gross weight) of 950 ℃ of burnings of dried fabric after 3 hours.
The expression recently of the ash content of the ash oontent during sclerosis inhibitor effect inhibiting when not containing inhibitor, in the table I, represent with tee:
Ash content %
Washing composition T in the fiber contrast washing composition example 2
(4) 3.7% 1.9% 52%
(8) 4.1% 2.5% 60%
The table I
Claims (17)
1, the agent composition is washed in the work that is component with a kind of polyimide biopolymer or derivatives thereof at least, it is characterized in that this component has to be higher than 5 * 10
-4The COO of mol/ gram polymkeric substance
-Ionic concn is that also it can improve COO in the washing soln
-Ionic concn.
2,, it is characterized in that the initial COO of said polyimide biopolymer according to the detergent composition of claim 1
-Ionic concn is less than or equal to 2 * 10
-3Mol/ restrains polymer.
3,, it is characterized in that indication polyimide biopolymer is by dibasic aminoacid or its precursor polymeric and get according to the detergent composition of claim 1 or 2.
4,, it is characterized in that indication polyimide biopolymer is by aspartic acid and/or L-glutamic acid or its precursor polycondensation and get according to claim 1,2 or 3 detergent composition.
5,, but it is characterized in that the partial hydrolysis of indication polyimide biopolymer according to one detergent composition in the claim 1 to 4.
6, according to each detergent composition among the claim 1-5, it is characterized in that said polyimide biopolymer has weight-average molecular weight 300 to 10
7
7,, it is characterized in that indication polyimide biopolymer has weight-average molecular weight 500-60,000 according to the detergent composition of claim 6.
8, according to each detergent composition among the claim 1-7, it is characterized in that indication polyimide biopolymer accounts for 0.2-80%(weight in the indication detergent composition).
9, according to the detergent composition of claim 8, it is characterized in that indication polyimide biopolymer accounts for 2-50%(weight in the indication detergent composition).
10, according to each detergent composition among the claim 1-9, it is characterized in that tensio-active agent accounts for 2-50%(weight in said composition).
11, the application of a kind of polyimide biopolymer or derivatives thereof in powder detergent composition, it has and is higher than 5 * 10
-4The COO of mol/g polymkeric substance
-Ionic concn, and can increase COO in the washing lotion
-Ionic concn, it is as produce the material of the polypeptide washing assistant of partially biodegradable at least in washing lotion.
12, according to the application of claim 11, its spy is that said polyimide biopolymer is by dibasic aminoacid or its precursor polycondensation and get.
13,, it is characterized in that said polyimide biopolymer is by aspartic acid and/or L-glutamic acid or its precursor polycondensation and get according to the application of claim 12 or 11.
14,, but it is characterized in that also partial hydrolysis of polyimide according to each application in the claim 11 to 13.
15, according to each application among the claim 11-14, it is characterized in that said polyimide biopolymer has weight-average molecular weight 300-10
7
16,, it is characterized in that said polyimide biopolymer has weight-average molecular weight 500-60,000 according to the application of claim 15.
17, according to one application among the claim 11-16, it is characterized in that said polyimide biopolymer accounts for 0.2-80%(weight in said powder detergent composition).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9211831A FR2696473A1 (en) | 1992-10-06 | 1992-10-06 | Detergent composition incorporating a polyimide biopolymer hydrolyzable in a washing medium. |
| FR9211831 | 1992-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1085599A true CN1085599A (en) | 1994-04-20 |
Family
ID=9434185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93118644 Pending CN1085599A (en) | 1992-10-06 | 1993-10-05 | Mix can be in washing lotion the detergent composition of the polyimide biopolymer of hydrolysis |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0592265A1 (en) |
| JP (1) | JPH07122075B2 (en) |
| CN (1) | CN1085599A (en) |
| CA (1) | CA2107815A1 (en) |
| FR (1) | FR2696473A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288783A (en) * | 1992-05-14 | 1994-02-22 | Srchem Incorporated | Preparation of salt of polyaspartic acid by high temperature reaction |
| US5610267A (en) * | 1992-05-14 | 1997-03-11 | Bayer Ag | Process for preparing polysuccinimide by high temperature reaction |
| US5389303A (en) * | 1993-09-10 | 1995-02-14 | Srchem Incorporated | Mixtures of polyamino acids and citrate |
| ATE188497T1 (en) * | 1993-11-02 | 2000-01-15 | Bayer Ag | METHOD FOR PRODUCING POLYMERS CONTAINING ASPARAGIC ACID |
| US5531934A (en) * | 1994-09-12 | 1996-07-02 | Rohm & Haas Company | Method of inhibiting corrosion in aqueous systems using poly(amino acids) |
| KR960022448A (en) * | 1994-12-21 | 1996-07-18 | 미우라 아끼라 | Method for preparing polyaspartic acid and salts thereof |
| DE19528059A1 (en) * | 1995-07-31 | 1997-02-06 | Bayer Ag | Detergent and cleaning agent with imino disuccinates |
| DE10027624A1 (en) * | 2000-06-02 | 2001-12-06 | Zschimmer & Schwarz Mohsdorf G | Final cleaning of dyed or printed polyester-containing textiles, comprises oxidative washing in bath containing perborate, ethoxylated fatty acid or alkaryl sulfonate dispersant and alkali |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA6706930B (en) * | 1966-11-19 | |||
| DE1806502A1 (en) * | 1968-11-02 | 1970-05-21 | Henkel & Cie Gmbh | Textile washing agent contg a softener |
| JPS4851995A (en) * | 1971-11-01 | 1973-07-21 | ||
| CH667874A5 (en) * | 1985-12-19 | 1988-11-15 | Battelle Memorial Institute | BIODEGRADABLE SYNTHETIC POLYPEPTIDE AND ITS USE FOR THE PREPARATION OF MEDICAMENTS. |
| DE3724460A1 (en) * | 1986-07-29 | 1988-02-04 | Lion Corp | Wetting agent composition compatible with skin |
| DE3626672A1 (en) * | 1986-08-07 | 1988-02-11 | Bayer Ag | POLYASPARAGINAMID ACID |
| IT1240684B (en) * | 1990-04-26 | 1993-12-17 | Tecnopart Srl | POLYAMINO ACIDS SUCH AS BUILDERS FOR DETERGENT FORMULATIONS |
-
1992
- 1992-10-06 FR FR9211831A patent/FR2696473A1/en active Pending
-
1993
- 1993-09-21 EP EP93402296A patent/EP0592265A1/en not_active Withdrawn
- 1993-10-05 CN CN 93118644 patent/CN1085599A/en active Pending
- 1993-10-06 JP JP27297993A patent/JPH07122075B2/en not_active Expired - Lifetime
- 1993-10-06 CA CA 2107815 patent/CA2107815A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0592265A1 (en) | 1994-04-13 |
| CA2107815A1 (en) | 1994-04-07 |
| FR2696473A1 (en) | 1994-04-08 |
| JPH07122075B2 (en) | 1995-12-25 |
| JPH06192690A (en) | 1994-07-12 |
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