EP2064294A2 - Additif pour peinture - Google Patents

Additif pour peinture

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Publication number
EP2064294A2
EP2064294A2 EP07808589A EP07808589A EP2064294A2 EP 2064294 A2 EP2064294 A2 EP 2064294A2 EP 07808589 A EP07808589 A EP 07808589A EP 07808589 A EP07808589 A EP 07808589A EP 2064294 A2 EP2064294 A2 EP 2064294A2
Authority
EP
European Patent Office
Prior art keywords
kda
groups
modified
glucan
weight
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.)
Withdrawn
Application number
EP07808589A
Other languages
German (de)
English (en)
Inventor
Theodoor Maximiliaan Slaghek
Johannes Wilhelmus Timmermans
Ingrid Karin Haaksman
Hendrik Jacobus Arie Breur
Jurgen Scheerder
Gerritdina Hendrika Van Geel-Schutten
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.)
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Original Assignee
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
DSM IP Assets BV
Materials Innovation Centre BV
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 Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO, DSM IP Assets BV, Materials Innovation Centre BV filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority to EP07808589A priority Critical patent/EP2064294A2/fr
Publication of EP2064294A2 publication Critical patent/EP2064294A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B13/00—Preparation of cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • 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
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the invention relates to the use of chemically modified carbohydrates as corrosion inhibitors and/or preservatives, especially in coatings, and to a composition suitable for coating solid surfaces, in particular metals, for the purpose of enhancing resistance to degradation of the surfaces.
  • Coatings based on vinyl chloride polymer binders show, when properly formulated, excellent anti-corrosive performance, which is due to their high barrier against oxygen. However, for many applications and for environmental reasons, the presence of chloride is not preferred.
  • Coatings based on styrene-acrylic or acrylic polymer binders have a much lower barrier against oxygen and therefore their anticorrosive performance is often inferior to that of the vinyl chloride based binders. Therefore, even more of the anti-corrosive performance relies on using anti-corrosive pigments and flash rust inhibitors.
  • the use of zinc and flash rust inhibitors like sodium nitrite is not preferred from an environmental point of view. Therefore, there is a need for additives that can partially or completely replace anti-corrosive pigments and/or flash rust inhibitors and which do not have the same negative environmental impact as metals or nitrite.
  • WO 03/008618 discloses certain high molecular weight bacterial ⁇ -glucans, some of which have anti-corrosive properties, e.g. for ship hulls. These are a 8 MDa highly branched ⁇ -l,3-glucan and a 36 MDa branched alternan-type ( ⁇ -l,3/ ⁇ -l,6) glucan.
  • the modified polysaccharide contains anionic groups.
  • a part of the hydroxyl groups may be blocked by hydrophobic alkyl or alkanoyl groups.
  • the coating compositions of the invention are water-based and contain conventional components such as pigments, binders, etc. and are characterised by containing 0.1-5 wt.% of the modified polysaccharide.
  • the polysaccharide to be used according to the invention can be any polysaccharide having repeating anhydroglycose units or their derivatives such as deoxyanhydroglycose or anhydroglycuronic acid units.
  • the polysaccharide preferably contains at least 30% of monosaccharide units having a hydroxymethyl group (-CH 2 OH), either as such, or as its oxidised form (uronic acid).
  • the polysaccharide is a glucan, which may be either an ⁇ -glucan (starch family etc.), or a ⁇ -glucan or xyloglucan (cellulose and chitin, tamarind kernel, ⁇ -1,3 and/or ⁇ -1,6 glucans, e.g (hetero)glucans in which at least 30% of the units are ⁇ -1,3, such as curdlan and scleroglucan).
  • ⁇ -glucan starch family etc.
  • xyloglucan cellulose and chitin, tamarind kernel, ⁇ -1,3 and/or ⁇ -1,6 glucans, e.g (hetero)glucans in which at least 30% of the units are ⁇ -1,3, such as curdlan and scleroglucan.
  • the polysaccharide is of the starch group, which may be from any source, including potato, corn, rice, tapioca, etc.
  • the starch Prior to its oxidation, the starch may be gelatinised in a manner known per se, such as heat treatment in water at 60°C, or treatment with alkali or the starch is modified via a granular process.
  • the starch may be derivatised in its granular form, e.g. using extrusion techniques.
  • the polysaccharide is a glucan having both ⁇ -1,3 and ⁇ -1,6 links, for example having between 10 and 50%, preferably between 20 and 40% of ⁇ -1,3 links, and between 20 and 70%, preferably between 30 and 60% of ⁇ -1,6 links, together with e.g. 5-20% of branching.
  • Examples include the alternan-type glucans from Leuconostoc mesenteroid.es, such as e.g.
  • the modified polysaccharide should have a molecular weight of at least 10 kDa (degree of polymerisation (DP) of about 60), and the molecular weight may be as high as 10,000 kDa (DP about 60,000) or even higher.
  • the average molecular weight is at least 15 kDa or even 20 kDa, up to 3000 kDa, or especially 1000 kDa; the most preferred molecular weight is between 20 and 800 kDa (DP between about 120 and 5,000).
  • a first fraction has an average molecular weight between 20 and 160 kDa, especially between 20 and 60 kDa, and/or at least 20% (by weight, up to e.g. 50% by weight) of the polysaccharide has a molecular weight between 20 and 160 kDa, especially between 20 and 60 kDa, while a second fraction having an average molecular weight between 200 and 800 kDa, e.g. accounting for 10-60% by weight, may also be present.
  • Average molecular weights as used herein are to be understood as weight-average. Molecular weights can be determined as described in the Example section below.
  • the molecular weight of a polysaccharide can be reduced to the desired values by chemical treatment, such as hydrolysis, prior to or after modification, or even during modification by adapting the modification conditions (e.g. the temperature and/or pH during oxidation).
  • the modified polysaccharide contains from 0.1 to 0.9 anionic groups per monosaccharide unit, preferably between 0.2 and 0.6 anionic groups per unit.
  • the anionic groups may be derived from carboxylic, phosphoric, sulphuric acid, and the like groups.
  • the acid groups can be present as a result of substitution or addition of suitable acid-containing reagents.
  • carboxylic groups may result from carboxyalkylation, in particular carboxymethylation, or from reaction with an anhydride such as maleic or succinic anhydride.
  • Phosphonic groups may be present as phosphate groups, resulting e.g. from reaction with phosphorylating agents (see e.g.
  • WO 97/28298 or as phosphonic or phosphinic acid groups, resulting e.g. from reaction with halomethyl phosphonic acids.
  • Sulphonic acids may be present e.g. as sulphate groups or as a result of sulphite addition to polysaccharide aldehydes (see e.g. WO 99/29354) or to maleic anhydride adducts (products with -0-CO-CH 2 - CH(COOH)-SO 3 H groups).
  • the anionic groups are carboxylic groups resulting from oxidation, e.g.
  • a (primary) hydroxymethyl group (-CH 2 OH, usually at C6 of a monosaccharide unit, but also optionally of hydroxymethyl groups in substituents, such as hydroxyethyl or hydroxypropyl groups), or of a bis(hydroxymethylene) group (-CHOH- CHOH-, usually at C2-C3 of a monosaccharide unit).
  • the anionic groups stem from TEMPO-mediated oxidation of hydroxymethyl groups.
  • TEMPO-mediated oxidation is well documented in the art, see e.g. De Nooy, Synthesis 1996, 1153-1174, WO 95/07303, WO 00/50388, WO 00/50621, WO 01/00681, WO 02/48197 and EP 1149846.
  • oxidising agent such as hypochlorite, hypobromite, hydrogen peroxide, or a peracid, or even oxygen
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • mediators such as halide ions, metal complexes or oxidative enzymes (e.g. peroxidase or phenol oxidase or laccase), leading to 6-carboxylic acid derivatives (uronic acids) in glucans and other aldohexose polymers.
  • a catalytic amount of nitroxyl is preferably 0.05-5% by weight, based on dry starch, or 0.05-5 mol% with respect to dry starch. Most preferably, these catalytic amounts are between 0.1 and 1 %.
  • the oxidation can be performed in aqueous solution or dispersion, e.g. by first adding TEMPO and optionally further catalysts or mediators, and then gradually or at once adding the oxidising agent, such a sodium hypochlorite solution, and reacting at temperatures between 0 and 50°C, preferably between 10 and 30°C, while maintaining neutral to mildly alkaline conditions, especially at a pH between 6 and 11, depending on the particular oxidising agent, preferably between 8 and 9.5.
  • the degree of oxidation determines the proportion of carboxyl groups in the modified polysaccharide, and can be varied by adapting the amount of oxidising agent. Any aldehyde groups remaining after oxidation may be further oxidised to carboxyl groups using additional of other oxidising agents, such as chlorite.
  • Oxidation of bis(hydroxymethylene) groups which produces two carboxyl groups in the same monosaccharide unit with ring opening, can be performed as well-known on the art, e.g. in a two-step process using periodate followed by e.g. chlorite oxidation, or in a one-step process using e.g. hypochlorite, with or without bromide.
  • the hypochlorite oxidation is usually accompanied with some chain length reduction.
  • the carboxyl groups may already be present in the native polysaccharide, such as in glycuronans.
  • Combinations of different anionic groups are also well suited for the invention. It is preferred that the anionic groups are in the ionised (salt) form, e.g. as alkali metal, alkaline earth metal, other metal, or ammonium salts.
  • Esterification can be done with activated Ci-Cs monocarboxylic acids, such as acid halides or anhydrides of Q-C O alkanoic, C 3 -C 8 cycloalkanoic or C 7 -C 8 benzoic or substituted benzoic acids.
  • C 2 -C 4 acyl groups are preferred.
  • the total degree of substitution (DS) of alkyl and acyl groups, preferably with acyl groups is from 0.01 to 2.2 per monosaccharide unit.
  • the DS is from 0.025 to 0.05 groups per unit, or between about 1 and 2% of the available hydroxyl groups being etherified or esterified.
  • the content of alkyl and acyl groups mentioned herein refers to those groups when attached to oxygen atoms of original hydroxyl groups of the parent polysaccharide, even though a minor substitution of anionic groups with such alkyl or acyl groups - resulting in partial esters and anhydrides respectively - is not detrimental to the effectiveness of the derivatives, as long as a major part of anionic groups is still anionic (including the neutral acid form).
  • Effective derivatives include those which contain two different types of groups on the hydroxyl positions, at least one of the two being an alkanoyl group.
  • the other may be another alkanoyl or other acyl group or an alkyl group.
  • a combination may e.g. be a methyl or ethyl group and an acetyl or propionyl group, an acetyl group and a propionyl or buryryl group, or a propionyl group and a butyryl group.
  • the degree of substitution is preferably between 0.01 to 1.1, especially from 0.02 to 0.1 group per monosaccharide unit.
  • the etherification and/or esterification can be carried out before or after the introduction of anionic groups.
  • the alkylation or acylation can be performed at the same conditions as most oxidation reactions, i.e. ambient temperature, a pH between 7 and 10, and in aqueous solution, preferably at relatively high concentration (e.g. between 5 and 75% dry substance of the reaction mixture).
  • the invention furthermore relates to modified glucans as such, which are modified in such a manner to contain from 0.1 to 0.6, preferably and from 0.2 to 0.5 carboxyl groups per monosaccharide, and from 0.01 to 0.2, preferably from 0.02 to 0.1 C2-C4 alkanoyl groups per monosaccharide unit.
  • the modified glucan has an average molecular weight between 20 kDa and 800 kDa, especially between 20 kDa and 500 kDa.
  • the glucan has a bimodal molecular weight distribution, e.g.
  • a glucan is defined herein as a polysaccharide containing at least 50% of optionally modified anhydroglucose units.
  • the invention also pertains to an aqueous coating composition
  • a polymeric binder and 0.1-10 wt.%, on polymeric binder weight, preferably 0.25-5 wt% and in particular 0.35-2 wt.%, of a modified polysaccharide as described above.
  • Any polymer can be used, but particularly useful are polymers that are suitable for anti-corrosive applications.
  • the polymeric binder can be waterborne or solvent-borne or can be prepared in a solvent which is O
  • the polymeric binders employed in the invention are vinyl polymers.
  • a vinyl polymer herein is meant a homo- or copolymer derived from the addition polymerisation (using a free radical process) of at least one olefinically unsaturated monomer which are also known as vinyl monomers.
  • the polymeric binder can be, but is not limited to, a polyacrylic, styrene-acrylic, epoxy, epoxy-acrylic, urethane, urethane-acrylic, polyester, polyamide, alkyd, chlorinated polymers, fluorinated polymers, or mixtures thereof.
  • the vinyl polymers may contain vinyl monomers which provide an adhesion and/or crosslinking functionality to the resulting polymer coating. Examples of these include (meth)acrylic monomers having at least one free carbonyl, hydroxyl, epoxy, aceto acetoxy, or amino group; allyl methacrylate, tetraethylene glycol methacrylate, and divinyl benzene. Adhesion promoting monomers include amino, urea, or N-heterocyclic groups.
  • the vinyl monomers bearing ionic or potentially ionic water- dispersing groups are vinyl monomers bearing anionic or potentially anionic water- dispersing groups, more preferably vinyl monomers bearing carboxylic acid groups and most preferably (meth)acrylic acid.
  • Especially preferred polymeric binder materials include styrene acrylic copolymers.
  • the styrene acrylic copolymers comprise monomers selected from i) styrenic monomers (such as for example styrene, alpha-methyl styrene); ii) Cl to C8 alkyl (meth)acrylates; iii) monomers carrying water-dispersing or potentially water-dispersing groups; and iv) other monomers.
  • the monomers carrying water-dispersing or potentially water-dispersing groups are preferably anionic or potentially anionic groups (e.g. (meth)acrylic acid).
  • the polymeric binder materials preferably comprise less than 10 wt% of functionalised monomers (e.g. carbonyl functional).
  • the polymeric binder materials, especially when they are styrene acrylic copolymers, preferably have an acid value in the range of from 3 to 80 mg KOH/g.
  • the polymeric binder materials have a weight-average molecular weight in the range of from 1,000 to 200,000, more preferably 1,000 to 100,000 g/mol as measured by GPC.
  • Molecular weights of polymers may be determined by using gel permeation chromatography using a polymer, such as polystyrene, of known molecular weight as a standard.
  • the polymeric binder materials have a Tg (glass transition temperature as calculated using the Fox equation) in the range of from 0 to 100 0 C, more preferably 0 to 60 0 C.
  • Tg glass transition temperature
  • the Tg of a polymer herein stands for the glass transition temperature and is well known to be the temperature at which a polymer changes from a glassy, brittle state to a rubbery state.
  • Tg values of polymers may be calculated using the well-known Fox equation.
  • Tg in Kelvin, of a copolymer having "n" copoly- merised comonomers is given by the weight fractions W of each comonomer type and the Tg' s of the homopolymers (in Kelvin) derived from each comonomer according to the equation:
  • the calculated Tg in Kelvin may be readily converted to 0 C.
  • the polymeric binders can optionally be crosslinked.
  • This can be a self-crosslinking system, i.e. a coating that crosslinks without the need for the addition of a compound that reacts with the polymeric binder, examples of which are Schiff-base, auto -oxidative or silane crosslinking.
  • Crosslinking may also be achieved by adding reagents that react with the binders, such as a (poly)amine compounds that react with epoxy-based polymeric binders, melamine or isocyanate compounds that react with OH or acid functional binders at ambient or elevated temperatures, and if required in the presence of a catalyst.
  • the vinyl polymers are normally made using free radical addition polymerisation o
  • the pH of the composition containing the vinyl polymer may be raised to neutralise sufficiently any acidic groups (i.e. render them sufficiently ionised) to allow the preparation of an aqueous composition by the addition of a base, such as an organic or inorganic base, examples of which include organic amines such as trialkylamines (e.g. triethylamine, tributylamine), morpholine and alkanolamines, and inorganic bases such as ammonia, NaOH, KOH and LiOH.
  • a base such as an organic or inorganic base, examples of which include organic amines such as trialkylamines (e.g. triethylamine, tributylamine), morpholine and alkanolamines, and inorganic bases such as ammonia, NaOH, KOH and LiOH.
  • Average molecular weight of polysaccharides can be determined by Size Exclusion Chromatography (HPLC) using a Waters Associates (Etten-Leur, NL) series liquid chromatography system with a refractive index (RI 410 nm) detector, a guard column (7.5 mm ID * 7.5 cm, particles size 12 ⁇ m) and two size exclusion columns (7.5 mm ID * 30 cm, particles size 17 ⁇ m). The temperature of the columns is maintained at 35°C. A phosphate buffer (100 mM sodium phosphate with 0.02% sodium azide, pH 7) is used as a mobile phase (flow 1 mL/min).
  • HPLC Size Exclusion Chromatography
  • the columns are calibrated with dextran standards with a molecular weight of 5,000, 10,000 and 500,000 (Pharmacia, Sweden), respectively.
  • a 100 mg sample is diluted with 10 mL phosphate buffer.
  • the solid content of the coating composition is 30-70 wt%, preferably 35-60 wt% and more preferably 40-55 wt%.
  • the polysaccharide can be added during any stage during the preparation of the polymer binders, or it can be added after completion of the polymeric binder, or it can be added during any stage during the paint preparation. Preferably the polysaccharide is added directly after completion of the polymeric binders.
  • the polysaccharide can be added as a solid component or it can first be dispersed or dissolved in water or a suitable solvent. If needed a surfactant can be used to aid dispersion of the polysaccharide in water. Preferably the polysaccharide is added as a solid or dissolved in water.
  • the polysaccharide can be applied first onto the substrate that needs to be protected followed by the application of an anti-corrosive polymer. The polysaccharide is then preferably applied as a solution in water. However preferably the polysaccharide is applied together with the polymeric binder.
  • the combination of polysaccharide and polymeric binder can be used as a primer, a topcoat or both.
  • the coating composition according to the invention further contains usual components for coating surfaces, such as extenders (e.g. calcium carbonate and china clay), pigments, dispersants such as pigment dispersion aids, fillers, binders, lubricants, surfactants, wetting agents, rheology modifiers, levelling agents, anti-cratering agents, biocides, antifoam agents, sedimentation inhibitors, UV absorbers, heat stabilisers, and antioxidants, solvents, other anti-corrosive agents, etc.
  • extenders e.g. calcium carbonate and china clay
  • dispersants such as pigment dispersion aids
  • fillers e.g. calcium carbonate and china clay
  • binders e.g. calcium carbonate and china clay
  • lubricants e.g. calcium carbonate and china clay
  • surfactants e.g. calcium carbonate and china clay
  • the composition is essentially free of heavy metals, meaning that the weight ratio between any heavy metals and modified polysaccharide is below 0.1, preferably below 0.02.
  • the modified polysaccharides and the coating compositions containing them can be used for coating metal like iron, steel like Cold Rolled Steel (CRS), galvanised steel, aluminium and other surfaces so as to provide them with an anti-corrosive coating. Such coatings are used to protect metals from corrosion.
  • the coatings can be applied by conventional coating applications techniques such as spraying or roll coating. The coatings are typically allowed to dry at ambient temperatures or dried at elevated temperatures depending on the application.
  • the surface Prior to applying the coatings, the surface may be prepared in conventional ways, for example, by cleaning (with for example a solvent or a water-based alkaline cleaner or an acidic solution), by mechanically treatment (for example abrasion), and/or conversion coating (phosphodising).
  • cleaning with for example a solvent or a water-based alkaline cleaner or an acidic solution
  • mechanically treatment for example abrasion
  • conversion coating phosphodising
  • the degree of substitution was determined by pretreating a sample by dissolving in water for free acid and in 0.5 M NaOH for total acid analysis.
  • the sample was analysed using HPLC (column Aminex HPX-87H 300 mm x 7.8 mm, eluent 0.01 M sulphuric acid, and PJ detection) and the analysis showed a degree of acetyl substitution of 0.03.
  • the degree of substitution was determined by pretreating a sample by dissolving in water for free acid and in 0.5 M NaOH for total acid analysis.
  • the sample was analysed using HPLC (column Aminex HPX-87H 300 mm x 7.8 mm, eluent 0.01 M sulphuric acid, and PJ detection) and the analysis showed a degree of acetyl substitution of 0.03.
  • the molecular weight measurements showed two peaks which correspond to MW's of 310 kDa and 33 kDa respectively.
  • Example 3 Example 2 was repeated with 41 % oxidised EPS LB 180.
  • Example 5 Carboxymethyl starch having a degree of carboxymethyl substitution of 0.20 (20%), obtained by reaction Paselli SA-2 with sodium monochloroacetate, was acetylated as described in Example 1.
  • 2,3-Dicarboxy starch having a DO of 24% obtained by hypochlorite oxidation of Paselli SA-2 in the presence of sodium bromide, was acetylated as described in Example 1.
  • 2,3-Dicarboxy starch having a DO of 22% obtained by hypochlorite oxidation of Paselli SA-2 in the absence of sodium bromide, was acetylated as described in Example 1.
  • a pigment paste was prepared by mixing under high shear demineralised water (21.6 gram), 2-aminopropanol (0.30 gram, as a 90% solution), Disperse-Ayd W-33 (3.60 gram) (a pigment dispersant commercially available from Sasol Servo), Butyl glycol (13.50 gram), Kronos 2190 (33,90 gram, TiC>2 available from Kronos), MicroTalc it extra (24,00 gram, a filler available from Mondo Minerals Oy), Heucophos ZPO (32.10 gram, Zinc Phosphate available from Heubach) and Hostaint Black (3.60 gram, black pigment available from Clarant).
  • NeoCryl XK-87 160.50 gram, a styrene- acrylic dispersion polymer commercially available from DSM NeoResins
  • Texanol 5.10 gram
  • Drew 210 693 (0.90 gram, a defoamer available from Ashland
  • Viscoatex 46 (0.15 gram, an acrylic thickener available from Codex)
  • Ser-AD FA179 (0.90 gram, a flash rust inhibitor available from Sasol Servo
  • the C6- oxidised carbohydrate from Example 1 or 2 was added (1.60 gram).
  • the same formulation was used without the C6-oxidised starch from Example 1 or 2.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement qui comprend un polysaccharide modifié, en particulier un α-glucane, contenant entre 0,1 et 0,9 groupes anioniques par unité monosaccharide et entre 0,01 et 1,0 groupes alkyle ou alcanoyle C1-C6 par unité monosaccharide. Le polysaccharide modifié présente un poids moléculaire relativement élevé compris entre 20 kDa et 3000 kDa.
EP07808589A 2006-09-22 2007-09-24 Additif pour peinture Withdrawn EP2064294A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07808589A EP2064294A2 (fr) 2006-09-22 2007-09-24 Additif pour peinture

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06121137 2006-09-22
PCT/NL2007/050465 WO2008035975A2 (fr) 2006-09-22 2007-09-24 Additif pour peinture
EP07808589A EP2064294A2 (fr) 2006-09-22 2007-09-24 Additif pour peinture

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EP2064294A2 true EP2064294A2 (fr) 2009-06-03

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Publication number Priority date Publication date Assignee Title
WO2012150904A1 (fr) * 2011-05-04 2012-11-08 Kth Holding Ab Barrière contre l'oxygène pour applications d'emballage
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