WO2008014914A1 - Matériaux de revêtement à base d'amidon présentant un comportement de dissolution contrôlable, sa fabrication et son utilisation - Google Patents

Matériaux de revêtement à base d'amidon présentant un comportement de dissolution contrôlable, sa fabrication et son utilisation Download PDF

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Publication number
WO2008014914A1
WO2008014914A1 PCT/EP2007/006614 EP2007006614W WO2008014914A1 WO 2008014914 A1 WO2008014914 A1 WO 2008014914A1 EP 2007006614 W EP2007006614 W EP 2007006614W WO 2008014914 A1 WO2008014914 A1 WO 2008014914A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
wrapping material
material according
ratio
starch
Prior art date
Application number
PCT/EP2007/006614
Other languages
German (de)
English (en)
Inventor
Stefano Bruzzano
Jörg BOHRISCH
Joachim Storsberg
Arvid Zimmermann
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Fit Gmbh
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 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., Fit Gmbh filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Publication of WO2008014914A1 publication Critical patent/WO2008014914A1/fr

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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
    • C11D3/20—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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • C09D103/08—Ethers
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to a coating and / or wrapping material containing a starch derivative which is O-alkylated at least partially with an ethylamino nofunktionlois a hydroxy group of the carbon atom C 2 of the monomers. Furthermore, the invention relates to a method for producing the coating and / or wrapping material. Likewise, uses of the coating material are specified.
  • the controlled release of active ingredients is usually sought in order to optimally utilize the various functionalities of active substances, for example in the laundry process.
  • the consumer usually doses the different types of active agent in the form that he fills two different products before the washing process in two chambers of the washing machine.
  • washing machine in this context are meant machines with which textiles or dishes can be cleaned.
  • One way of controlled release of active agents is to coat them with a sensitive material. This envelope loses on a certain stimulus or as
  • Temperature-sensitive means that when a certain temperature or a certain temperature interval is exceeded or undershot, the temperature-sensitive enveloping material loses its integrity in whole or in part, for example by melting or dissolving.
  • a pH-sensitive coating material completely or partially loses its integrity when it exceeds or falls below a defined pH or pH range, for example by dissolution.
  • a water-soluble polymeric film is described for the release of washing additives in the rinse cycle of washing machines.
  • the film remains intact during the normal wash cycle, but dissolves quickly in the rinse cycle.
  • a material having a pH-dependent solution behavior is combined with a material exhibiting a negative temperature-dependent solution behavior. This is to ensure that the films do not dissolve even at high temperatures.
  • controllably releasable active substances are present in the form of additives consisting of core and cladding.
  • a composition for use in a dishwashing machine is described in the published patent application DE 198 34 180 A1. This is characterized by a base composition which performs its function essentially in the main dishwashing cycle of the dishwasher, in the form of a tablet, and at least one particle with at least one
  • a core comprising at least one substance which functions essentially in the final rinse cycle of the dishwasher, and a coating substantially completely surrounding the core (s), which comprises at least one compound, whose solubility decreases as the concentration of a specific Ion in the surrounding medium, at least one particle being arranged in or on the tablet such that the surface of the particle (s) is at most partially in direct contact with the surface of the base composition surrounding it and the concentration of the specific ion in the local environment of the particle (s) to the substantially complete dissolution of the tablet is sufficiently high to prevent substantial dissolution of the cladding or substantial detachment of the cladding from the core (s), and method of performing a dishwashing cycle in a dishware sp WASHER using the composition.
  • Basic groups are amine groups, in particular secondary or tertiary amines.
  • a coating and / or wrapping material which contains a starch derivative which is at least partially O-alkylated with an ethyl-amino functionality at the hydroxyl group of the carbon atom C 2 of the monomers according to formula I,
  • R 1 to R 4 are selected from linear or branched alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, hydroxy, alkoxy, amino substituents and except for R 3 and R 4 also hydrogen and may be the same or different and / or R 1 together with R 2 and / or R 3 together with R 4 form a ring which may be aliphatic or aromatic and may contain heteroatoms,
  • R 5 is selected from hydrogen, linear or branched C 1 -C 12 -alkyl, alkenyl, alkynyl, aralkyl, aryl and / or heteroaryl substituents and / or carboxymethyl, which as free acid, as alkali metal salt and / or as esters may be present
  • R 6 is selected from C 1 -C 12 alkyl, alkenyl, alkynyl, aralkyl, aryl and / or heteroaryl substituents
  • the ratio of a / (a + b + c) is between 0.01 and 0.8
  • the advantageous properties according to the invention are particularly evident when the ratio a / (a + b + c) is in the range between 0.2 and 0.6. Furthermore, it is preferred if the ratio b / (a + b + c) is between 0.1 and 0.3.
  • the ratio b / (a + b + c) is between 0.8 and 0.3.
  • the application of the coating and / or wrapping material can take place both in one or in several layers.
  • the layer / particle to be protected is coated with starch derivatives with an amine switching functionality (with or without adhesion promoter).
  • alternating anionic starch derivatives for example starch sulphates, carboxymethyl starches
  • symplex alternating anionic starch derivatives
  • each layer thickness of each layer is between 0.01 and 2000 .mu.m, preferably between 0.1 and 1000 .mu.m. Above a pH of 8, the coating material according to the invention is largely water-insoluble.
  • the coating and / or wrapping material has the property that it exhibits an abrupt increase in solubility in a pH range ⁇ 8.
  • This can be demonstrated by thermoturbidimetric measurements of aqueous solutions of the coating material according to the invention. The results of these measurements are shown in FIGS. 2 to 5.
  • the average molecular masses (M w ) of the starch derivative of the coating and / or coating material are between 0.5 ⁇ 10 4 and 3 ⁇ 10 7 g / mol, preferably between 5 ⁇ 10 5 and 1, 1 '10 7 g / mol, very particularly preferably between 10 s and 1.1 • 10 7 g / mol.
  • starches which have been substituted according to formula 1 show particular properties as coating materials and / or coating materials compared with the compounds mentioned in DE 198 34 180 A1: in particular diisopropylethylamine groups - without restricting this to the present invention - are distinguished as particularly advantageous representatives. This shows up i.a. in that they show a greatly improved effect which far exceeds the state of the art (see Table 3, Comparative experiments on calgonite * - sphere).
  • the starch derivative coating / coating materials of the present invention are characterized by releasing a coated surfactant / active substance mixture more efficiently than known at the time of the prior art.
  • the coating / coating material according to the invention is characterized in that it - as can be seen from Tab. 3 - with significantly lower amounts of surfactant (to achieve the same performance) gets along with respect to the prior art.
  • the described advantages of the controlled release of active ingredient of the coating material according to the invention can be demonstrated by tensiometric measurements in comparison with a calgonite ball. The results are shown in FIGS. 6 to 8.
  • the coating and / or wrapping material according to the invention containing a starch derivative can are prepared according to methods known from the literature, comprising the following steps:
  • R 7 is selected from the group consisting of halogens, tosylate or phosphoric acid esters, d) optionally etherification of free hydroxy functionalities of the starch to the other Hydrophobing by optionally repeating steps a) and b) and then adding a reagent having the formula R 5 -
  • step d) can also be carried out before step c). This means that initially a hydrophobing of the starch is carried out and only then an aminoalkylation with the alkylating agent according to formula I-II.
  • the alkylating agent according to formula III and the alkylating agent from step d) can also be added simultaneously to the deprotonated starch, so that a simultaneous hydrophobing and O-alkylation can be carried out.
  • the liquor used in step a) is selected from alkali metal hydroxides, in particular sodium hydroxide and / or further customary Bronsted bases.
  • phase transfer catalyst Furthermore, it is advantageous if tetrabutylammonium hydrogen sulfate is selected as the phase transfer catalyst and / or other common phase transfer catalysts.
  • An important criterion according to the invention is the feasibility of derivatization in aqueous homogeneous phase.
  • Alkylating agents particularly suitable for the process are selected from the group consisting of N- (2-chloroethyl) -dimethylammonium chloride (CEDMAC), N- (2-chloroethyl) diisopropylammonium chloride (CEDEAC), N- (2-chloroethyl) - morpholinium chloride (CEMC), N- (2-chloroethyl) piperidinium chloride (CEPIC), N- (2- (2-(CEDMAC), N- (2-chloroethyl) diisopropylammonium chloride (CEDEAC), N- (2-chloroethyl) - morpholinium chloride (CEMC), N- (2-chloroethyl) piperidinium chloride (CEPIC), N- (2- (2-(CEDMAC), N- (2-chloroethyl) diisopropylammonium chloride (CEDEAC), N- (2-chloroeth
  • Chloroethyl) -pyrrolidinium chloride and / or mixtures thereof.
  • the extraction and purification of the product advantageously takes place in the process via dialysis.
  • steps b) and c) are carried out at a temperature between 40 and 100 ° C., preferably between 50 and 70 ° C.
  • the coating and / or wrapping materials are used in detergents. It is favorable if the starch derivative forms the coating and / or encapsulation of the active detergent, of a detergent-active substance and / or of the surfactant.
  • the coating and / or wrapping materials described in the present invention are used as wrapping materials, for example but not limited thereto, for surfactants and / or detergents and / or active-ingredient formulations such as, but not limited to, used in washing machines or dishwashers used. Especially preferred the Diisopropylethylaminrestn be used.
  • Surfactants are understood to mean surface-active compounds, for example polyethylene glycols and their derivatives, and mixtures thereof, without restricting the present invention to these.
  • the present invention can be used as a protective barrier for an underlying substance / substance mixture. Only by a defined pH change of the substance / substance mixture to be protected by releasing the integrity of the protective layer / shell layer is released. Prerequisite here, however, is that the melting point of the substance / substance mixture to be protected is greater than 55 0 C.
  • the invention can also be used for protective coatings of buildings, structures, wood, metals, plastics, etc. If the protective layer is soiled, for example by "graffiti" without limiting the present invention, it can be removed from the substrate together with the paint adhering to the protective layer etc., for example by treatment with an aqueous solution adjusted pH / pH range.
  • a preferred embodiment here is when the protective coating is an anti-graffiti coating.
  • Example 1 Procedure for the synthesis of a coating material according to the invention
  • CMS carboxymethyl starch
  • a Standardtensidgemisch 60: 40 mixture (wt .-%) of Polyglycol 35000PS (Clariant) and Dehypon "3697 gram (Cognis)) having a melting range> 55 0 C was placed in an extrusion press wide by cutting the 8 mm each and. cubes were obtained after each 8 mm of high strand, which were mixed with PVA powder and rounded in a commercially available mixer.
  • Fluid bed coater coated with various materials All are based on the pH-dependent soluble diisopropylethylamine starch.
  • the mass of the rounded cubes is -0.4 g, that of the comparative calgonite ball -0.8 g.
  • HP-AO-3 cube + 30 mg diisopropylamino carboxymethyl starch
  • HP-A0-D3 Dice + 3 double layers of 8 mg each Cation. Potato starch and 8 mg diisopropylamine carboxymethyl starch
  • HP-A1-D3 cube + 40 mg hydroxypropyl starch + 3 bilayers of 8 mg cation each. Potato starch and 8 mg diisopropylamino carboxymethyl starch
  • the rinsing performance is determined by an internal comparison method of fit GmbH, which will be explained in more detail below.
  • the hard water is prepared according to DIN EN 60734 part B from NaHCO 3 , MgSO 4 • 7H 2 O and CaCl 2 "2H 2 O and provided in tank pallets of 1000 1.
  • the hard water is after one day with the tank open or after one Week with the tank closed to renew.
  • ballast dirt consisting of margarine, drinking milk, ketchup, mustard, gravy, potato starch, egg yolk, benzoic acid and water is added in the cleaning cycle.
  • the assessment is based on a 6-step scale according to Table 1.
  • FIG. 1 An exemplary synthesis scheme for representing a coating material according to the invention-without limiting the invention to the selected example-is shown in FIG. 1 shown.
  • FIGS. 2 to 5 show the results of thermoturbidimetric measurements of the coating material HP-AO-3 according to the invention.
  • FIGS. 6 to 8 show the advantages of the controlled release of active substance when using the coating material according to the invention on the basis of tensiometric measurements in direct comparison with Calgonit-Kuglen.
  • the material according to the invention depends on the environmental conditions depending on sharp cloud points in a pH range between 8 and
  • a 21-cup is filled with a 0.4% detergent solution (fully soluble, without surfactant), with the SITA device immersed in the solution. Subsequently, the surfactant body is immersed in a sieve in the solution. This is heated with gentle stirring to 60 0 C and held for 10 min at this temperature. Then the sieve with capsule and the SITA device are transferred to a second 21-beaker filled with cold water. After 5 min, this beaker is heated to 65 0 C. The temperature and the surface tension are measured over time (Fig. 6-8).
  • the figures show the surfactant release depending on the time and the respective phase in the dishwashing cycle (cleaning phase, final rinse phase).
  • the aim of the selective surfactant release only in the final rinse phase is achieved exclusively by the coatings according to the invention (FIGS. 7, 8), whereas the commercial material "loses" surfactant already in the cleaning phase, recognizable by the decrease in the surface tension (FIG. 6).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Biochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un matériau de revêtement et/ou d'enrobage, ledit matériau contenant un dérivé d'amidon qui est au moins en partie O-alkylé par une fonctionnalité éthylamino d'un groupement hydroxy de l'atome de carbone C2 du monomère. L'invention concerne également un procédé de fabrication du matériau de revêtement et/ou d'enrobage. L'invention concerne également l'utilisation du matériau de revêtement.
PCT/EP2007/006614 2006-07-31 2007-07-25 Matériaux de revêtement à base d'amidon présentant un comportement de dissolution contrôlable, sa fabrication et son utilisation WO2008014914A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610035659 DE102006035659B4 (de) 2006-07-31 2006-07-31 Beschichtungsmaterialien auf Stärkebasis mit kontrollierbarem Auflöseverhalten, sowie deren Verwendung
DE102006035659.4 2006-07-31

Publications (1)

Publication Number Publication Date
WO2008014914A1 true WO2008014914A1 (fr) 2008-02-07

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PCT/EP2007/006614 WO2008014914A1 (fr) 2006-07-31 2007-07-25 Matériaux de revêtement à base d'amidon présentant un comportement de dissolution contrôlable, sa fabrication et son utilisation

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DE (1) DE102006035659B4 (fr)
WO (1) WO2008014914A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271920A (zh) * 2014-06-03 2016-01-27 安庆余 一种墙面装饰涂料的制造工艺及其应用工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970140A (en) * 1957-08-09 1961-01-31 American Maize Prod Co Process for preparing amino ethers of starch
US2975124A (en) * 1957-08-28 1961-03-14 Nat Starch Chem Corp Flocculation of fine particles by starch ethers
DE1643011A1 (de) * 1966-03-10 1972-03-16 Scholten Chemische Fab Verfahren zur Herstellung von Polysaccharidderivaten und daraus hergestellte Filme
EP0284334A2 (fr) * 1987-03-24 1988-09-28 The Clorox Company Composition de rinçage soluble de polymère film pour additifs de lavage
DE19729305A1 (de) * 1997-07-09 1999-01-14 Hoechst Ag Thermoplastische Mischung auf Basis von Stärke enthaltend mindestens eine kationische und mindestens eine anionische Stärke, Verfahren zu ihrer Herstellung sowie Verwendung
US20040071742A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917506A (en) * 1956-11-21 1959-12-15 Nat Starch Chem Corp Cold water soluble amino alkyl ethers of starch
US2935436A (en) * 1957-05-09 1960-05-03 Nat Starch Chem Corp Method of making paper containing a starch ether and product produced thereby
US3332792A (en) * 1963-09-27 1967-07-25 Gen Aniline & Film Corp Manufacture of antihalation layers
US3598623A (en) * 1968-04-24 1971-08-10 Staley Mfg Co A E Carboxyl starch amine ethers and paper coating compositions containing same
US4374673A (en) * 1980-12-31 1983-02-22 Hercules Incorporated Stable dispersions of fortified rosin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970140A (en) * 1957-08-09 1961-01-31 American Maize Prod Co Process for preparing amino ethers of starch
US2975124A (en) * 1957-08-28 1961-03-14 Nat Starch Chem Corp Flocculation of fine particles by starch ethers
DE1643011A1 (de) * 1966-03-10 1972-03-16 Scholten Chemische Fab Verfahren zur Herstellung von Polysaccharidderivaten und daraus hergestellte Filme
EP0284334A2 (fr) * 1987-03-24 1988-09-28 The Clorox Company Composition de rinçage soluble de polymère film pour additifs de lavage
DE19729305A1 (de) * 1997-07-09 1999-01-14 Hoechst Ag Thermoplastische Mischung auf Basis von Stärke enthaltend mindestens eine kationische und mindestens eine anionische Stärke, Verfahren zu ihrer Herstellung sowie Verwendung
US20040071742A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271920A (zh) * 2014-06-03 2016-01-27 安庆余 一种墙面装饰涂料的制造工艺及其应用工艺

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DE102006035659B4 (de) 2014-12-24
DE102006035659A1 (de) 2008-02-07

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