EP2904018A1 - Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères - Google Patents

Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères

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Publication number
EP2904018A1
EP2904018A1 EP13770481.3A EP13770481A EP2904018A1 EP 2904018 A1 EP2904018 A1 EP 2904018A1 EP 13770481 A EP13770481 A EP 13770481A EP 2904018 A1 EP2904018 A1 EP 2904018A1
Authority
EP
European Patent Office
Prior art keywords
monomers
acid
weight
polymer
protective colloid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13770481.3A
Other languages
German (de)
English (en)
Inventor
Oral Aydin
Andrea SCHINDLER
Florian BÜSCH
Jürgen SIROKY
Matthias Gerst
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
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 EP13770481.3A priority Critical patent/EP2904018A1/fr
Publication of EP2904018A1 publication Critical patent/EP2904018A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the invention relates to a process for the preparation of an aqueous polymer dispersion based on (meth) acrylate ester monomers with a high solids content, the preparation being carried out in the presence of certain protective colloids and preferably emulsifier-free.
  • the aqueous polymer dispersions may i.a. be used as an adhesive.
  • adhesives based on aqueous dispersions with good performance properties are i.a. be used as an adhesive.
  • Water-based adhesive systems have the advantage of reducing organic solvent emissions.
  • acrylate ester polymer dispersions also known as acrylate latex.
  • Acrylate ester based adhesives are e.g. described in WO 98/23656 and WO 00/50480.
  • a high proportion of water often means undesirable expense for drying and filming the aqueous systems. Therefore, dispersions with the highest possible solids content and thus the lowest possible water content are sought.
  • Emulsion polymers are often prepared by emulsion polymerization in the presence of non-polymeric, low molecular weight emulsifiers.
  • the emulsifiers contained in the dispersion as a result of the preparation can undesirably adversely affect the performance properties. Therefore, emulsifier-free or emulsifier-free polymer dispersions are sought.
  • Typical protective colloids are acid group-containing polymers which are water-soluble upon neutralization of the acid groups at elevated pHs.
  • Protective colloid-containing polymer dispersions having high solids contents of e.g. more than 55% by weight or more than 60% by weight often have the disadvantage of poor rheological properties and are too viscous or no longer sufficiently flowable for coatings of substrates
  • the invention provides a process for preparing an aqueous polymer dispersion, wherein the polymer dispersion has a solids content of greater than 60% by weight, for example at least 61% by weight, at least 63% by weight or at least 65% by weight, and a water-dispersed polymer A is prepared in an aqueous medium by free-radical emulsion polymerization in the presence of a polymeric protective colloid B, and wherein the polymer A is formed to at least 80% by weight of (meth) acrylate ester monomers,
  • (Meth) acrylate ester monomers and acid monomers of the protective colloid at least 80% by weight, or at least 90% by weight, e.g. 80 to 100 wt.% Or 90 to 100 wt.%;
  • Protective colloids are fed in during the emulsion polymerization in the feed process
  • the invention also relates to aqueous polymer dispersions prepared by the process according to the invention and to the use of the aqueous polymer dispersions according to the invention for the production of adhesives.
  • the polymer dispersions prepared according to the invention are obtainable by free-radical emulsion polymerization of ethylenically unsaturated compounds (monomers).
  • the polymerization is preferably carried out emulsifier-free or emulsifier poor in the sense that no emulsifier is added to stabilize the polymer dispersion of the invention.
  • Emulsifiers are added to the polymerization mixture, non-polymeric, amphiphilic, surface-active substances. Small amounts of emulsifiers, e.g. are caused by the use of emulsifier-stabilized polymer seed are harmless.
  • the protective colloid B is formed, among others, from acid monomers.
  • Acid monomers are ethylenically unsaturated, radically polymerizable compounds which have at least one acid group.
  • the acid monomers are used in an amount of preferably from 10 to 50% by weight, in particular from 15 to 45% by weight, based on the total amount of monomers of which the protective colloid is formed.
  • the acid monomers are copolymerized with monomers without acid groups, especially nonionic monomers.
  • the weight ratio of monomers having acid groups to monomers without acid groups is preferably in the range from 10:90 to 50:50, in particular from 15:88 to 45:55.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate. Preference is given to acrylic acid and methacrylic acid and their mixture, acrylic acid being particularly preferred.
  • the acid groups of the protective colloid can be partially or completely neutralized with suitable bases.
  • Sodium hydroxide solution, potassium hydroxide solution or ammonia are preferably used as neutralizing agent.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene.
  • the protective colloid B has crosslinkable groups.
  • the crosslinkable groups are preferably obtained by copolymerizing with monomers, which contain crosslinkable groups.
  • Preferred crosslinkable groups are, for example, the keto group or at least one further (second) free-radically polymerizable ethylenically unsaturated double bond.
  • a suitable ketomonomer is, for example, acetoacetoxyethyl methacrylate (AA-EMA).
  • the protective colloid B is formed from
  • polymer A is preferably formed to 80 to 100 wt.% Of C1 -10 alkyl (meth) acrylates.
  • At least one molecular weight regulator is used in the polymerization of the protective colloid. This can be reduced by a chain termination reaction, the molecular weight of the emulsion polymer.
  • the regulators are bound to the polymer, generally to the chain end.
  • the amount of regulator is in particular 0.05 to 4 parts by weight, more preferably 0.05 to 0.8 parts by weight and most preferably 0.1 to 0.6 parts by weight, based on 100 Parts by weight of the monomers to be polymerized. Suitable regulators are e.g.
  • the regulators are generally low molecular weight compounds having a molecular weight of less than 2000, in particular less than 1000 g / mol.
  • the number-average molecular weight of the protective colloids is preferably above 1000 g / mol, in particular above 2000 g / mol and preferably up to 50 000 g / mol or up to 20 000 g / mol. for example, from 1000 to 50,000 g / mol, from 1,000 to 20,000 g / mol or from 2,000 to 20,000 g / mol.
  • seed latex is an aqueous dispersion of finely divided polymer particles having an average particle diameter of preferably from 20 to 100 nm. Seed latex is used in an amount of preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight, based on the total amount of monomers. Suitable is, for example, a latex based on Polystyrene or based on polymethylmethacrylate. A preferred seed latex is polystyrene seed.
  • methyl acrylate methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, 2-propylheptyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • the polymer A may optionally be composed of other monomers.
  • the further monomers can be used in amounts of, for example, from 0 to 20% by weight or from 0.1 to 10% by weight.
  • the further monomers may be selected from the group consisting of acid monomers, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of from 1 to 10 carbon atoms. Atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers. Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for.
  • vinyl laurate stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated compounds substituted with chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene.
  • the polymer A may additionally be composed of allyl methacrylate (AMA).
  • the monomers for the polymerization of the polymer A may comprise further monomers, for example monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Other monomers are z. As well as hydroxyl-containing monomers, in particular Ci-Cio-hydroxyalkyl (meth) acrylates and (meth) acrylamide.
  • Other monomers which may also be mentioned are crosslinking monomers.
  • the monomers used for the polymerization of the polymer A comprise less than 5 wt .-%, less than 1 wt .-% or no monomers with acid groups.
  • the monomers for the polymerization of the polymer A are selected so that the calculated glass transition temperature in the range of -60 ° C to 0 ° C, in particular from -50 ° C to -20 ° C.
  • the monomers for the polymerization of the polymer A are selected so that the calculated glass transition temperature in the range of -60 ° C to 0 ° C, in particular from -50 ° C to -20 ° C.
  • the preparation of the polymer dispersion according to the invention is carried out by emulsion polymerization.
  • emulsion polymerization ethylenically unsaturated compounds (monomers) are polymerized in water, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers usually being used as surface-active compounds for stabilizing the monomer droplets and the polymer particles later formed from the monomers .
  • the production process according to the invention is distinguished by the fact that it is possible to dispense with emulsifiers as far as possible or completely.
  • the protective colloid B is used.
  • the neutralization of acid groups of the protective colloid preferably takes place before or during the polymerization of the polymer A. After all monomers have been added, the amount of neutralizing agent needed to neutralize at least 10%, preferably 30 to 100% or 30 to 90% acid equivalents is preferably contained in the polymerization vessel ,
  • the addition of protective colloid and monomers is carried out according to the invention in a characteristic Rampfahrweise.
  • the preparation process according to the invention is characterized in that at least 80% by weight, preferably 80 to 100% by weight of the total amount of the protective colloid are fed in during the emulsion polymerization in the feed process and that the monomer addition takes place in the feed process, wherein the feed rate increases with time, ie the final rate of monomer feed is higher than the initial rate.
  • the feed rate preferably increases continuously or incrementally in several steps, e.g. in at least three or at least five steps.
  • the feed rate for the protective colloid also increases continuously or in several steps, e.g. incrementally in at least three or at least five steps.
  • protective colloid preferably begins only after the polymerization has been started and at least 1% by weight, at least 2% by weight or at least 5% by weight of the total amount of monomer has already been added to the polymerization vessel.
  • the addition of protective colloid is preferably carried out continuously or incrementally and in parallel with the continuous or incremental addition of the remaining monomers.
  • the polymerization preferably takes place in such a way that during the emulsion polymerization a maximum of 10% by weight of the monomers used to form the polymer A are added in the initial rate of the monomer feed or in a feed rate which is less than the terminal rate of the monomer feed.
  • the emulsion polymerization can be started with water-soluble initiators.
  • Water-soluble initiators are e.g. Ammonium and alkali metal salts of peroxodisulphuric acid, e.g. Sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. tert
  • Butyl hydroperoxide also suitable as an initiator are so-called reduction-oxidation (redox) initiator systems.
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is, for example, the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for example, alkali metal salts of sulfurous acid, such as sodium sulfite, sodium bisulfite, alkali metal salts of the disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid.
  • alkali metal salts of sulfurous acid such as sodium sulfite, sodium bisulfite
  • alkali metal salts of the disulfurous acid such as sodium disulfite
  • bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
  • Typical redox initiator systems are, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl Butyl hydroperoxide / Na hydroxymethanesulfinic.
  • the individual components for example the reduction component, may also be mixtures, for example a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the initiators mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water.
  • the concentration of initiators 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 to 10 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • the molecular weight regulators mentioned above for the preparation of the protective colloid can be used.
  • aqueous dispersions of the polymer are generally obtained with solids contents of greater than 60% by weight, for example at least 61% by weight, at least 63% by weight or at least 65% by weight.
  • a bimodal or polymodal particle size can be adjusted in order to obtain an even better rheological behavior, in particular a lower viscosity.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the size distribution of the dispersion particles may be monomodal, bimodal or multimodal. In the case of monomodal particle size distribution, the average particle size of the polymer particles dispersed in the aqueous dispersion is preferably less than 400 nm, in particular less than 200 nm.
  • average particle size is meant the dso value of the particle size distribution, ie 50% by weight of the total mass of all particles a smaller particle diameter than the dso value.
  • the particle size distribution can be determined in a known manner with the analytical ultracentrifuge (W. Gurchtie, Makromolekulare Chemie 185 (1984), page 1025-1039).
  • the particle size can be up to 1000 nm.
  • the pH of the polymer dispersion is preferably adjusted to pH greater than 5, in particular to a pH of between 5.5 and 8.
  • the invention also relates to the aqueous polymer dispersions prepared according to the invention.
  • the invention also relates to the use of the aqueous polymer dispersions prepared according to the invention for the production of adhesives, in particular for the production of pressure-sensitive adhesives or laminating adhesives, e.g. for the production of composite films or for protective film lamination.
  • the present invention thus also relates to a process for the preparation of adhesive articles, e.g. Labels or composite films in which an aqueous adhesive preparation is used which comprises at least one inventive polymer dispersion and wherein a substrate is coated with the aqueous adhesive preparation.
  • the aqueous polymer dispersions can be used as such or after packaging with customary auxiliaries.
  • auxiliaries are, for example, wetting agents, thickeners, further protective colloids, light stabilizers, biocides, defoamers, etc.
  • the adhesive formulations according to the invention may be mixed with softening resins (Tackifiern) or other plasticizers.
  • Tackifiern softening resins
  • the process for producing composite films at least two films are bonded together using the aqueous polymer dispersion.
  • the polymer dispersion of the invention or a correspondingly prepared preparation is preferably applied to a substrate to be bonded with a layer thickness of 0.1 to 20 g / m 2 , more preferably 1 to 7 g / m 2 z. B. by doctoring, brushing, etc. applied.
  • Conventional coating methods can be used, eg roll coating, reverse roll coating, gravure roll coating, countergraduate roll coating, brush coating, bar brushing, spray coating, airbrush coating, Meniscus coating, curtain coating or dip coating. After a short time to vent the dispersion water (preferably after 1 to 60 seconds), the coated substrate can then be further processed.
  • the polymer dispersion according to the invention is preferably used as one-component agent, ie without additional crosslinking agents, in particular without isocyanate crosslinkers.
  • the polymer dispersion of the present invention may also be used as a two-component adhesive in which a crosslinking component such as a water-emulsifiable isocyanate is added.
  • the protective colloid contains at least one crosslinkable group, e.g. Keto groups.
  • the adhesive formulation then preferably contains at least one keto- group-reactive compound, e.g. Diamines, preferably propylenediamine, diethylenetriamine, dipropylenetriamine, N- (2-aminoethyl) aminopropylamine, N, N-bis (3-aminopropyl) methylamine, N ⁇ -Bis ⁇ -aminopropy ⁇ ethylenediamine, preferably in an amount of a few weight percent (eg 235 ⁇ _ propylene diamine to 100 ml dispersion).
  • Other reactive groups (detailed description: J.W. Taylor, M.A.
  • Suitable substrates are e.g. Paper or polymer films. The films may be printed or metallized on the side coated with the adhesive. Suitable substrates are z.
  • As polymer films in particular of polyethylene (PE), oriented polypropylene (OPP), unstretched polypropylene (CPP), polyamide (PA), polyethylene terephthalate (PET), polyacetate, cellophane, with metal, for.
  • PE polyethylene
  • OPP oriented polypropylene
  • CPP unstretched polypropylene
  • PA polyamide
  • PET polyethylene terephthalate
  • polyacetate cellophane
  • metal for.
  • coated (steamed) polymer films in short: metallized films
  • metal foils for. B. aluminum.
  • the films mentioned can each other or with a film of another type, for.
  • a surface treatment of the film substrates is not absolutely necessary before coating with a polymer dispersion according to the invention. Better results can be obtained, however, by modifying the surface of the film substrates prior to coating.
  • conventional surface treatments can be used, eg Corona treatment to enhance the adhesion.
  • the corona treatment or other surface treatments are performed to the extent necessary for sufficient wettability with the coating composition. Usually, a corona treatment of about 10 watts per square meter per minute is sufficient for this purpose.
  • primers or intermediate layers between the film substrate and the adhesive coating it is optionally also possible to use primers or intermediate layers between the film substrate and the adhesive coating.
  • the composite films, further, additional functional layers have, for example, barrier layers, printing layers, dye or lacquer layers or protective layers. The functional layers may be located outside, ie on the side of the film substrate facing away from the adhesive side, or inside, between the film substrate and the adhesive layer.
  • the temperature is raised from 75 to 95 ° C in 3 hours.
  • other functionalities can be introduced into the protective colloids, for example keto groups via AAEMA as monomer, so that post-crosslinking is possible after film formation. This can be detected by DMA measurements.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'une dispersion polymère aqueuse présentant une teneur élevée en substance solide, supérieure à 60% en poids. Selon l'invention, un polymère dispersé est fabriqué par polymérisation en émulsion radicalaire en présence d'un colloïde protecteur polymère. Ce polymère est formé d'au moins 80% en poids de monomères esters de (méth)acrylate et le colloïde protecteur polymère est formé de monomères acides et d'au moins 10% en poids de monomères esters de (méth)acrylate, et la somme des monomères esters de (méth)acrylate et des monomères acides du colloïde protecteur s'élève au moins à 80% en poids. La polymérisation en émulsion se produit pendant le procédé d'apport en masse de monomères, la vitesse de départ d'apport en masse de monomères étant inférieure à la vitesse de fin d'apport en masse de monomères. Les dispersions polymères peuvent être utilisées entre autres en tant que colle.
EP13770481.3A 2012-10-05 2013-09-27 Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères Withdrawn EP2904018A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13770481.3A EP2904018A1 (fr) 2012-10-05 2013-09-27 Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201261710015P 2012-10-05 2012-10-05
EP12187454 2012-10-05
EP13770481.3A EP2904018A1 (fr) 2012-10-05 2013-09-27 Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères
PCT/EP2013/070178 WO2014053410A1 (fr) 2012-10-05 2013-09-27 Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères

Publications (1)

Publication Number Publication Date
EP2904018A1 true EP2904018A1 (fr) 2015-08-12

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EP13770481.3A Withdrawn EP2904018A1 (fr) 2012-10-05 2013-09-27 Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères

Country Status (4)

Country Link
US (1) US20150284482A1 (fr)
EP (1) EP2904018A1 (fr)
CN (1) CN104822710A (fr)
WO (1) WO2014053410A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3286274B1 (fr) * 2015-04-20 2019-12-25 Basf Se Colle à froid aqueuse
EP3390473A1 (fr) * 2015-12-17 2018-10-24 Basf Se Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites
ES2931335T3 (es) * 2018-04-20 2022-12-28 Basf Se Composición adhesiva con contenido de gel a base de reticulación mediante grupos ceto o aldehído
WO2021123196A1 (fr) 2019-12-20 2021-06-24 Basf Se Polymères en émulsion à haute teneur en solides stabilisés à l'aide de résine ensemencée
EP4448591A1 (fr) * 2021-12-15 2024-10-23 Basf Se Procédé de préparation d'une dispersion aqueuse de polymère

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004076581A1 (fr) * 2003-02-28 2004-09-10 Soken Chemical & Engineering Co., Ltd. Adhesif sensible a la pression de type emulsion et procede de fabrication associe
JP4250757B2 (ja) * 2003-02-28 2009-04-08 綜研化学株式会社 エマルジョン型粘着剤の製造方法
US7939572B2 (en) * 2004-08-31 2011-05-10 Rohm And Haas Company Aqueous dispersion of polymeric particles
US8999358B2 (en) * 2005-03-09 2015-04-07 Basf Aktiengesellschaft Aqueous insecticidal compositions and the use thereof for protecting lignocellulose-containing materials

Non-Patent Citations (1)

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Title
See references of WO2014053410A1 *

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WO2014053410A1 (fr) 2014-04-10
CN104822710A (zh) 2015-08-05
US20150284482A1 (en) 2015-10-08

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