+

WO2013041649A1 - Utilisation d'une dispersion aqueuse de polyesters biodégradables - Google Patents

Utilisation d'une dispersion aqueuse de polyesters biodégradables Download PDF

Info

Publication number
WO2013041649A1
WO2013041649A1 PCT/EP2012/068584 EP2012068584W WO2013041649A1 WO 2013041649 A1 WO2013041649 A1 WO 2013041649A1 EP 2012068584 W EP2012068584 W EP 2012068584W WO 2013041649 A1 WO2013041649 A1 WO 2013041649A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
mol
paper
acid
weight
Prior art date
Application number
PCT/EP2012/068584
Other languages
German (de)
English (en)
Inventor
Liqun Ren
Gimmy Alex Fernandez Ramirez
Hermann Seyffer
Gabriel Skupin
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Priority to EP12759762.3A priority Critical patent/EP2758594A1/fr
Priority to CA2849663A priority patent/CA2849663A1/fr
Publication of WO2013041649A1 publication Critical patent/WO2013041649A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • the present invention relates to the use of an aqueous dispersion of at least one biodegradable polyester in the form of a coating for improving the barrier properties of packaging materials made of paper or cardboard, in particular packaging materials made of recycled paper or cardboard, compared to mineral oils.
  • the present invention also relates to a process for the preparation of barrier coatings on paper or board, in particular on recycled paper or board.
  • Paper and cardboard packaging is often made from recycled paper.
  • the recycled paper may contain mineral oil residues, e.g. B. from the commonly used for newspaper printing inks contain. Even at room temperature volatiles of these residues evaporate and beat in the case of food packaging on the packaged in the box food, such. As noodles, grits, rice or cornflakes, down. Most of the inner bags made from polymer films used today also do not provide adequate protection. Studies by the Cantonal Laboratory of Zurich have revealed significant levels of residual oil in food packaged in recycled paper packaging. The volatile mineral oil constituents are predominantly harmful paraffin and naphthenic hydrocarbons and aromatic hydrocarbon substances, in particular those having 15 to 25 C atoms.
  • Paper or paperboard packaging materials are often provided with a barrier coating to reduce penetration of the vegetable or animal fats or oils contained in food.
  • coatings based on water-based (meth) acrylate polymer dispersions for.
  • styrene-acrylate polymer dispersions described for paper and cardboard The polymers show good barrier properties against liquid oils and fats.
  • a good barrier action against liquid oils and fats does not necessarily have a good barrier action against volatile mineral oils, in particular with respect to gaseous mineral oils, eg. B. health-critical paraffin and naphthenic hydrocarbons and aromatic hydrocarbons, especially those having 15 to 25 carbon atoms, given because it is different transport mechanisms for the substances passing through.
  • fats and oils differ from hydrocarbons, ie from mineral oil constituents in their polarity and thus in their diffusion behavior through barrier layers.
  • aqueous polyester dispersions of biodegradable polyester are known. The polyester dispersions are used inter alia for coating paper. Coatings produced in this way have a good barrier action against vegetable oils and fatty acids. A barrier effect against mineral oils, in particular volatile substances, is not mentioned.
  • the present invention relates to the use of aqueous dispersions of at least one biodegradable polyester, as defined herein and in the following, in the form of a coating to improve the barrier properties of paper or paperboard packaging material to mineral oils, especially volatile mineral oils, especially gaseous mineral oils , especially those having 15 to 25 carbon atoms, for. B. harmful paraffin and naphthenic hydrocarbons and aromatic hydrocarbons.
  • the aqueous dispersions of the at least one biodegradable polyester are particularly suitable for the production of barrier coatings on paper or paper Cardboard produced from recycled paper and thus mineral oil residues, in particular volatile mineral oil residues, especially those with 15 to 25 carbon atoms, eg. For example, contain harmful paraffin and naphthenic hydrocarbons and aromatic hydrocarbons.
  • a preferred embodiment of the invention relates to the use of aqueous dispersions of at least one biodegradable polyester, as defined herein and in the following, in the form of a coating to improve the barrier properties of paper or paperboard packaging material to mineral oils, the packaging material at least in part , was usually at least 30 wt .-% (wt .-%, based on total fiber mass), in particular at least 50 wt .-% or completely made of mineral oil loaded recycled paper.
  • a preferred embodiment of the invention relates to the use of aqueous dispersions of at least one biodegradable polyester, as defined herein and in the following, in the form of a coating to improve the barrier properties of paper or paperboard to mineral oils, the Paper or the cardboard or the packaging material at least in part, generally at least 30 wt .-% (wt .-%, based on total fiber mass), in particular at least 50 wt .-% or was completely made of mineral oil loaded recycled paper, in particular, such a packaging material intended for food packaging.
  • These include sales packaging, such as boxes or papers, but also consumer packaging, such as disposable tableware, z.
  • the coating according to the invention is located on at least one of the paper or board surfaces or on at least one surface of the packaging material. It can also be at least one, z. B. at least one or in particular two, of a plurality of layers of a multilayer coating of the paper, or the carton or the packaging material.
  • the coating according to the invention can be arranged directly on a surface of the flat carrier material (paper or cardboard). However, other layers may also be present between the carrier material and the coating according to the invention, eg. B. primer layers, other barrier layers or colored or black and white ink layers.
  • the coating according to the invention is preferably located on the inner side of the packaging material facing the packaged product.
  • a sufficient barrier effect is achieved if the coating has a coverage of at least 1 g / m 2 , often at least 2 g / m 2 , especially at least 3 g / m 2 and especially at least 5 g / m 2 , calculated as solids per m 2 coated surface.
  • the coating preferably has a coating thickness in the range from 2 to 50 g / m 2 , in particular from 3 to 40 g / m 2 , especially from 5 to 30 g / m 2 , calculated as solids per m 2 of the coated surface.
  • the coating thickness is accordingly on average at least 1 ⁇ , often at least 2 ⁇ , in particular at least 3 ⁇ and especially at least 5 ⁇ , z. B. in the range of 2 to 50 ⁇ , in particular 3 to 40 ⁇ , especially 5 to 30 ⁇ .
  • a specific embodiment of the invention relates to the use for coating cardboard, in particular cardboard, which at least in part, as a rule at least 30 wt .-% (wt .-%, based on total fiber mass), in particular at least 50 wt. -% or completely made from mineral oil loaded recycled paper.
  • the coating usually has a coverage of at least 2 g / m 2 , often at least 3 g / m 2 , especially at least 4 g / m 2 and especially at least 5 g / m 2 , calculated as solids per m 2 of the coated cardboard top - surface, up.
  • the coating preferably has a coating thickness in the range of 3 to 50 g / m 2 , in particular 4 to 40 g / m 2 , especially 5 to 30 g / m 2 , calculated as solids per m 2 of the coated board surface.
  • the coating thickness is accordingly on average at least 2 ⁇ , often at least 3 ⁇ , in particular at least 4 ⁇ and especially at least 5 ⁇ , z. B. in the range of 2 to 50 ⁇ , in particular 3 to 40 ⁇ , especially 5 to 30 ⁇ .
  • a further embodiment of the invention relates to the use for coating paper, in particular paper, which is at least partially, as a rule at least 30% by weight (wt .-%, based on total fiber mass), in particular at least 50 wt .-% or made entirely of mineral oil-loaded recycled paper.
  • the coating has a coating thickness of generally at least 1 g / m 2 , often at least 2 g / m 2 , in particular at least 3 g / m 2 , calculated as solids per m 2 of the coated paper surface on.
  • the coating preferably has a coating thickness in the range of 1 to 30 g / m 2 , in particular 2 to 25 g / m 2 , especially 3 to 20 g / m 2 , calculated as solids per m 2 of the coated paper surface.
  • the coating thickness is accordingly on average at least 1 ⁇ , often at least 2 ⁇ , in particular at least 3 ⁇ , z. B. in the range of 12 to 30 ⁇ , in particular 2 to 25 ⁇ , especially 3 to 20 ⁇ .
  • the coating of the invention may be one or more preferably, for. B. two, three, four or five, arranged on each other layers, which were prepared using the aqueous polyester dispersion.
  • the thickness of the individual layers of the coating will generally amount to at least 0.5 g / m 2 , often at least 1 g / m 2 , in particular at least 2 g / m 2 , especially at least 3 g / m 2 and is typically in the Range of 1 to 30 g / m 2 , in particular 1 to 25 g / m 2 , especially 2 to 20 g / m 2 or 2 to 12 g / m 2 , calculated as solids per m 2 of the coated surface.
  • the coating according to the invention at least two, in particular two, three, four or five and especially two or three layers arranged on one another, which have been produced using the aqueous polyester dispersion.
  • biodegradability means that the polyesters disintegrate in a reasonable and detectable period of time.
  • the degradation is usually hydrolytic and is mainly caused by the action of microorganisms such as bacteria, yeasts, fungi and algae or by the hydro- rolases contained therein.
  • the biodegradability can be z. B. determine by mixing polyester with compost and stored for a certain time.
  • C0 2 -free air is allowed to flow through ripened compost during composting and subjected to a defined temperature program.
  • biodegradability is defined as the ratio of the net CO 2 release of the sample (after subtraction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample).
  • Biodegradable polyester usually show after a few days of composting significant degradation phenomena such as fungal growth, crack and hole formation. Such polyesters are known to those skilled in the art and are commercially available.
  • the polyesters contained in the aqueous dispersions are typically insoluble in water and are therefore present in the form of particles in the dispersion used according to the invention.
  • the weight-average particle diameter of the polymer particles (weight average, determined by light scattering) in these dispersions will generally not exceed 10 ⁇ m, often 5 ⁇ m, in particular 2000 nm, especially 1500 nm and is typically in the range from 50 nm to 10 ⁇ , often in the range of 100 nm to 5 ⁇ , in particular in the range of 150 to 2000 nm, especially in the range of 200 to 1500 nm.
  • less than 90 wt .-% of the polymer particles have a particle diameter of 10 ⁇ , in particular 5 ⁇ and especially 2 ⁇ not exceed.
  • the determination of the particle size is carried out in a conventional manner by light scattering on dilute dispersions (0.01 to 1 wt .-%).
  • Biodegradable polyesters are, for example, the polyesters from the groups of aliphatic polyesters, aliphatic copolyesters, aliphatic-aromatic copolyester. Also suitable are blends of the aforementioned biodegradable polyesters with one another or blends with other, biodegradable, preferably water-insoluble polymers, eg. As starch or polyalkylene.
  • Blends are blends of at least one aliphatic copolyester with at least one polymer from the group starch, polyalkylene and aliphatic polyesters such as polylactic acid or polyhydroxyalkanoates and blends of at least one aliphatic-aromatic copolyester with at least one polymer from the group starch, polyalkylene and aliphatic polyesters such as polylactic acid or polyhydroxyalkanoates.
  • the proportion of the biodegradable polyester will be at least 30% by weight, in particular at least 40% by weight, based on the total solids content of the dispersion.
  • those dispersions are used in which the polyester is the sole water-insoluble, ie dispersed, polymer constituent or the proportion of the biodegradable polyester is at least 80% by weight, in particular at least 90% by weight, based on the total solids content of the dispersion, is.
  • those dispersions are used which contains, in addition to the biodegradable polyester, at least one further water-insoluble, ie dispersed, polymer constituent, which is preferably likewise biodegradable.
  • the proportion of the biodegradable polyester will then generally be from 30 to 90% by weight, in particular from 40 to 80% by weight, based on the total solids content of the dispersion.
  • the proportion of the dispersed polymer component other than the polyester is then usually from 10 to 70% by weight, in particular from 20 to 60% by weight, based on the total amount of the polymers dispersed in the dispersion.
  • Suitable further dispersed polymer constituents which may be included in the dispersion together with the polyester are also preferably biodegradable and selected, for example, from starch and polyalkylene carbonates.
  • the polyesters contained in the dispersions used according to the invention typically have a number average molecular weight MN in the range from 5000 to 1,000,000 daltons, in particular in the range from 8,000 to 800,000 daltons and especially in the range from 10,000 to 500,000 daltons.
  • the weight-average molecular weight Mw of the polymer is typically in the range of 20,000 to 500,000 daltons, often in the range of 30,000 daltons to 4,000,000 daltons, and more preferably in the range of 40,000 to 2,500,000 daltons.
  • the polydispersity index MW / MN is generally at least 2 and is often in the range from 3 to 20, in particular in the range from 5 to 15. Molecular weight and polydispersity index can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1 ,
  • the viscosity number of the polyesters which is indirectly a measure of the molecular weight, is typically in the range of 50 to 500 ml / g, often in the range of 80 to 300 ml / g and especially in the range of 100 to 250 ml / g (determined according to EN ISO 1628-1 at 25 ° C on a 0.5 wt .-% solution of the polymer in o-dichlorobenzene / phenol (1: 1 w / w)).
  • the polyesters contained in the dispersions used according to the invention may be amorphous or partially crystalline.
  • the polyester contained in the dispersion is essentially unbranched, ie the degree of branching generally has a value of ⁇ 0.005 mol / kg, in particular ⁇ 0.001 mol / kg and especially ⁇ 0.0005 mol / kg ,
  • the polyester is branched, wherein the degree of branching preferably does not exceed a value of 1 mol / kg, in particular 0.5 mol / kg and especially 0.3 mol / kg.
  • the degree of branching is understood to mean the number of monomer units condensed in which more than two, e.g. B. three, four, five or six suitable for condensation functional groups that react with carboxylic acid or hydroxyl groups under bond formation, for.
  • the polyester has a degree of branching of generally 0.0005 to 1 mol / kg, preferably 0.001 to 0.5 mol / kg, and more preferably 0.005 to 0.3 mol / kg.
  • the biodegradable polyester is selected from the group of aliphatic polyesters, aliphatic copolyesters, aliphatic-aromatic copolyesters and mixtures thereof.
  • An aliphatic polyester is understood as meaning a polyester which is composed exclusively of aliphatic monomers.
  • An aliphatic copolyester is understood as meaning a polyester which is composed exclusively of at least two, in particular at least three, aliphatic monomers, the acid component and / or the alcohol component preferably comprising at least two mutually different monomers.
  • An aliphatic-aromatic copolyester is understood as meaning a polyester which is composed both of aliphatic monomers and of aromatic monomers, wherein the acid component preferably comprises at least one aliphatic acid and at least one aromatic acid.
  • polylactides polylactic acid
  • polycaprolactone block copolymers of polylactide with P0IV-C2-C4-alkylene glycol
  • block copolymers of polycaprolactone with poly-C2-C4-alkylene glycol and the copolyesters defined below consist of at least one aliphatic or cycloaliphatic dicarboxylic acid or an ester-forming derivative thereof and at least one aliphatic or cycloaliphatic diol component and, if appropriate, further components.
  • polylactides is to be understood as meaning polycondensation products of lactic acid. Suitable polylactides are described in WO 97/41836, WO 96/18591,
  • the degree of polymerization n in formula (B) is in the range from 1000 to 4000, preferably from 1500 to 3500 and more preferably from 1500 to 2000 (number average).
  • the average molecular weights (number average) of these products are in the range of 71,000 to 284,000 g / mol according to the degree of polymerization.
  • Suitable polylactides are for. Available from Cargill Dow LLC (eg PLA Polymer 404ID, PLA Polymer 4040D, PLA Polymer 4031D, PLA Polymer 2000D or PLA Polymer 1 100) or from Mitsui Chemicals (Lactea).
  • block copolymers are marketed, for example, by Aldrich (eg, product number 659649). These are polymers comprising polylactide blocks and poly-C 2 -C 4 -alkylene oxide blocks.
  • Such block copolymers are z. B. by condensation of lactic acid or by ring-opening polymerization of lactic acid lactone (A) in the presence of poly-C2-C4-alkylene glycols available.
  • Biodegradable polyesters suitable according to the invention are also polycaprolactones.
  • polycaprolactones By those skilled in the art means polymers which are described by the formula D shown below, where n is the number of repeating units in the polymer, d. H. means the degree of polymerization.
  • the degree of polymerization n in formula (D) is in the range of 100 to 1000, preferably 500 to 1000 (number average).
  • the number average molecular weights of these products are in the range of 10,000 g / mol to corresponding degree of polymerization
  • Particularly preferred polymers of the formula (D) have average molar masses (number average) of 50,000 g / mol (CAPA 6500), 80,000 g / mol (CAPA 6800) and 100,000 g / mol (CAPA FB 100).
  • Polycaprolactones are generally prepared by ring-opening polymerization of ⁇ -caprolactone (compound C) in the presence of a catalyst.
  • Polycaprolactones are available from Solvay under the designation CAPA polymers, e.g. CAPA 6100, 6250, 6500 or CAPA FB 100, commercially available.
  • Such polymers may, for. B. by polymerization of caprolactone in the presence of polyalkylene glycols, for example, analogously to the Macromolecules 2003, 36, pp 8825- 8829 described method can be prepared.
  • Biodegradable polyesters which are suitable according to the invention are in particular copolyesters which are synthesized from at least one aliphatic or cycloaliphatic dicarboxylic acid or an ester-forming derivative thereof and at least one aliphatic or cycloaliphatic diol component and optionally further components.
  • the polymer to be dispersed according to the invention is an aliphatic or aliphatic-aromatic copolyester which is essentially composed of:
  • At least one diol component B selected from aliphatic and cycloaliphatic diols and mixtures thereof;
  • component A optionally one or more compounds D, the at least three, z.
  • aliphatic copolyesters are understood to mean those copolyesters which contain, as component A, exclusively component a1).
  • aliphatic-aromatic copolyesters are understood as meaning those copolyesters which contain as component A both the component a1) and the component a) and optionally a3) in a condensed form.
  • the statements in% by weight based on the ester-forming constituents refer to the constituents of the components A, B, C and D in a condensed form and thus to the total mass of the polyester and not to the amounts used to prepare the polyester, unless otherwise stated.
  • the acid component A preferably comprises
  • a2) 0 to 70 mol%, in particular 10 to 65 mol% or 10 to 60 mol% of at least one aromatic dicarboxylic acid or its ester-forming derivative or mixtures thereof,
  • aqueous dispersions of copolyesters are used whose acid component A comprises the following constituents:
  • a3) 0 to 5 mol%, in particular 0 to 3 mol% or 0 to 2 mol%, of one or more aromatic dicarboxylic acids which have at least one sulfonic acid group, or their ester-forming derivatives or mixtures thereof the molar percentages of components a1), a2) and a3) together amount to 100%.
  • the acid component A may contain small amounts of a sulfonated aromatic dicarboxylic acid z.
  • a sulfonated aromatic dicarboxylic acid z As sulfoisophthalic acid or a salt thereof, condensed, wherein the proportion of sulfonated carboxylic acid usually not more than 5 mol%, often not more than 3 mol%, in particular not more than 2 mol% is and z.
  • B in the range of 0.1 to 5 mol% or 0.1 to 3 mol% or 0.2 to 2 mol%, based on the total amount of compounds of component A.
  • the amount of sulfonated carboxylic acids is less than 1 mol%, in particular less than 0.5 mol%, based on the component A.
  • such copolyesters have from 0.01 to 0 , 2 mmol / g, in particular 0.05 to 0.15 mmol / g sulfonic acid groups. In a further embodiment of the invention, such copolyesters have less than 0.05 mmol / g, in particular less than 0.01 mmol / g sulfonic acid groups.
  • the proportion of diol component B is 98 to 102 mol%, in particular 99 to 101 mol%, based on the total amount of components a1), a2) and optionally a3).
  • the polyester-forming constituents contain not more than 2% by weight, in particular not more than 1% by weight, based on the total weight of the polyester, of one or more further bifunctional compounds C which react with carboxylic acid or hydroxyl groups to form bonds.
  • polyester-forming constituents contain not more than 2% by weight, in particular not more than 1% by weight, based on the total weight of the polyester, of one or more compounds D which are at least three , z. B. have three, four or five functionalities which react with carboxylic acid or hydroxyl groups to form bonds.
  • components a1), a2), a3) and b) in particular comprise 96 to 100% by weight, in particular 98 to 100% by weight, of such copolyesters.
  • aqueous dispersions of partially aromatic or aliphatic-aromatic copolyesters which are characterized by the following composition:
  • a2) 20 to 40 mol%, often 20 to 35 mol%, in particular 25 to 34 mol%, based on the total amount of components a1) and a2), terephthalic acid or their ester-forming derivatives or mixtures thereof;
  • the components a1), a2) and b) 80 to 99.8 wt .-%, in particular 90 to 99.7 wt .-%, and especially 95 to 99.6 wt .-% of the polyester make up.
  • Aliphatic dicarboxylic acids a1) which are suitable according to the invention generally have 2 to 10 carbon atoms, preferably 4 to 8 and in particular 6 carbon atoms. They can be both linear and branched.
  • the cycloaliphatic dicarboxylic acids which can be used in the context of the present invention are as a rule those having 7 to 10 carbon atoms and in particular those having 8 carbon atoms. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • malonic acid succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 1, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-Norbornandicarbonklare.
  • ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are likewise usable are the di-C 1 to C 6 alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters.
  • Anhydrides of dicarboxylic acids can also be used.
  • Preferred dicarboxylic acids are succinic acid, adipic acid, sebacic acid, azelaic acid and brassylic acid and their respective ester-forming derivatives or mixtures thereof. Particularly preferred are adipic acid, sebacic acid or succinic acid and their respective ester-forming derivatives or mixtures thereof.
  • the aromatic dicarboxylic acids a2 are generally those having 8 to 12 carbon atoms and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1, 5-naphthoic acid and ester-forming derivatives thereof.
  • the D1-C1-C6 alkyl esters, z As dimethyl, diethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, di- iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester.
  • the anhydrides of the dicarboxylic acids a2 are also suitable ester-forming derivatives. In principle, however, it is also possible to use aromatic dicarboxylic acids a2 having a larger number of carbon atoms, for example up to 20 carbon atoms.
  • the aromatic dicarboxylic acids or their ester-forming derivatives a2 may be used singly or as a mixture of two or more thereof. Particularly preferred is terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate used.
  • the sulfonated aromatic dicarboxylic acids and their ester-forming derivatives are typically derived from the aforementioned non-sulfonated aromatic dicarboxylic acids and carry one or two sulfonic acid groups.
  • the diols B are selected from branched or linear alkanediols of 2 to 12 carbon atoms, preferably 4 to 8 or more preferably 6 carbon atoms, or cycloalkanediols of 5 to 10 carbon atoms.
  • alkanediols examples include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2,4-dimethyl-2-ethylhexane-1, 3 diol, 2,2-dimethyl-1, 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl 1, 6-hexanediol, in particular ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol (neopentyl glycol); Cyclopentanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedi
  • the diol component B is preferably selected from C 2 -C 12 -alkanediols and mixtures thereof. Preference is given to 1, 3-propanediol and in particular
  • component B can be used in excess.
  • the molar ratio of the components A used to B in the range from 0.4: 1 to 1, 1: 1, preferably in the range of 0.6: 1 to 1, 05: 1 and in particular in the range of 0 , 7: 1 to 1, 02: 1.
  • the molar ratio of the component A incorporated in the polymer to the component B incorporated in the polymer is preferably in the range from 0.8: 1 to 1:01: 1, preferably in the range from 0.9: 1 to 1: 1, and in particular in the range of 0.99: 1 to 1: 1.
  • the polyesters may contain further bifunctional components C in condensed form.
  • These bifunctional compounds have two functional groups which react with carboxylic acid groups or preferably hydroxyl groups to form bonds.
  • Examples of functional groups, wel- surface with OH groups, are in particular isocyanate groups, epoxy groups, oxazoline groups, carboxyl groups in free or esterified form and amide groups.
  • Functional groups which react with carboxyl groups are in particular hydroxyl groups and primary amino groups. These are in particular so-called bifunctional chain extenders, in particular the compounds of groups c3) to c7).
  • the components C include: c1) dihydroxy compounds of the formula I.
  • A is a C2-C4-alkylene unit such as 1,2-ethanediyl, 1,2-propanediyl,
  • Aminocarboxylic acids for example, are selected from natural amino acids, polyamides having a molecular weight of at most 18000g / mol, obtainable by polycondensation of a dicarboxylic acid having 4 to 6 carbon atoms and a diamine having 4 to 10 carbon atoms, compounds of formulas IV a and IVb
  • R 3 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, phenyl which is unsubstituted or monosubstituted or substituted by C 1 -C 4 -alkyl groups or is tetrahydrofuryl;
  • component c1 are diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran (polyTHF), particularly preferably diethylene glycol, triethylene glycol and polyethylene glycol, mixtures of which or compounds having different alkylene units A (see formula I),
  • the latter are obtainable, for example, by polymerization according to known methods of first ethylene oxide and subsequently propylene oxide.
  • the molecular weight (number average M n ) of the polyethylene glycol is usually selected in the range from 250 to 8000, preferably from 600 to 3000 g / mol. According to one embodiment, for example, 80 to 99.8, preferably 90 to 99.5 mol% of the diols B and 0.2 to 20, preferably 0.5 to 10 mol% of the dihydroxy compounds c1, based on the molar Amount of B and c1, used for the preparation of copolyesters.
  • Examples of preferred components c2 are glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, their cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D-, L-dilactide ( 3,6-dimethyl-1, 4-dioxane-2,5-dione), p-hydroxybenzoic acid and also their oligomers and polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (for example as EcoPLA® (from Cargill)) ) and a mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter being available under the name Biopol® from Zeneca).
  • glycolic acid D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid
  • their cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D-, L-dilact
  • copolyesters are the low molecular weight and cyclic derivatives thereof.
  • the hydroxycarboxylic acids, or their oligomers and / or polymers can be used, for example, in amounts of from 0.01 to 20, preferably from 0.1 to 10,% by weight, based on the amount of A and B.
  • Preferred components c3 are amino-C2-C6-alkanols such as 2-aminoethanol,
  • Preferred components c4) are diamino-C 4 -C 6 -alkanes, such as 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.
  • bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1, 2-bis (2-oxazolinyl) ethane, 1, 3-bis (2-oxazolinyl) propane or 1,4-bis (2-oxazolinyl) butane, 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazolinyl) benzene or 1,3-bis (2-oxazolinyl) called benzene.
  • Bisoxazolines of general formula III are generally obtainable by the process of Angew. Chem. Int. Edit, Vol. 11 (1972), pp. 287-288.
  • up to 20 mole% c3, e.g. B. 0.5 to 20 mol% c3, up to 20 mol%, z. B. 0.5 to 20 mol% c4, and up to 20 mol%, z. B. 0.5 to 20 mol% c5, in each case based on the sum of the molar amounts of components B, c3, c4 and c5, are used.
  • natural aminocarboxylic acids can be used. These include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, tyrosine, asparagine or glutamine.
  • Preferred aminocarboxylic acids of the general formulas IVa and IVb are those in which s is an integer from 1 to 1000 and t is an integer from 1 to 4, preferably 1 or 2 and T is selected from the group consisting of phenylene and - (Chkju-, wherein u is 1, 5 or 12.
  • c6 can also be a polyoxazoline of the general formula V.
  • component c6 can also be a mixture of different aminocarboxylic acids and / or polyoxazolines.
  • c6 can be used in amounts of from 0.01 to 20, preferably from 0.1 to 10,% by weight, based on the total amount of components A and B.
  • aromatic diisocyanates are toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1,5-diisocyanate or xylylene diisocyanate.
  • aliphatic diisocyanates are, above all, linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, eg. B. 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane).
  • Further suitable components c7 are tri (4-isocyanatophenyl) methane and the cyanurates, uretdiones and biurets of the abovementioned diisocyanates.
  • the component c7 in amounts of from 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol% based on the sum of the molar amounts of A and B used .
  • Other components which may optionally be used to prepare the polyesters include compounds D which contain at least three groups / functionalities which react with carboxylic acid or hydroxyl groups to form bonds.
  • functional groups which react with OH groups are, in particular, isocyanate groups, epoxide groups, oxazoline groups, carboxyl groups in free or esterified form and amide groups.
  • Functional groups which react with carboxyl groups are in particular hydroxyl groups and primary amino groups. Such compounds are also referred to as crosslinkers.
  • biodegradable copolyesters with a structural viscosity can be built up.
  • the rheological behavior of the melts improves;
  • the biodegradable copolyesters are easier to process, for example, better by melt consolidation to remove films.
  • the compounds D act scherentzä- Hend, ie the viscosity under load is lower.
  • the compounds D preferably contain three to ten, z. , Three, four, five or six, functional groups capable of forming ester bonds.
  • Particularly preferred compounds D have three to six functional groups of this kind in the molecule, in particular three to six hydroxyl groups and / or carboxyl groups.
  • Examples include: polycarboxylic acids and hydroxycarboxylic acids such as tartaric acid, citric acid, malic acid; trimesic; Trimellitic acid, anhydride; Pyromellitic acid, dianhydride and hydroxyisophthalic acid and polyols such as trimethylolpropane, trimethylolethane; Pentaerythritol, polyether triols and glycerine.
  • Preferred compounds D are polyols, preferably trimethylolpropane, pentaerythritol and especially glycerol.
  • the compounds D are, if desired, usually in amounts of 0.0005 to 1 mol / kg, preferably 0.001 to 0.5 mol / kg and in particular 0.005 to 0.3 mol / kg, based on the total amount of components A, B. , C and D, or on the total weight of the polyester used. If desired, the compounds D are preferably 0.01 to 5% by weight, in particular 0.05 to 3% by weight and in particular 0.1 to 2% by weight, especially 0.2 to 2% by weight. %, based on the total amount of components A, B, C and D, or on the total weight of the polyester used.
  • bi- or polyfunctional epoxides for the preparation of the copolyesters which are preferred according to the invention (component E).
  • Suitable bi- or polyfunctional epoxides are, in particular, epoxide-group-containing copolymers based on styrene, acrylates and / or methacrylates.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
  • Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proved to be advantageous.
  • the epoxide equivalent weight (EEW) in these polymers is preferably Example 150 to 3000 and particularly preferably 200 to 500 g / equivalent.
  • the weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000.
  • the number average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000.
  • the polydispersity (Q) is generally between 1 .5 and 5 epoxy groups, copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR. Particularly suitable as component E Joncryl ® ADR 4368.
  • the component E is most commonly used as a chain. With regard to the quantity, the statements made above for component E, in particular for components c2), c3), c4), c5) and c6), apply.
  • copolyesters are partially known, for. Example, from EP-A 488 617, W096 / 15173 and WO 04/67632, or can be prepared by methods known per se. More preferably, the copolyesters are prepared by the continuous process described in EP Publ. No. 08154541.0.
  • the synthesis of the copolyesters described is carried out according to a first embodiment in a two-stage reaction cascade.
  • the dicarboxylic acids or their derivatives A are first reacted together with component B and optionally D in the presence of an esterification catalyst (or when the carboxylic acids A are used in the form of their esters, in the presence of a transesterification catalyst) to give a prepolyester.
  • This prepolyester generally has a viscosity number (CV) of 50 to 100 ml / g, preferably 60 to 90 ml / g.
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the literature, such as tin dioctanoate, that residual amounts of catalyst remaining in the product or secondary products of the catalyst are less toxic. This fact is particularly important in the case of biodegradable polyesters, since, for example, they are released directly into the environment as composting bags or mulch films.
  • the polyesters according to the invention are optionally subsequently chain-extended according to the processes described in WO 96/15173 and EP-A 488 617.
  • the prepolyester is, for example, chain extenders C), z. B. with diisocyanates or with epoxy-containing polymethacrylates in a chain extension reaction to a polyester with a VZ of 60 to
  • component A is first condensed in the presence of an excess of component B and optionally D together with the catalyst. Subsequently, the melt of the prepolyester thus obtained, usually at an internal temperature of 200 to 250 ° C, while releasing distilled diol to the desired viscosity with a viscosity number (VZ) of 60 to 450 mL / g and preferably 80 to 250 mL / g condensed. This condensation is usually carried out within 3 to 6 hours at reduced pressure. If appropriate, a reaction with the chain extender of component D is also carried out hereinafter. More preferably, the copolyesters are prepared by the continuous process described in EP Publ. No. 08154541.0.
  • the product obtainable from 2.) - preferably in a cage reactor - polycondensed up to a viscosity number according to DIN 53728 of 70 to 130 mL / g and optionally
  • the product obtainable from 3.) is continuously converted to a viscosity number according to DIN 53728 of 80 to 250 ml / g in a polyaddition reaction with a chain extender in an extruder, a list reactor or a static mixer.
  • the copolyesters of the invention may also be prepared in a batch process.
  • the components A, B and optionally D are mixed in any metering order and condensed to form a prepolyester.
  • a polyester can be adjusted with the desired viscosity number.
  • the preferred copolyesters generally have a number average molecular weight MN in the range from 5000 to 1,000,000 daltons, in particular in the range from 8,000 to 800,000 daltons and especially in the range from 10,000 to 500,000 daltons.
  • the weight-average molecular weight M w of the copolyesters preferred according to the invention is generally in the range from 20,000 to 500,000 daltons, often in the range from 30,000 Daltons to 4,000,000 Daltons, and more particularly in the range of 40,000 to
  • the polydispersity index MW / MN is generally at least 2 and is often in the range of 3 to 25, in particular in the range of 5 to 20.
  • the copolyesters are partially crystalline and have a melting point or melting range in the range of 80 to 170 ° C, in particular in the range of 90 to 150 ° C.
  • the viscosity number of the copolyesters is typically in the range of 50 to 500 ml / g, often in the range of 80 to 300 ml / g and in particular in the range of 100 to 250 ml / g (determined according to EN ISO 1628-1 at 25 ° C on a 0.5% strength by weight solution of the polymer in o-dichlorobenzene / phenol (1: 1 w / w)).
  • the preferred copolyesters are on the one hand by a high melt viscosity ⁇ , which at 180 ° C usually at least 60 Pa-s, often at least 80 Pa-s, in particular at least
  • the copolyesters preferably have substantially no functional groups which impart water solubility to the polymers. Accordingly, the number of sulfonic acid groups in the copolyester is generally less than 0.1 mmol / g, in particular less than 0.05 mmol / g or less than 0.01 mmol / g of polymer.
  • the aqueous dispersions of the copolyester generally have a solids content in the range from 10 to 60% by weight, in particular in the range from 20 to 55% by weight and especially in the range from 30 to 50% by weight.
  • the viscosity of the dispersions according to the invention determined according to Brookfield, at 20 ° C at a value of at most 5 Pa-s, often at a maximum of 2 Pa-s, z. B. in the range of 10 to 5000 mPa-s, in particular in the range of 50 to 2000 mPa-s (measured using a Brookfield viscometer at 20 ° C, 20 rpm, spindle 4).
  • the aqueous dispersion generally contains at least one surface-active substance for stabilizing the polymer particles dispersed in the dispersion.
  • the proportion of surface-active substances will generally not exceed 20% by weight, based on the total solids content, and is typically in the range from 0.1 to 20% by weight and frequently in the range from 0.2 to 10% by weight. , based on the total solids content.
  • Suitable surfactants include polymeric surfactants having molecular weights in excess of 2000 daltons (number average), e.g.
  • the surfactants may be cationic, anionic or neutral.
  • the aqueous dispersion medium contains at least one protective colloid, for example a neutral, anionic or cationic protective colloid, optionally in combination with one or more emulsifiers.
  • protective colloids are water-soluble polymers such as
  • neutral protective colloids for example polysaccharides, e.g. B. water-soluble
  • Starches, starch derivatives and cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, furthermore polyvinyl alcohols, including partially saponified polyvinyl acetate with a degree of saponification of preferably at least 40%, in particular at least 60%, polyacrylamide, polyvinylpyrrolidone, polyethylene glycols, graft polymers of
  • anionic water-soluble polymers whose polymer backbone has a multiplicity of carboxyl groups, sulfonic acid groups or sulfonate groups and / or phosphonic acid groups or phosphonate groups, for example carboxymethylcellulose, homo- and copolymers of ethylenically unsaturated monomers which are at least 20% by weight, based on the total amount of the monomers, at least one ethylenically unsaturated monomer which contains at least one carboxyl group, sulfonic acid group and / or phosphonic acid group in copolymerized form, and their salts, in particular the
  • water-soluble polymers are usually in the aqueous usually bound to the polymer backbone sulfonic acid groups in the salt form, d. H. as sulfonate groups, and the phosphonic acid groups accordingly as
  • alkali metal and alkaline earth metal ions such as sodium ions, eg the chlorides
  • anionic or cationic modified starches examples include carboxymethylated starches and n-octenylsuccinyl-modified starch, for example as available as products from the company Cargill (CEmCap / CEmTex / CDeliTex n-octenylsuccinylated starches);
  • cationically modified starches are starches modified with 2-hydroxy-3- (trimethylammonium) propyl groups, e.g. B.
  • Starches which are obtainable by reacting conventional starches with A / - (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride (CHPTAC), and which preferably have a substituent. degree of completion of 0.02 to 0.1. Examples of these are the products Hi-Cat 21370 from Roquette and Perlcore 134P from Lyckeby.
  • anionic water-soluble polymers whose polymer backbone has a multiplicity of carboxyl groups, sulfonic acid or sulfonate groups and / or phosphonic acid or phosphonate groups include, for example:
  • monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms hereinafter monoethylenically unsaturated C3-C6 monocarboxylic acids
  • Copolymers of monoethylenically unsaturated C 3 -C 6 -monocarboxylic acids with neutral monomers such as, for example, vinylaromatics, such as styrene, C 1 -C 10 -alkyl esters of monoethylenically unsaturated C 3 -C 6 monocarboxylic acids and / or C 4 -C 6 -dicarboxylic acids, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, hydroxy ethyl ester, especially hydroxyethyl and hydroxypropyl esters of the neutral
  • Homo- and copolymers of monoethylenically unsaturated sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid, 2-Acryloxypropansulfonklare etc. and their copolymers with the aforementioned neutral monomers, and the salts of the aforementioned homopolymers and copolymers , in particular the alkali metal and ammonium salts;
  • the proportion of the neutral comonomers in the aforementioned copolymers usually will not exceed a proportion of 80% by weight, in particular 70% by weight, based on the total amount of the monomers constituting the copolymer.
  • water-soluble copolyesters the aromatically bound sulfonic acid or sulfonate groups in an amount of 0.3 to 1, 5 mmol / g, in particular 0.5 to
  • 5-sulfoisophthalic acid or its salts in particular the sodium salt of sulfoisophthalic acid, or their ester-forming derivatives;
  • aromatic dicarboxylic acids which have no sulfonyl groups and which are preferably selected from terephthalic acid and isophthalic acid and mixtures thereof, or their ester-forming derivatives;
  • iv 95 to 105 mol%, based on the total amount of components i), ii), and iii), one or more aliphatic diols such as.
  • ethylene glycol ethylene glycol
  • Such water-soluble copolyesters are known, for example, from US Pat. No. 6,521,679, to the disclosure of which reference is hereby made in its entirety.
  • Common nonionic emulsifiers are z. B.
  • C2-C3-alkoxylated especially ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation of 3 to 50, alkyl: CA to C12) and C2-C3-alkoxylated, in particular ethoxylated fatty alcohols (degree of ethoxylation of 3 to 80; : Cs to C36).
  • Lutensol® A grades C12 to C fatty alcohol ethoxylates, degree of ethoxylation from 3 to 8
  • Luten sol® AO grades C13 to cis oxo alcohol ethoxylates, degree of ethoxylation from 3 to 30
  • Lutensol® AT grades C16 to Cis fatty alcohol ethoxylates, degree of ethoxylation from 1 to 80
  • Lutensol® ON grades C10 oxo alcohol ethoxylates, degree of ethoxylation from 3 to 1 liter
  • Lutensol® TO grades C13 oxo alcohol ethoxylates, ethoxylation level from 3 to 20
  • Typical anionic emulsifiers are the salts of amphiphilic substances which have an anionic functional group, eg. As a sulfonate, phosphonate, sulfate or The phosphate group.
  • these include, for example, the salts, in particular the alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), the salts, in particular the alkali metal and ammonium salts of amphiphilic compounds containing a sulfated or phosphated oligo-C 2 -C 3 -alkylene oxide group, in particular have a sulfated or phosphated oligoethylene oxide group, such as, for example, the salts, in particular the alkali metal and ammonium salts of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation from 2 to 50, in particular 4 to 30, alkyl radical: C10 to C30, in particular
  • Alkali metal and ammonium salts of Phosphorklaschestern ethoxylated alkanols (degree of ethoxylation of 2 to 50, especially 4 to 30, alkyl: C10 to C30, especially C12 to Cie) the salts, in particular the alkali metal and ammonium salts of PhosphorTalkrerenzestern ethoxylated alkylphenols (degree of ethoxylation of 2 to 50 , Alkyl radical: C 4 to C 12), the salts, in particular the alkali metal and ammonium salts of alkylsulfonic acids (alkyl radical: C 12 to Cie), the salts, in particular the alkali metal and ammonium salts of alkylarylsulfonic acids (alkyl radical: C9 to Cie), and the salts, in particular the alkali metal and ammonium salts of Alkylbiphenylethersulfonkla- ren (alkyl radical: C6 to Cie) such.
  • Suitable cationic emulsifiers are generally a C6-C18-alkyl, C1-C10-alkylaryl or heterocyclic radical-containing cationic salts, for example primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolines salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts, in particular their sulfates, methoxides, acetates, chlorides, bromides, phosphates, hexafluorophosphates and the like.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinklaer, N-Cetylpyridiniumsulfat, N-Laurylpyridiniumsulfat and N-cetyl- ⁇ , ⁇ , ⁇ -trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl- ⁇ , ⁇ , ⁇ -trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini-surfactant N, N '- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl-N-methylammonium sulfate and the ge
  • the aqueous dispersion contains at least one neutral protective colloid, in particular a neutral, OH-group-bearing protective colloid, optionally in combination with one or more emulsifiers, preferably anionic or nonionic emulsifiers, in particular anionic emulsifiers containing a sulfate or sulfonate group.
  • neutral OH-bearing protective colloids are polysaccharides, e.g.
  • water-soluble starches, starch derivatives and cellulose derivatives such as methylcellulose, hydroxypropyl cellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose se, further polyvinyl alcohols, including partially saponified polyvinyl acetate with a degree of saponification of preferably at least 40%, in particular at least 60%.
  • the neutral OH-bearing protective colloid is selected from polyvinyl alcohols, including partially hydrolyzed polyvinyl acetates having a saponification degree of preferably at least 40%, especially at least 60%.
  • the preparation of the dispersions of biodegradable polyester can be carried out in analogy to that in the earlier patent application PCT / EP201 1/054471 method.
  • a composition of the polyester which is usually at least 99% by weight of the polyester or a blend of the polyester with a different polymer and optionally one or more surface-active substances, at a temperature above the melting temperature or the softening temperature of the polyester or of the blend is introduced into an aqueous dispersion medium, which usually contains at least one surface-active substance, and the resulting aqueous emulsion is quenched.
  • an aqueous dispersion medium which usually contains at least one surface-active substance
  • the thermoplastic polyester in the case of an amorphous polyester at a temperature above the softening point of the polyester or in the case of a crystalline or partially crystalline polyester above the melting point of the polyester, is introduced into the aqueous dispersing medium.
  • the softening temperature is understood to mean the temperature which corresponds to the glass transition temperature, as can be determined, for example, by means of differential scanning calorimetry (DSC) according to ASTM D 3418 or preferably according to DIN 53765 or by dynamic mechanical analysis (DMA).
  • DSC differential scanning calorimetry
  • DMA dynamic mechanical analysis
  • the melting temperature is understood to mean the temperature that leads to a
  • polyester Melting or softening of the polyester leads and can be determined in a conventional manner by means of differential scanning calorimetry (DSC) according to DIN 53765 or differential thermal analysis (DTA).
  • DSC differential scanning calorimetry
  • DTA differential thermal analysis
  • an amorphous polyester is meant a polyester that is less than
  • a crystalline or a partially crystalline polyester is understood as meaning a polyester which has more than 1% by weight, in particular at least 5% by weight, of crystalline regions.
  • the degree of crystallinity of a polyester can be determined in a manner known per se by X-ray diffractometry or by thermochemical methods such as DTA or DSC in a manner known per se.
  • the rotor-stator mixers used for the production of the aqueous dispersion of the biodegradable polyester are familiar to the person skilled in the art and basically include all types of dynamic mixers in which a high-speed, preferably rotationally symmetrical rotor in cooperation with a stator forms one or more workspaces essentially annular in shape.
  • the mix is exposed to strong shear and shear stresses, which often prevail in the annular gaps strong turbulence, which also favor the mixing process.
  • the rotor-stator device is operated at a relatively high speed of typically 1000 to 20,000 rpm. This results in high peripheral speeds and a high shear rate, whereby the emulsion is exposed to high shear and shear stresses, which lead to an effective division of the melt and thus to a very effective emulsification.
  • the rotor-stator mixers include, for example, sprocket dispersers, annular gap mills and colloid mills.
  • rotor-stator mixers which have means for generating cavitation forces.
  • Such means may be projections arranged on the rotor and / or stator side which project into the mixing chamber and which have at least one surface whose surface normal has a tangential component, such as pins, teeth or knives or coaxial rings with radially arranged slots.
  • the rotor-stator mixer on the rotor side at least one rotationally symmetrically arranged sprocket and / or at least one rotationally symmetrical ring with radial slots (tooth spaces) on.
  • Such devices are also referred to as Zahnkranzdispergatoren or Zahnkranzdispergiermaschinen.
  • the rotor-stator mixer both rotor side and stator on at least one rotationally symmetrical sprocket and / or ring with radial slots (tooth spaces), wherein the rotor and stator side arranged sprockets / rings are arranged coaxially and mesh to form an annular gap.
  • the rotor-stator mixer is a Zahnkranzdispergiermaschine having a conical stator with a concentric frusto-conical recess and a likewise concentric conical rotor, wherein the rotor protrudes into the frustoconical working chamber of the stator, that an annular working space is formed in which rotor and stator side teeth protrude, each in the form of one or more, for. B. two, three or four rotor side and one or more, z. B. one, two, three or four stator-side coaxial sprockets are respectively arranged on the rotor and the stator, that the sprockets offset mesh.
  • the composition of the polyester is mixed with the aqueous dispersing medium at a temperature above the softening point of the polymer.
  • the composition of the polyester is usually heated to a temperature above the softening temperature and fed to the mixing device, preferably continuously.
  • the required amount of aqueous dispersing medium preferably continuously supplied to the mixing device. The amount of dispersing medium is usually chosen so that the desired solids content of the dispersion is adjusted.
  • the dispersing medium in a larger amount and then to concentrate the dispersion obtained. It is likewise possible first to prepare a more concentrated dispersion and to dilute it with further dispersant and / or water.
  • the mass ratio of polymer fed to the total amount of aqueous dispersing medium is typically in the range of 1:20 to 1.2: 1, often in the range of 1:10 to 1: 1, 1, and more preferably in the range of 1: 3 to 1: 1. With continuous addition of polymer and aqueous dispersion medium, the mass ratio of the supplied material flows in the aforementioned ranges.
  • the mass ratio of polymer fed to the total amount of aqueous dispersing medium fed in the first to the penultimate stage can also be up to 4: 1 or up to 2.3: 1.
  • the supply of polymer and aqueous dispersing medium occurs at a constant rate of addition, ie the mass ratio of thermoplastic polymer and dispersing medium is constant during the process or does not deviate more than 10% from the preselected mass ratio.
  • the introduction of the composition of the polyester in the aqueous dispersing medium is typically carried out at a temperature of at least 5 K, often at least 10 K and in particular at least 20 K, z. In the range of 5 to 150 K, often in the range of 10 to 100 K and in particular in the range of 20 to 80 K above the melting or softening temperature of the composition. This temperature is also referred to below as the mixing temperature.
  • the introduction of the composition into the aqueous dispersion medium at a temperature of at most 300 ° C, z. B. in the range of 50 to 300 ° C, often 60 to 250 ° C and especially 100 to 200 ° C.
  • the introduction of the composition into the aqueous dispersion medium usually takes place at a pressure above atmospheric pressure, generally at a pressure in the range from 1 to 50 bar, frequently 1, 1 to 40 bar, in particular in the range of 1, 5 up to 20 bar.
  • the mixing process can be in one or more, z. B. two, three, four or five stages are performed, wherein at least one stage in a rotor-stator mixer is carried out. In a multi-stage process, preferably all stages are carried out in rotor-stator mixers.
  • the mixing takes place in one stage, i. H.
  • the mixing device comprises a rotor-stator mixer.
  • the composition and dispersing medium are generally supplied to the rotor-stator mixer in the amounts required for the preparation of the dispersion.
  • it has proven useful to heat the dispersant prior to feeding to the desired mixing temperature or a temperature of at least 20 K below the mixing temperature, preferably to a temperature in the range of +/- 20 K of the mixing temperature.
  • the mixing takes place in several stages, ie in a mixing device, the more, z. B. two, three, four or five, in particular three or four, serially interconnected rotor-stator mixer. It has proven useful in the first stage, ie in the first rotor-stator mixer to give the composition of the polyester and a subset of the dispersing medium and there at a temperature above the melting or softening temperature of the composition with the subset of the aqueous dispersing medium mix.
  • the partial amount of the dispersing medium added to the first stage is usually from 10 to 60% by weight, in particular from 15 to 40% by weight, based on the total amount of the dispersing medium introduced into the mixing device.
  • the introduction of the composition into the subset of the aqueous dispersion medium is typically carried out at a temperature of at least 5 K, often at least 10 K and in particular at least 20 K, z. In the range of 5 to 150 K, often in the range of 10 to 100 K and in particular in the range of 20 to 80 K above the melting or softening temperature of the composition.
  • the mixing temperature in the first rotor-stator mixer will be a maximum of 300 ° C, and is z. B. in the range of 50 to 300 ° C, often 80 to 250 ° C and especially 100 to 200 ° C.
  • the first rotor-stator mixer subset of dispersant before feeding to the desired mixing temperature or a temperature of at least 20 K below the mixing temperature, preferably to a temperature in the range of +/- 20 K of To heat the mixing temperature.
  • the aqueous dispersion obtained in the first rotor-stator mixer is then transferred to another rotor-stator mixer where it is mixed with a further portion or the remainder of the dispersing medium.
  • the second rotor-stator mixer one or more, z. B.
  • the temperature at which the dispersion obtained in the first rotor-stator mixer is mixed with further dispersion medium in the second rotor-stator mixer can be adjusted to the temperature. in the first rotor-stator mixer or above or below it. Preferably, it is below the temperature in the first rotor-stator mixer.
  • the mixing temperature in the first of the series-connected rotor-stator mixer at least 20 K, preferably at least 30 K, z. B. 20 to 200 K, in particular 30 to 120 K above the temperature in the last of the serially interconnected rotor-stator mixer.
  • the temperature in the last of the serially interconnected rotor-stator mixer is at least 5 K, in particular at least 10 K, z. B. 5 to 200 K, in particular 10 to 150 K below the melting or softening temperature of the composition.
  • the composition of the polyester and the aqueous dispersion medium will be fed simultaneously, preferably continuously and in particular at a constant volume rate, to the rotor-stator mixer or the rotor-stator mixers and the dispersion removed to the same extent ,
  • an upstream step it is also possible in an upstream step to mix the composition of the polyester with the aqueous dispersion medium to obtain a primary emulsion at a temperature above the melting or softening temperature of the composition of the polyester and to supply this mixture to the rotor-stator mixer .
  • This upstream step is preferably carried out in a kneader or extruder.
  • the pre-emulsion thus obtained is then fed to the rotor-stator mixer (s).
  • the preemulsion is maintained at a temperature above the melting or softening temperature of the composition of the polyester.
  • the initially obtained aqueous emulsion of the polymer in the aqueous dispersing medium, which is obtained in the mixing device, is then, d. H. after leaving the mixer, quenched, d. H. cooled rapidly to a temperature below the softening temperature of the composition of the polyester to avoid agglomeration of the polymer particles in the emulsion.
  • the quenching can be carried out in a conventional manner, for example by suitable cooling devices and / or by dilution with cooled dispersant.
  • the emulsion should not dwell for more than 20 seconds, especially not more than 10 seconds, after leaving the mixing apparatus at temperatures above the melting or softening temperature of the polymer.
  • the quenching can also take place in the second and possibly further rotor-stator mixers.
  • the dispersions suitable for use according to the invention may consist solely of water, optionally surface-active substance and those dispersed in water Consist of polymers. But it can also contain other additives, eg. As fillers, antiblocking agents, dyes, leveling agents, thickeners for adjusting the rheology or wetting aids. These additives will usually constitute no more than 50% by weight, based on the total solids content of the dispersion. As a rule, these additives are added to the dispersion after dispersion of the polymer (s).
  • the aqueous dispersion of the polyester contains up to 50% by weight, based on the total solids content of the dispersion, of one or more platelet-shaped pigments. Examples of platelet-shaped pigments are talc, clay or mica (mica). Preferred is talc. Preferred form factors (length to thickness ratio) are greater than 10.
  • the present invention also relates to a process for producing a barrier coating on paper or board, comprising applying at least one aqueous dispersion of at least one biodegradable polyester as defined herein to at least one surface of the paper or board.
  • the application of the aqueous dispersion (s) of the at least one biodegradable polyester can be carried out in a manner known per se.
  • the application of the polymer dispersion can be carried out, for example, by applying to the support material, d. H. Paper or board which applies polymer dispersion by means of suitable coating machines. If web-like materials are used, the polymer dispersion is usually applied from a trough over an applicator roll and leveled with the aid of an air brush. Other ways to apply the polymer dispersion, succeed z. Example with the aid of the reverse gravure process, with spraying or with a roller blade or with other coating methods known in the art.
  • the carrier substrate is provided on at least one side with a coating, d. H. It can be coated on one side or on both sides.
  • Preferred application methods for paper and board are curtain coating, air knife, bar brushing or knife coating.
  • volatile constituents, especially water are evaporated.
  • the material can pass through a dryer channel, which can be equipped with an infrared irradiation device. Thereafter, the coated and dried packaging material is usually passed over a cooling roll and finally wound up.
  • the polymer dispersion is applied to the carrier in an amount of at least 1 g / m 2 , often at least 2 g / m 2 , especially at least 3 g / m 2 and especially at least 5 g / m 2 , calculated as solids per m 2 of the coated surface, applied to the carrier substrate.
  • the polymer dispersion is preferably applied to the carrier in an amount of from 2 to 50 g / m 2 , in particular from 3 to 40 g / m 2 , especially from 5 to 30 g / m 2 , calculated as solid per m 2 of the coated surface, applied to the carrier substrate.
  • the resulting coating thickness is accordingly on average at least 1 ⁇ , often at least 2 ⁇ , in particular at least 3 ⁇ and especially at least 5 ⁇ , z. B. in the range of 2 to 50 ⁇ , in particular 3 to 40 ⁇ , especially 5 to 30 ⁇ .
  • a specific embodiment of the invention relates to a method for coating cardboard, in particular cardboard, which is at least partially, as a rule, at least 30% by weight (wt .-%, based on total fiber mass), in particular at least 50 wt .-% or made entirely of mineral oil-loaded recycled paper.
  • the dispersion in a total amount in the range of 3 to 50 g / m 2 , in particular 4 to 40 g / m 2 , especially 5 to 30 g / m 2 , calculated as solids per m 2 , applied to the board surface to be coated ,
  • the coating thickness is accordingly on average at least 2 ⁇ , often at least 3 ⁇ , in particular at least 4 ⁇ and especially at least 5 ⁇ , z. B. in the range of 2 to 50 ⁇ , in particular 3 to 40 ⁇ , especially 5 to 30 ⁇ .
  • a further embodiment of the invention relates to a process for coating paper, in particular paper, which is at least partially, as a rule at least 30% by weight (% by weight, based on total fiber mass), in particular at least 50% by weight. or made entirely of mineral oil-loaded recycled paper.
  • the dispersion is brought in a total amount in the range of 1 to 30 g / m 2 , in particular 2 to 25 g / m 2 , especially 3 to 20 g / m 2 , calculated as the solid per m 2 , on the paper surface to be coated.
  • the coating thickness is accordingly on average at least 1 ⁇ , often at least 2 ⁇ , in particular at least 3 ⁇ , z. B. in the range of 12 to 30 ⁇ , in particular 2 to 25 ⁇ , especially 3 to 20 ⁇ .
  • a first layer is produced and then preferably in at least one further step, for. B. in one, two, three or four further steps, in particular in one or two further steps, by applying the aqueous dispersion to the first layer obtained in the first step at least one further, arranged on the first layer layer.
  • drying steps can be made.
  • the individual coatings can also be applied wet-on-wet, ie no separate drying steps are carried out.
  • the application rate of the polymer dispersion is generally selected such that in the individual steps the application rate is at least 0.5 g / m 2 , often at least 1 g / m 2 , especially at least 2 g / m 2 , especially at least 3 g / m 2 and typically in the range of 1 to 30 g / m 2 , especially 2 to 25 g / m 2 , especially 2 to 20 g / m 2 or 3 to 20 g / m 2 , especially 2 to 12 g / m 2 or 3 to 12 g / m 2 , calculated as the solid per m 2 of the coated surface.
  • a coating which is made up of a plurality of layers arranged on top of one another, wherein a coating thickness results per layer in accordance with the solids discharge.
  • the number of layers and the application amount per layer is naturally chosen so that the total amount of solid applied and thus the resulting coating thickness preferably in the range of 2 to 50 g / m 2 , in particular 3 to 40 g / m 2 , especially 5 to 30 g / m 2 results.
  • the number of layers and the amount applied per layer is often chosen so that the total amount of solid applied and thus the resulting coating thickness preferably in the range of 3 to
  • the number of layers and the amount applied per layer is frequently chosen so that the total amount of solid applied and thus the resulting coating thickness preferably in the range of 1 to 30 g / m 2 , in particular 2 to 25 g / m 2 , especially 3 to 20 g / m 2 , calculated as solids per m 2 .
  • composition of the aqueous dispersion of the at least one polyester as well as with respect to preferred polyesters and the substrates, the same applies.
  • a preferred embodiment of the present invention also relates to a method for producing a barrier coating on paper or board in the manner described above, in which the paper or the cardboard at least in part, usually at least 30 wt .-% (wt. %, based on total fiber mass), in particular at least 50 wt .-% or completely made of mineral oil loaded recycled paper.
  • the invention relates to such a method. where the paper or board is intended for food packaging.
  • Coated paper or board obtainable by the method according to the invention is likewise an object of the present invention.
  • it also has a good barrier action against mineral oils, in particular against volatile mineral oils, ie. H. towards gas permeating mineral oils, especially those having 15 to 25 carbon atoms, z. B. harmful paraffin and naphthenic hydrocarbons and aromatic hydrocarbons.
  • good blocking strengths are achieved, and papers coated according to the invention can be rolled up without sticking together.
  • the polymer melts were I. Analysis ⁇ To determine the zero shear viscosity by dynamic viscosity measurements s determined at 180 ° C with oscillatory shear at low amplitude at shear rates in the range of 0.01 to 500 _1 and a thrust amplitude of 100 Pa viscosity curves, and from this, the zero shear viscosity ⁇ by Extrapolation to a shear rate of 0 s _1 determined. To determine the viscosity curves, a rheometer of the type "Dynamic
  • DSR Stress Rheometer
  • the determination of the shear viscosity of the polymer melt under the dispersing conditions was carried out by means of dynamic viscosity measurement of the polymer melts with a rotational rheometer (SR5) from Rheometrics at the temperature indicated in the examples.
  • SR5 rotational rheometer
  • the viscosity of the dispersing medium under the dispersing conditions was determined according to Brookfield with a MCR301 rotational rheometer of
  • the viscosity number was determined according to EN ISO 1628-1 at 25 ° C on a 0.5 wt .-% solution of the polymer in o-dichlorobenzene / phenol (1: 1 w / w). Molecular weights were determined by gel permeation chromatography (GPC) according to DIN 55672-1. The particle size distribution was determined on a 1 wt .-% dilution of the dispersion by light scattering at 25 ° C.
  • the Brookfield viscosity of the dispersions was determined at 20 ° C. according to DIN EN ISO 2555 using a Physika MCR Couette geometry CC 27 rotational viscometer.
  • Polyester 1 aliphatic-aromatic copolyester
  • Polybutylene terephthalate adipate which was prepared as follows: 1095.2 g of terephthalate (47 mol%), 700 g of 1, 4-butanediol (65 mol%), 1 ml of glycerol (0.05% by weight, based on the polymer) were combined with 1, 1 ml
  • Tetrabutyl orthotitanate (TBOT) first mixed and heated to 160 ° C. The resulting methanol was distilled off within 1 h. After that, the
  • Adipic acid 53 mol%), 700 g of 1,4-butanediol (65 mol%) and 1 ml of glycerol (0.05 wt%, based on the polymer) together with 1.04 ml of tetrabutyl orthotitanate (TBOT).
  • TBOT tetrabutyl orthotitanate
  • the viscosity number VZ was 106.
  • the zero shear viscosity no at 180 ° C was 136 Pa.s.
  • the acid number was less than 1 mg KOH / g.
  • Polyester 2 aliphatic-aromatic copolyester
  • Polybutylene terephthalate adipate prepared as follows: 1388.5 g of terephthalate (55 mol%), 1000 g of 1, 4-butanediol (85 mol%), 1 ml of glycerol
  • Tetrabutylorthotitanate (TBOT) first mixed, and heated to 160 ° C, the resulting methanol was distilled off within 1 h. Thereafter, the kettle was cooled to about 140 ° C. Subsequently, this was added 854.9 g
  • TBOT tetrabutyl orthotitanate
  • the reaction mixture was heated to a temperature of 190 ° C, and at this temperature, the resulting water was distilled off over a period of 1 h. Subsequently, the temperature was raised to 240 ° C and gradually evacuated. Excess 1,4-butanediol was distilled off in vacuo ( ⁇ 1 mbar) over a period of 1 h.
  • the viscosity number VZ was 91.
  • the acid number was less than 1 mg KOH / g.
  • Polyester 3 aliphatic copolyester
  • Polybutylene succinate sebacinate prepared as follows: 6.8 kg sebacic acid (5 mol%), 75.7 kg succinic acid (95 mol%), 79.1 kg 1, 4-butanediol (130 mol%), 298 g of glycerin (0.25% by weight, based on the polymer) were mixed and heated to 120 ° C. Subsequently, 1 1 g of tetrabutyl orthotitanate (TBOT) was mixed together and heated to 200 ° C. The resulting water was distilled off within 1 h. Thereafter, the kettle was cooled to about 140 ° C. Subsequently, 22 g of tetrabutyl orthotitanate (TBOT) were added. Subsequently, the temperature was increased to 250 ° C and gradually evacuated.
  • TBOT tetrabutyl orthotitanate
  • the viscosity number VZ was 153.
  • the zero shear viscosity no at 180 ° C was 271 Pa.s.
  • the acid number was less than 1 mg KOH / g.
  • the rotor-stator mixer used was a 12-stage inline dispersing device, the device being provided with toothed ring-type shear elements.
  • Polyester 1 was continuously drawn through the hopper in an amount of 1, 2 kg / h in the single-screw extruder (Tech -ine E 16 T from Dr. Colin GmbH) and melted there at 155 ° C.
  • the polymer melt was fed to the first stage disperser (4000 rpm).
  • the shear rate was 12566 S -1 .
  • the polymer viscosity at this shear rate was 35 Pa s.
  • a 7% strength by weight aqueous solution of a partially saponified polyvinyl alcohol (Kuraray Poval 224E) containing 1% by weight of an anionic surfactant (Emulphor FAS 30 from BASF SE) having a solution viscosity of 0.038 Pa s was added to the in-line Dispersing device fed so that in the first and the fourth stage resulted in solids contents of 55% by weight and 45% by weight, respectively.
  • the solids content was adjusted to 43% by weight.
  • the temperature in the first ten stages was 155 ° C; in the eleventh and twelfth stages the temperature was 130 ° C.
  • the total residence time was 1.2 minutes.
  • the dispersion was quenched by means of a cooling bath to 20 ° C.
  • the rotor-stator mixer used was a 12-stage in-line dispersing device in which the device was provided with toothed ring-type shear elements.
  • the polymer melt was fed to the first stage disperser (4000 rpm).
  • the shear rate was 12,566 sec _1.
  • the polymer viscosity at this shear rate was 36 Pa s measured using a capillary rheometer Göttfert-Rheograph 2003.
  • the solids content was adjusted to 46% by weight.
  • the temperature in the first ten stages was 155 ° C; in the eleventh and twelfth stages the temperature was 130 ° C.
  • the total residence time was 1, 8 min.
  • the dispersion was quenched by means of a cooling bath to 30 ° C.
  • the machine has the following specification: Working width: 330 mm; Machine speed: 10 - 150 m / min; Unwinding: max. 600 mm dia; Core diameter: 70, 76 and 150 mm; Application system: roller; Drying: 6 drying hoods: air heater 47 kW, heater 14 kW; with a dosing system: roller scraper or rod squeegee.
  • Example 1 Simple Coating on Cardboard
  • the dispersion of Dispersing Example 1 was applied to the raw board (300 g / m 2 Smurfit Kappa Gernsbach) in one pass with a roller scraper using the Mini Plant Coater.
  • the machine speed was 50 m / min, the order quantity: 10 g / m 2 (solid).
  • the dispersion of Dispersing Example 1 was applied to the raw board (300 g / m 2 Smurfit Kappa Gernsbach) in two passes with a roller scraper using the Mini Plant Coater.
  • the machine speed was 50 m / min, the order quantity per pass 5 g / m 2 (solid).
  • the dispersion of dispersion example 1 was applied to raw paper (Stora-Enso cable 37 g / m 2 LWC) in one pass using a rod wiper using the Mini Plant coater.
  • the machine speed was 50 m / min, the order quantity: 10 g / m 2 (solid).
  • the dispersion of dispersion example 1 was applied to raw paper (Magnostar base paper 58 g / m 2 ) in one pass using a rod wiper using the Mini Plant coater.
  • the machine speed was 50 m / min, d application rate: 10 g / m 2 (solid).
  • Example 5 Double Coating on Raw Paper Magnostar
  • the dispersion of Dispersing Example 1 was applied to raw paper (Magnostar base paper 58 g / m 2 ) in two passes with a rod wiper using the Mini Plant Coater.
  • the machine speed was 50 m / min, the order in the passage 5 g / m 2 (solid) in the second round 4 g / m 2 (solid).
  • the barrier properties of the uncoated papers / cardboards and the papers / cardboards coated with the polyester dispersions were investigated according to the "Oil Penetration Test". For this purpose, the coated paper side was wetted with 2 ml of oleic acid. Then the paper was stored at 60 ° C for a certain time. Then, the back side of the coated paper was visually inspected for the extent of staining at various times. 100% means a complete penetration, 0% no penetration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne l'utilisation d'une dispersion aqueuse d'au moins un polyester biodégradable, sous forme d'un revêtement destiné à améliorer les propriétés de barrière de matériaux d'emballage en papier ou carton, notamment de matériaux d'emballage en papier ou carton recyclé, vis-à-vis d'huiles minérales. La présente invention concerne également un procédé de réalisation de revêtements barrières sur du papier ou carton, notamment sur du papier ou carton recyclé.
PCT/EP2012/068584 2011-09-23 2012-09-21 Utilisation d'une dispersion aqueuse de polyesters biodégradables WO2013041649A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12759762.3A EP2758594A1 (fr) 2011-09-23 2012-09-21 Utilisation d'une dispersion aqueuse de polyesters biodégradables
CA2849663A CA2849663A1 (fr) 2011-09-23 2012-09-21 Utilisation d'une dispersion aqueuse de polyesters biodegradables

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11182610 2011-09-23
EP11182610.3 2011-09-23

Publications (1)

Publication Number Publication Date
WO2013041649A1 true WO2013041649A1 (fr) 2013-03-28

Family

ID=46875854

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/068584 WO2013041649A1 (fr) 2011-09-23 2012-09-21 Utilisation d'une dispersion aqueuse de polyesters biodégradables

Country Status (3)

Country Link
EP (1) EP2758594A1 (fr)
CA (1) CA2849663A1 (fr)
WO (1) WO2013041649A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9328247B2 (en) 2011-11-10 2016-05-03 Basf Se Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
US9950502B2 (en) 2011-12-06 2018-04-24 Basf Se Paper and cardboard packaging with barrier coating
CN113755687A (zh) * 2021-07-20 2021-12-07 宁国市华丰耐磨材料有限公司 一种用于磨球生产的淬火热处理工艺

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017151595A1 (fr) 2016-02-29 2017-09-08 Michelman, Inc. Dispersion à base aqueuse hydrolytiquement stable d'un polymère biodégradable
JP2020503198A (ja) 2016-12-20 2020-01-30 マイケルマン，インコーポレーテッド 堆肥化可能な被覆を含む被覆基材及びそれを製造する方法
WO2021256381A1 (fr) * 2020-06-16 2021-12-23 日本製紙株式会社 Papier couché

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045418A (en) 1975-01-28 1977-08-30 Gulf Oil Corporation Copolymers of D,L-lactide and epsilon caprolactone
US4057537A (en) 1975-01-28 1977-11-08 Gulf Oil Corporation Copolymers of L-(-)-lactide and epsilon caprolactone
EP0488617A2 (fr) 1990-11-26 1992-06-03 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
US5142023A (en) 1992-01-24 1992-08-25 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247058A (en) 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
WO1994005484A1 (fr) 1992-09-09 1994-03-17 Basf Aktiengesellschaft Procede de fabrication de corps moules en polyactide
US5310865A (en) 1991-12-18 1994-05-10 Mitsui Toatsu Chemicals, Incorporated Polyhydroxycarboxylic acid and preparation process thereof
US5428126A (en) 1993-04-02 1995-06-27 Mitsui Toatsu Chemicals, Inc. Aliphatic polyester and preparation process thereof
US5440008A (en) 1993-05-28 1995-08-08 Mitsui Toatsu Chemicals, Inc. Process for preparing polyhydroxycarboxylic acid
US5484881A (en) 1992-10-02 1996-01-16 Cargill, Inc. Melt-stable amorphous lactide polymer film and process for manufacturing thereof
DE4440858A1 (de) * 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
WO1996018591A1 (fr) 1994-12-12 1996-06-20 Mee Young Song Engrais de type matrice a liberation regulee et son procede de preparation
US5540962A (en) * 1992-10-16 1996-07-30 Leonard Pearlstein Degradable package for containment of liquids
WO1997037848A1 (fr) * 1996-04-04 1997-10-16 Upm-Kymmene Oy Materiau en couches
WO1997041836A1 (fr) 1996-05-06 1997-11-13 Debio Recherche Pharmaceutique S.A. Compositions pharmaceutiques pour la liberation prolongee de principes actifs insolubles
EP0815454A1 (fr) 1995-03-13 1998-01-07 Duromer Kunststoffverarbeitungs-GmbH Transformateur de tension
WO1998009613A1 (fr) 1996-09-04 1998-03-12 Romano Deghenghi Procede de fabrication d'implants contenant des peptides bioactifs
WO1998053141A1 (fr) * 1997-05-23 1998-11-26 Cargill, Incorporated Papier enduit de polylactide
US5849374A (en) * 1995-09-28 1998-12-15 Cargill, Incorporated Compostable multilayer structures, methods for manufacture, and articles prepared therefrom
DE19805672A1 (de) * 1998-02-12 1999-08-19 Rasch Gmbh & Co Geb Vollständig kompostierbarer mehrlagiger Wandbekleidungsverbund und Verfahren zu dessen Herstellung
DE10024813A1 (de) 2000-05-19 2001-11-22 Cavitron Vom Hagen & Funke Gmb Maschine zur Verarbeitung von Flüssigkeiten
US20020076639A1 (en) 2000-10-27 2002-06-20 Dainippon Ink And Chemicals, Inc. Method for producing polyester resin particle dispersion material, method for producing polyester resin particles, and method for producing electrophotographic spherical toner
US6521679B1 (en) 1999-07-02 2003-02-18 Mitsui Chemicals, Inc. Polyester aqueous dispersion and method for preparation thereof
US6645584B1 (en) * 1998-07-07 2003-11-11 Enso Oyj Compostable coated paper or paperboard, a method for manufacturing the same and products obtained thereof
WO2004067632A1 (fr) 2003-01-27 2004-08-12 Basf Aktiengesellschaft Polyesters biodegradables a comportement en traitement ameliore
US20040248486A1 (en) * 2003-06-03 2004-12-09 Hodson Simon K. Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends
WO2006053849A1 (fr) 2004-11-18 2006-05-26 Ciba Specialty Chemicals Water Treatments Limited Emballage de distribution alimentaire
WO2010034712A1 (fr) * 2008-09-29 2010-04-01 Basf Se Procédé de revêtement de papier

Patent Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057537A (en) 1975-01-28 1977-11-08 Gulf Oil Corporation Copolymers of L-(-)-lactide and epsilon caprolactone
US4045418A (en) 1975-01-28 1977-08-30 Gulf Oil Corporation Copolymers of D,L-lactide and epsilon caprolactone
EP0488617A2 (fr) 1990-11-26 1992-06-03 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
US5310865A (en) 1991-12-18 1994-05-10 Mitsui Toatsu Chemicals, Incorporated Polyhydroxycarboxylic acid and preparation process thereof
US5142023A (en) 1992-01-24 1992-08-25 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247058A (en) 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
WO1994005484A1 (fr) 1992-09-09 1994-03-17 Basf Aktiengesellschaft Procede de fabrication de corps moules en polyactide
US5484881A (en) 1992-10-02 1996-01-16 Cargill, Inc. Melt-stable amorphous lactide polymer film and process for manufacturing thereof
US5540962A (en) * 1992-10-16 1996-07-30 Leonard Pearlstein Degradable package for containment of liquids
US5428126A (en) 1993-04-02 1995-06-27 Mitsui Toatsu Chemicals, Inc. Aliphatic polyester and preparation process thereof
US5440008A (en) 1993-05-28 1995-08-08 Mitsui Toatsu Chemicals, Inc. Process for preparing polyhydroxycarboxylic acid
DE4440858A1 (de) * 1994-11-15 1996-05-23 Basf Ag Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
WO1996018591A1 (fr) 1994-12-12 1996-06-20 Mee Young Song Engrais de type matrice a liberation regulee et son procede de preparation
EP0815454A1 (fr) 1995-03-13 1998-01-07 Duromer Kunststoffverarbeitungs-GmbH Transformateur de tension
US5849374A (en) * 1995-09-28 1998-12-15 Cargill, Incorporated Compostable multilayer structures, methods for manufacture, and articles prepared therefrom
WO1997037848A1 (fr) * 1996-04-04 1997-10-16 Upm-Kymmene Oy Materiau en couches
WO1997041836A1 (fr) 1996-05-06 1997-11-13 Debio Recherche Pharmaceutique S.A. Compositions pharmaceutiques pour la liberation prolongee de principes actifs insolubles
WO1998009613A1 (fr) 1996-09-04 1998-03-12 Romano Deghenghi Procede de fabrication d'implants contenant des peptides bioactifs
WO1998053141A1 (fr) * 1997-05-23 1998-11-26 Cargill, Incorporated Papier enduit de polylactide
DE19805672A1 (de) * 1998-02-12 1999-08-19 Rasch Gmbh & Co Geb Vollständig kompostierbarer mehrlagiger Wandbekleidungsverbund und Verfahren zu dessen Herstellung
US6645584B1 (en) * 1998-07-07 2003-11-11 Enso Oyj Compostable coated paper or paperboard, a method for manufacturing the same and products obtained thereof
US6521679B1 (en) 1999-07-02 2003-02-18 Mitsui Chemicals, Inc. Polyester aqueous dispersion and method for preparation thereof
DE10024813A1 (de) 2000-05-19 2001-11-22 Cavitron Vom Hagen & Funke Gmb Maschine zur Verarbeitung von Flüssigkeiten
US20020076639A1 (en) 2000-10-27 2002-06-20 Dainippon Ink And Chemicals, Inc. Method for producing polyester resin particle dispersion material, method for producing polyester resin particles, and method for producing electrophotographic spherical toner
WO2004067632A1 (fr) 2003-01-27 2004-08-12 Basf Aktiengesellschaft Polyesters biodegradables a comportement en traitement ameliore
US20040248486A1 (en) * 2003-06-03 2004-12-09 Hodson Simon K. Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends
WO2006053849A1 (fr) 2004-11-18 2006-05-26 Ciba Specialty Chemicals Water Treatments Limited Emballage de distribution alimentaire
WO2010034712A1 (fr) * 2008-09-29 2010-04-01 Basf Se Procédé de revêtement de papier

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ADV. MATER., vol. 12, 2000, pages 1841 - 1846
ANGEW. CHEM. INT. EDIT., vol. 11, 1972, pages 287 - 288
MACROMOLECULES, vol. 36, 2003, pages 8825 - 8829

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9328247B2 (en) 2011-11-10 2016-05-03 Basf Se Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
US9950502B2 (en) 2011-12-06 2018-04-24 Basf Se Paper and cardboard packaging with barrier coating
CN113755687A (zh) * 2021-07-20 2021-12-07 宁国市华丰耐磨材料有限公司 一种用于磨球生产的淬火热处理工艺
CN113755687B (zh) * 2021-07-20 2024-02-02 宁国市华丰耐磨材料有限公司 一种用于磨球生产的淬火热处理工艺

Also Published As

Publication number Publication date
CA2849663A1 (fr) 2013-03-28
EP2758594A1 (fr) 2014-07-30

Similar Documents

Publication Publication Date Title
EP2550090B1 (fr) Procede de fabrication d'une dispersion aqueuse contenant du polyester thermoplastique
US20130101865A1 (en) Use of an aqueous dispersion of biodegradable polyesters
EP2331602B2 (fr) Procédé de revêtement de papier
WO2013041649A1 (fr) Utilisation d'une dispersion aqueuse de polyesters biodégradables
US8604101B2 (en) Process for producing aqueous dispersions of thermoplastic polyesters
EP2740685B1 (fr) Procédé de fabrication d'un matériau d'emballage revêtu et matériau d'emballage doté d'au moins une couche d'arrêt pour compositions hydrophobes
EP3752673A1 (fr) Papier barrière thermosoudable
DE69322155T2 (de) Papier mit einer beschichtung aus schmelzstabilem polymer und dessen verfahren zur herstellung
WO1998012245A1 (fr) Dispersion aqueuse d'un polyester biodegradable et son utilisation
EP1656423A1 (fr) Melange de polyester biodegradable
DE60223473T2 (de) Biologisch abbbaubare biaxial gereckte Polyesterfolie und Verbundfolie
EP3559080B1 (fr) Polyesters contenant de l'acide furane dicarboxylique
WO2002022736A1 (fr) Film polyester
EP2718497A1 (fr) Composition pulvérulente et utilisation de ladite composition pour la production de papier
DE1546415A1 (de) Verfahren zur Erhoehung der Nassfestigkeit von Papier
EP4408659A1 (fr) Film de stratification biodégradable
EP4466403A1 (fr) Papiers couchés comportant une couche de peinture semi-cristalline servant de matériau d'emballage
EP1129131A1 (fr) Compositions constituees de polymeres biodegradables et de colorants a fluorescence
DE102022214453A1 (de) Kompostierbares verpackungsmaterial
DE1917054C3 (de) Flüssigkeits-, wasserdampf- und gasdichtes Papier bzw. papierartiges Material und ein Verfahren zu seiner Herstellung
DE10046398A1 (de) Polyesterfolie
WO2015040015A2 (fr) Dispersion polymère aqueuse de polymères aliphatiques de polycarbonate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12759762

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2849663

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2012759762

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载