EP0854908A1 - Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose - Google Patents

Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose

Info

Publication number
EP0854908A1
EP0854908A1 EP96927113A EP96927113A EP0854908A1 EP 0854908 A1 EP0854908 A1 EP 0854908A1 EP 96927113 A EP96927113 A EP 96927113A EP 96927113 A EP96927113 A EP 96927113A EP 0854908 A1 EP0854908 A1 EP 0854908A1
Authority
EP
European Patent Office
Prior art keywords
formulation according
microfibrils
acid
less
formulation
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.)
Granted
Application number
EP96927113A
Other languages
English (en)
French (fr)
Other versions
EP0854908B1 (de
Inventor
Véronique Guillou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0854908A1 publication Critical patent/EP0854908A1/de
Application granted granted Critical
Publication of EP0854908B1 publication Critical patent/EP0854908B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to descaling and cleaning formulations based on cellulose microfibrils.
  • the detergent formulations used for descaling have very specific characteristics.
  • the products entering into its composition must be capable of remaining stable and of retaining their properties at very acidic pHs, most of the time less than 2 and very often less than 1.
  • these formulations, for optimal use must have a low viscosity when they are subjected to a high shear as is the case during the application of the product, then a high viscosity when the shear stresses are low. , so as to allow a slow flow along the walls to be descaled.
  • the present invention aims to provide a descaling formulation having a pseudo-plastic rheological profile, stable over time.
  • the subject of the invention is a descaling formulation comprising cellulose microfibrils, of which at least 80%, preferably at least 85% of the cells are with primary walls and at most 20%, preferably at most 15% of the cells are with secondary walls, having a degree of crystallinity of at most 50%, preferably at most 40%.
  • microfibrils mentioned above confer on the formulation a rheology of pseudo-plastic character, moreover and that these microfibrils, surprisingly, remain stable and retain their properties in very acidic media, c that is to say whose pH is between 0 and 1.
  • the microfibrils used in the composition of the formulations according to the invention therefore consist of cellulose.
  • Cellulose represents the essential element of the walls of plant cells.
  • the latter consist of primary walls (parenchyma cells) and secondary walls, in different proportions depending on the nature of the plant from which they come.
  • the primary walls mainly comprise certain pectins and proteins and little cellulose, generally around 5%, and depend on the development of the cell.
  • the fibrils of the secondary walls constitute networks forming lamellae in which there is a layer Si (thickness of 0.2 to 0.35 ⁇ m) comprising very entangled and spiraled microfibrils, a layer S2 (thickness of 1.8 to 3, 8 ⁇ m) essentially based on cellulose in a very compact, oriented form, with slightly tangled microfibrils forming concentric lamellae, and finally a layer S3 (thickness of 0.1 to 0.15 ⁇ m) based on cellulose fibers tangled and spiraling.
  • Si thickness of 0.2 to 0.35 ⁇ m
  • S2 thinness of 1.8 to 3, 8 ⁇ m
  • a layer S3 thickness of 0.1 to 0.15 ⁇ m
  • microfibrils used as an additive in the formulations according to the invention have at least 80%, preferably at least 85% of cells with primary walls and at most 20%, preferably at most 15% of cells with secondary walls.
  • the cellulose microfibrils have an average diameter of between 20 and 40 ⁇ , preferably between 30 and 40 ⁇ .
  • the degree of crystallinity of the microfibrils is at most 50%, preferably at most 40%. More particularly, the degree of crystallinity is between 20 and 38%.
  • microfibrils The length of these microfibrils is of the order of 10 ⁇ m, and less. It is more particularly possible to use microfibrils with a length less than or equal to 2 ⁇ m.
  • the cellulose microfibrils are obtained from beet, bran from cereals or any other plant.
  • the cellulose microfibrils have a high purity because of the order of 90%.
  • the remaining 10% consists in particular of residual compounds such as water, pectins, such as galacturonic acid, rhamnose or even ferulic acid, hemicelluloses, such as arabinose, galactose, mannose, xylose as well as mineral salts.
  • pectins such as galacturonic acid, rhamnose or even ferulic acid
  • hemicelluloses such as arabinose, galactose, mannose, xylose as well as mineral salts.
  • microfibrils can be obtained by extraction by conventional means. Preferably, they can be obtained according to a process described below, implementing a treatment carried out on the pulp of plants with primary walls, such as for example beet pulp after it has undergone a stage d prior extraction of sucrose, according to methods known in the art. Said method comprises the following steps:
  • step (d) optionally bleaching the washed residue, (e) diluting the third solid residue obtained at the end of step (d) so as to obtain a dry matter content of between 2 and 10% by weight, (f) homogenization of the diluted suspension.
  • step (a) the term "pulp” means moist, dehydrated pulp, preserved by silage or partially defected.
  • the extraction step (a) can be carried out in an acid medium or in a basic medium.
  • the pulp is suspended in a solution of water for a few minutes so as to homogenize the acidified suspension at a pH between 1 and 3, preferably between 1, 5 and 2.5.
  • This operation is carried out with a concentrated solution of an acid such as hydrochloric acid or sulfuric acid.
  • This step can be advantageous for removing the calcium oxalate crystals which may be present in the pulp, and which, because of their significant abrasive nature, can cause difficulties in the homogenization step.
  • the pulp is added to an alkaline solution of a base, for example sodium hydroxide or potassium hydroxide, of concentration less than 9% by weight, more particularly less than 6% by weight.
  • a base for example sodium hydroxide or potassium hydroxide
  • concentration of the base is between 1 and 2% by weight.
  • Stage (a) is generally carried out at a temperature of between approximately
  • step (a) The duration of step (a) is between approximately 1 hour and approximately 4 hours.
  • step (a) a partial hydrolysis takes place with release and solubilization of most of the pectins and hemicelluloses, while preserving the molecular mass of the cellulose.
  • the solid residue is recovered from the suspension originating from stage (a) using known methods. Thus, it is possible to separate the solid residue by centrifugation, by filtration under vacuum or under pressure, with filter cloths, or filter presses for example, or even by evaporation.
  • the first solid residue obtained is optionally subjected to a second extraction step, carried out under alkaline conditions.
  • a second extraction step is carried out when the first has been carried out under acidic conditions. If the first extraction was carried out under alkaline conditions, the second step is only optional.
  • this second extraction is carried out with a base preferably chosen from sodium hydroxide and potash, the concentration of which is less than approximately 9% by weight, preferably between approximately 1% and approximately 6% by weight.
  • the duration of the alkaline extraction step is between approximately 1 and approximately 4 hours. It is preferably equal to approximately 2 hours. At the end of this second extraction, if it takes place, a second solid residue is recovered.
  • step (c) the residue from step (a) or (b) is washed thoroughly with water in order to recover the residue of cellulosic material.
  • step (c) The cellulosic material of step (c) is then optionally bleached, in step (d), according to conventional methods.
  • treatment can be carried out with sodium chlorite, sodium hypochlorite, hydrogen peroxide at a rate of 5-20% relative to the amount of dry matter treated.
  • Different concentrations of bleach can be used, at temperatures between about 18 ° C and 80 ° C, preferably between about 50 ° C and 70 ° C.
  • the duration of this step (c) is between approximately 1 hour and approximately 4 hours, preferably between approximately 1 and approximately 2 hours.
  • a cellulosic material is then obtained containing between 85 and 95% by weight of cellulose. At the end of this bleaching step, it may be preferable to wash the cellulose thoroughly with water.
  • the resulting suspension optionally bleached, is then rediluted in water at a rate of 2 to 10% of dry matter.
  • the homogenization step corresponds to a mixing, grinding or any high mechanical shearing operation, followed by one or more passages of the cell suspension through a small diameter orifice, subjecting the suspension to a pressure drop of at least 20 MPa and a high speed shearing action followed by a high speed deceleration impact.
  • the mixing or grinding is, for example, carried out by passage (s) in the mixer or grinder for a period ranging from a few minutes to about an hour, in a device of the type such as a WARING BLENDOR equipped with a four-blade propeller or grinder grinding wheel or any other type of grinder, such as a colloid mill.
  • a homogenizer of the MANTON GAULIN type in which the suspension is subjected to a shearing action at high speed and pressure in a narrow passage and against a shock ring.
  • MICRO FLUIDIZER is a homogenizer mainly consisting of a compressed air motor which will create very high pressures, an interaction chamber in which the homogenization operation will take place (elongational shear, shock and cavitation) and a low pressure chamber which allows depressurization of the dispersion.
  • the suspension is introduced into the homogenizer preferably after preheating at a temperature between 40 and 120 ° C, preferably between 85 and 95 ° C.
  • the temperature of the homogenization operation is maintained between 95 and 120 ° C, preferably above 100 ° C.
  • the suspension is subjected in the homogenizer to pressures of between 20 and 100 MPa, and preferably greater than 50 MPa.
  • the homogenization of the cellulosic suspension is obtained by a number of passages which can vary between 1 and 20, preferably between 2 and 5, until a stable suspension is obtained.
  • the homogenization operation can advantageously be followed by a high mechanical shearing operation, for example in a device such as the ULTRA TURRAX from SYLVERSON.
  • the amount of microfibrils used in the composition of the formulation according to the invention is between 0.05 and 1.5% by weight. Preferably, this amount is between 0.1 and 1% by weight.
  • the percentages by weight are expressed by weight of material (for example microfibrils) relative to the total weight of the formulation.
  • the formulation according to the invention also comprises an acidic compound.
  • the latter can be organic or mineral.
  • All organic acids are suitable insofar as their pKa is less than or equal to 6. More particularly, mention may be made of aliphatic mono- or polycarboxylic acids comprising 1 to 12 carbon atoms. As an example of acids of this type, mention may be made of formic, acetic, maleic, citric, sulfamic, oxalic, adipic, succinic, glutaric acids.
  • the amount of acid entering into the composition of the formulation is such that the pH of the final formulation is less than or equal to 2, more particularly less than 1.5.
  • the amount of acid used is such that the pH of the formulation is less than or equal to 1, and more particularly less than or equal to 0.5.
  • the acid content in the formulation is between 1 and 20% by weight. More particularly it is between 3 and 15% by weight.
  • the formulation according to the invention also comprises at least one detergent surfactant.
  • this compound is chosen from nonionic, cationic or amphoteric surfactants.
  • nonionic surfactant By way of example of a nonionic surfactant, mention may be made of polyoxyalkyienated alkylphenols, the alkyl substituent of which is Cg-C-
  • polyoxyalkyienated alkylphenols the alkyl substituent of which is Cg-C-
  • nonionic surfactants there may be mentioned glucosamides, glucamides, glycerolamides, the products resulting from the condensation of ethylene oxide or propylene oxide, with ethylenediamine, the oxides of amines such as alkyl oxides C10-C18 dimethylamines, alkoxy oxides CQ-C-22 ethyl dihydroxy ethylamines, alkylpolyglycosides described in US-A-4,565,647, fatty acid amides C8-C20. 'Are ethoxylated fatty amides, ethoxylated amines.
  • preferably polyoxyalkylene aliphatic alcohols and polyoxyalkylene alkylphenols are used, these surfactants being used alone or as a mixture.
  • alkylphenols use is more particularly made of compounds having 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms, in particular octyl, nonyl or dodecyl.
  • ethoxylated (OE units) or ethoxy-propoxylated (OE units + OP) alkylphenols generally have 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms, in particular octyl, nonyl or dodecyl.
  • surfactants of this type mention may be made most particularly of ethoxylated nonylphenol with 6 EO units, ethoxylated nonylphenol with 9 EO units, ethoxylated nonylphenol with 10 EO units, ethoxylated nonylphenol with 12 EO units, ethoxy-propoxylated nonylphenols with 25 OE + OP units, ethoxy-propoxylated nonylphenols with 30 OE + OP units, ethoxy-propoxylated nonylphenols with 40 OE + OP units.
  • the quaternary ammoniums are suitable for carrying out the invention.
  • the surfactants included in the formulation according to the invention can also be chosen from amphoteric surfactants.
  • alkyl betaines alkyl dimethyl betaines, alkylamidopropylbetaines, alkylamidopropyl-dimethylbetaines, alkyltrimethylsulphobetaines sulphobetaines, imidazoline derivatives such as alkyl amphoacetates •, alkylamphodiacetates, alkylamphopropionates, alkylampho dipropionates, the alkylsulta 'ines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, these compounds can be used alone or as a mixture.
  • Mirapon® Excel, Mirataine® CBS, Mirataine® CB surfactants the range of
  • Miranol®, Amphionic® SFB, Amphionic® XL may in particular be suitable for carrying out the present invention.
  • the amount of surfactants is between 0.1 and 5% by weight. Preferably, it is between 0.8 and 3% by weight.
  • the formulation according to the present invention can also comprise the conventional additives for this type of application in particular.
  • the formulations can contain dyes, perfumes, preservatives.
  • the additive content is less than 2% by weight, or even 1% by weight.
  • the content of these compounds is a function of the effect to be obtained and this is very often achieved with contents as low as 0.1 to 0.2% by weight.
  • the complement to 100% by weight of the formulation consists of water.
  • the cellulose microfibrils are first dispersed in at least a fraction of the water entering the formulation.
  • the viscosity characteristics of the formulation can be adapted according to the quality of the agitation.
  • the stirring is slow, that is to say with a speed of less than 1000 rpm
  • the viscosity of the resulting formulation is lower than the viscosity of a formulation obtained with the same amount of microfibrils, but prepared with intense stirring, for example greater than 5000 rpm. Therefore, more intense agitation will reduce the amount of microfibrils needed to achieve the desired level of viscosity.
  • the devices with which the formulation is prepared are conventional and are in particular devices of the Ultra-Turrax® type, devices with deflocculating or mixing paddles.
  • the acid or the mixture of acids is added, then the detergent surfactant (s) and finally the additive (s).
  • the agitation of the first stage that of the dispersion of the microfibrils in water, may or may not be preserved. It is indeed possible to carry out the dispersion of the microfibrils under strong agitation and then to reduce this during the introduction of the other elements of the formulation.
  • the preparation of the formulation is usually carried out at room temperature.
  • formulations according to the invention in particular find their application in the descaling of sanitary facilities whether in the household or institutional field (community).
  • a suspension comprising an amount of cellulose microfibrils in an aqueous solution comprising 10% hydrochloric acid, so as to obtain a pH of 0.
  • cellulose microfibrils were supplied by GENERALE SUCRIERE; they were prepared according to example 20 of European patent application 96 400261.2 filed on February 7, 1996.
  • Example 1a consists in suspending the microfibrils using a pale deflocculator, with a speed of 1400 rpm.
  • Example 1b consists in suspending the microfibrils using an Ultra-Turrax, with a speed of 500 revolutions / min.
  • the object of this example is to evaluate the viscosity of a suspension of microfibrils having a pH of 2.
  • the suspension comprises 0.8% of microfibrils and was obtained by stirring with a pale deflocculator rotating at 500 revolutions / min.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP96927113A 1995-10-03 1996-07-31 Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose Expired - Lifetime EP0854908B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9511697 1995-10-03
FR9511697A FR2739394B1 (fr) 1995-10-03 1995-10-03 Formulations detartrantes et nettoyantes a base de microfibrilles de cellulose
PCT/FR1996/001206 WO1997012954A1 (fr) 1995-10-03 1996-07-31 Formulations detartrantes et nettoyantes a base de microfibrilles de cellulose

Publications (2)

Publication Number Publication Date
EP0854908A1 true EP0854908A1 (de) 1998-07-29
EP0854908B1 EP0854908B1 (de) 2000-03-01

Family

ID=9483256

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96927113A Expired - Lifetime EP0854908B1 (de) 1995-10-03 1996-07-31 Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose

Country Status (21)

Country Link
US (1) US5998349A (de)
EP (1) EP0854908B1 (de)
JP (1) JP3014768B2 (de)
KR (1) KR100256136B1 (de)
CN (1) CN1105171C (de)
AT (1) ATE190088T1 (de)
AU (1) AU697812B2 (de)
BR (1) BR9610769A (de)
CA (1) CA2231512A1 (de)
CZ (1) CZ291536B6 (de)
DE (1) DE69606878T2 (de)
EA (1) EA000499B1 (de)
ES (1) ES2146011T3 (de)
FR (1) FR2739394B1 (de)
HU (1) HUP9900048A2 (de)
IL (1) IL123918A (de)
MX (1) MX9802600A (de)
PL (1) PL325996A1 (de)
PT (1) PT854908E (de)
TR (1) TR199800652T1 (de)
WO (1) WO1997012954A1 (de)

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DE69606878T2 (de) 2000-08-17
CZ291536B6 (cs) 2003-03-12
KR19990064005A (ko) 1999-07-26
CA2231512A1 (fr) 1997-04-10
CN1105171C (zh) 2003-04-09
CN1201484A (zh) 1998-12-09
EP0854908B1 (de) 2000-03-01
KR100256136B1 (ko) 2000-05-15
JP3014768B2 (ja) 2000-02-28
US5998349A (en) 1999-12-07
FR2739394B1 (fr) 1997-12-05
EA000499B1 (ru) 1999-08-26
JPH11500176A (ja) 1999-01-06
TR199800652T1 (xx) 1998-06-22
PL325996A1 (en) 1998-08-17
PT854908E (pt) 2000-06-30
AU6704896A (en) 1997-04-28
CZ99098A3 (cs) 1998-08-12
EA199800265A1 (ru) 1998-10-29
DE69606878D1 (de) 2000-04-06
AU697812B2 (en) 1998-10-15
FR2739394A1 (fr) 1997-04-04
IL123918A (en) 2001-03-19
MX9802600A (es) 1998-11-30
HUP9900048A2 (hu) 1999-05-28
BR9610769A (pt) 1999-07-13
ATE190088T1 (de) 2000-03-15
WO1997012954A1 (fr) 1997-04-10
ES2146011T3 (es) 2000-07-16

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