Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/11—Encapsulated compositions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F28—HEAT EXCHANGE IN GENERAL
  • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
  • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
  • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
  • F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/14—Thermal energy storage
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

• Microcapsules with hyperbranched polymers as crosslinkers are Microcapsules with hyperbranched polymers as crosslinkers
• the present invention relates to microcapsules comprising a capsule core and a capsule wall, obtainable by a process comprising the radical polymerization of an oil-in-water emulsion which comprises the following constituents:
• the present invention further relates to processes for their preparation and their use.
• Microcapsules are known in various embodiments and are used depending on the tightness of the capsule wall for very different purposes. For example, they serve to protect core materials.
• Such microcapsules contain, for example, latent heat storage materials often also referred to as PCM (phase change material), whose operation is based on the fact that the solid / liquid phase transition due to the enthalpy of conversion means an energy absorption or energy release to the environment. They can thus be used for temperature maintenance in a defined temperature range.
• PCM phase change material
• core materials are known which are intended to be released only by targeted mechanical destruction of the capsule wall, such as dyes for copying papers or encapsulated fragrances.
• capsule wall materials based on gelatin, polyurethane and polyurea and based on polyacrylates and methacrylates are known.
• E P-A-1 029 018 and EP-A 1 321 182 teach the use of microcapsules having a capsule wall of highly crosslinked methacrylic acid ester polymer and a latent heat storage core in binders such as concrete or gypsum.
• WO 2008/071649 describes microcapsules based on methacrylic acid esters and a crosslinker combination of butanediol diacrylate and pentaerythritol tetraacrylate.
• microcapsule dispersions A general requirement for microcapsule dispersions is good rheology. Microcapsule dispersions should show good flowability even under shear.
• microcapsule dispersions are desirable which have a high solids content, so that the proportion of the core material, which indeed determines the effect of the capsule, is higher. Neither by isolating the microcapsules and subsequent redispersing nor directly from the microencapsulation process itself are microcapsule dispersions with high solids contents available. In general, attempts to produce higher solids microcapsule dispersions will result in coagulation of the reaction mixture.
• microcapsule dispersions which can also be produced at a higher solids content.
• the production of microcapsule dispersions with high solids contents should be possible directly from the microencapsulation.
• the microcapsule dispersions should generally have improved rheology.
• microcapsules were found.
• the present application further relates to processes for the preparation of microcapsules and their use for copying papers, in cosmetics, in chemical synthesis, in crop protection, as crosslinkers in adhesives, paints, varnishes, paper coating slips or other coating or impregnating agents as well as latent heat storage.
• alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched C 1 -C 7 -alkyl, preferably C 1 -C 6 -alkyl and particularly preferably C 1 -C 4 -alkyl groups.
• Suitable longer-chain C 8 -C 20 -alkyl groups are straight-chain and branched alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include z.
• alkyl includes unsubstituted and substituted alkyl radicals.
• alkyl also apply to the alkyl moieties in arylalkyl.
• Preferred arylalkyl radicals are benzyl and phenylethyl.
• alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 7 carbon atoms, eg. As methylene, 1, 2-ethylene, 1, 3-propylene, etc ..
• Cycloalkyl is preferably Cs-Cz-cycloalkyl, such as cyclopentyl, cyclohexyl or cycloheptyl.
• aryl in the context of the present invention comprises mono- or poly-ring aromatic hydrocarbon radicals which may be unsubstituted or substituted.
• aryl is preferably phenyl, ToIyI, XyIyI, mesityl, Duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, said aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.
• the microcapsules according to the invention comprise a capsule core and a capsule wall.
• the capsule core consists predominantly, to more than 95 wt .-%, of nuclear material.
• the mean particle size of the capsules (Z means by means of light scattering) is 1 to 50 ⁇ m.
• the average particle size of the capsules is 1, 5 to 20 microns.
• preferably 90% of the particles have a particle size (diameter) D [v, 0.9] ⁇ 20 microns.
• the span value (D [v, 0.9] -D [v, 0.1]) / D [v, 0.5] of the microcapsule distribution is preferably 0.1 to 1.5, in particular 0.2 to 1, third
• the average particle size of the capsules is 1, 5 to 10 ⁇ m, preferably 2 to 6 ⁇ m.
• the span value (D [v, 0.9] -D [v, 0.1]) / D [v, 0.5] of the microcapsule distribution is preferably 0.1 to 1.5, in particular 0.1 to 1, second
• the weight ratio of capsule core to capsule wall is generally from 50:50 to 95: 5.
• Preferred is a core / wall ratio of 70:30 to 93: 7.
• Suitable monomers I are Ci-C24-alkyl esters of acrylic and / or methacrylic acid and the unsaturated C3 and C4 carboxylic acids such as acrylic acid, methacrylic acid and maleic acid, fumaric acid and itaconic acid.
• Suitable monomers I are isopropyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates, and particularly preferably methyl, ethyl, n-propyl and n-butyl acrylate and the corresponding methacrylates.
• the methacrylates and methacrylic acid are preferred.
• one or more highly branched polymeric crosslinkers are used according to the invention.
• the highly branched polymers on which the crosslinkers are based include star polymers, dendrimers and various highly branched polymers, in particular hyperbranched polymers, which in each case have ethylenically unsaturated groups, generally end groups and optionally side groups.
• Star polymers are polymers in which three or more chains originate from one center.
• the center can be a single atom or an atomic group.
• Dendrimers are derived structurally from the star polymers, but the individual chains are in turn branched star-shaped. They are formed starting from small molecules to which a branching unit-carrying monomer is added via a constantly repeating defined reaction sequence. Thus, with each reaction step, the number of monomer end groups increases, whereby at the end an, ideally spherical, tree structure is formed.
• a characteristic feature of dendrimers is the number of reaction stages (generations) performed to build them up. Due to their uniform structure (ideally, all branches contain exactly the same number of monomer units), dendrimers are essentially monodisperse, i. H. they usually have a defined molecular weight. Molecular as well as structurally uniform hyperbranched polymers are also referred to below uniformly as dendrimers.
• “Hyperbranched polymers” in the context of this invention are highly branched polymers which, in contrast to the abovementioned dendrimers, are both molecularly and structurally nonuniform. They have side chains and / or side branches of different length and branching as well as a molecular weight distribution.
• the width of the molecular weight distribution is preferably characterized by a value for the polydispersity (quotient of weight-average molecular weight M w and number-average molecular weight M n ) and is preferably at least 1.1, in particular at least 1, 2 and is preferably in the range of 1, 1 to 50, preferably from 1, 2 to 40, more preferably from 1, 3 to 30 and most preferably from 1, 5 to 10.
• the highly branched polymers used according to the invention preferably have a degree of branching (DB) per molecule of from 10 to 100%, preferably from 10 to 90% and in particular from 10 to 80%.
• T is the average number of terminal monomer units
• Z is the mean number of branching monomer units
• L is the average number of linearly bound monomer units.
• Dendrimers generally have a degree of branching DB of at least> 95%, in particular 99%, especially 99.9 to 100%.
• Hyperbranched polymers preferably have a degree of branching DB of 10 to 95%, preferably 25 to 90% and in particular 30 to 80%.
• Dendrimers as well as hyperbranched polymers can be used according to the invention as crosslinkers, with hyperbranched polymers being preferred as crosslinkers, since they are generally simpler and thus more economical to produce.
• the skeletons of hyperbranched polymers can often be prepared by one-step syntheses. Their synthesis is distinguished by various synthetic approaches (C. Gao, D. Yan, Prog. Polym., Vol. 29 (2004), 183-275).
• highly branched polymeric crosslinkers and in particular "hyperbranched polymeric crosslinkers” in the context of this invention generally designate polymers which have a highly branched structure and which carry ethylenically unsaturated groups, usually end and / or side groups. Furthermore, they preferably have a high functionality. Functionality means both the ethylenically unsaturated end and side groups as well as functional end groups or side groups which are not ethylenically unsaturated. The functional end or side groups are dependent on the polymer backbone and ultimately come from the educts or their reaction products.
• a high-functionality polycarbonate in the context of this invention means a product which, in addition to the carbonate groups forming the polymer backbone, has terminal or pendant functional radicals which are carbonate groups, carbamoyl chloride groups and / or OH groups and also ethylenically unsaturated groups contain.
• High functionality is understood to mean that the polymers have two or more ethylenically unsaturated end and / or side groups as well as a total of at least three, preferably at least six functional end and / or side groups.
• highly branched polymers see also PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499, referred to therein (deviating from the name chosen here as "hyperbranched polymers").
• the number of ethylenically unsaturated end and / or side groups of the polymeric crosslinker is on average (number average) at least 2, in particular at least 3.
• the maximum number of these radicals is often not more than 100. It can be determined analytically, for example by iodine number determination.
• Preference is given to polymeric crosslinkers whose functionality is 3 to 50.
• Preference is given to polymeric crosslinkers whose number of ethylenically unsaturated end and / or side groups is 2 to 10.
• the double bond content of the hyperbranched polymeric crosslinkers is 0.1 to 10, preferably 0.2 to 8, particularly preferably 0.3 to 6 mol / kg (determinable via the iodine number).
• hyperbranched polymeric crosslinkers which have a weight-average molecular weight Mw in the range from about 800 to 300,000, particularly preferably from 1000 to 100,000 and in particular from 1000 to 80,000 g / mol.
• the molar mass determination can be carried out by gel permeation chromatography using a standard, such as polymethyl methacrylate.
• the number average molecular weight Mn is preferably in the range of at least 500, preferably at least 600 and more preferably at least 750 g / mol to 100,000 g / mol. More preferably, it is not more than 80,000 and most preferably not more than 30,000 g / mol.
• Highly branched polymers are in principle suitable for those which are obtainable by polycondensation or polyaddition. Preference is given to highly branched polymeric crosslinkers, the polymeric skeleton of which is built up by polyaddition or polycondensation - in other words, the highly branched polymeric crosslinker is a polyaddition product or a polycondensation product.
• polycondensation is meant the repeated chemical reaction of functional compounds with suitable reactive compounds with elimination of low molecular weight compounds such as water, alcohols, amines, HCl, etc.
• polyaddition is meant the repeated chemical reaction of functional compounds with suitable reactive compounds without cleavage of low molecular weight compounds.
• Suitable polymeric backbones have linking groups, which are preferably selected from ether groups, ester groups, carbonate groups, amino groups, amide groups, urethane groups and urea groups.
• polymers of the class polycarbonates, polyesters, polyethers, polyurethanes, polyureas, polyamides, and their mixed forms such as poly (urea-urethanes), poly (ether-amines), poly (esteramines), polyols, can be used as highly branched crosslinkers. ly (ether amides), poly (esteramides), poly (amido amines), poly (ester carbonates), poly (ether carbonates), poly (ether esters) and poly (ether ester carbonates), etc. are used.
• hyperbranched polyethers according to WO 03/062306, WO 00/56802, DE 102 11 664 or DE 199 47 631, hyperbranched nitrogen-containing polymers (especially polyurethanes, polyureas, polyamides, poly (esteramides), Poly (esteramine), as in the
• WO 2006/087227 described, hyperbranched polyurethanes according to WO 97/02304 or DE 199 04 444,
• WO 2002/081071 hyperbranched poly (urea) according to WO97 / 02304 or DE 199 04 444, hyperbranched polyureas as in WO 03/066702, WO 2005/044897 and
• hyperbranched polymers containing amino groups especially poly (esteramines) according to WO 2005/007726, - hyperbranched poly (esteramides) according to WO 99/16810 or EP 1 036 106, hyperbranched polyamides as described in WO 2006/018125, hyperbranched poly (ester carbonates) as described in WO 2006/089940.
• the introduction of the ethylenically unsaturated groups can already take place during the polyaddition or polycondensation by adding, in addition to the polyfunctional compounds, a compound having single or multiple identical functionality and at least one ethylenically unsaturated radical.
• the ethylenically unsaturated end and / or side groups are preferably introduced by polycondensation or polyaddition subsequent to the construction of the skeleton. This polymer-analogous modification takes place, depending on the selected skeleton and thus existing end groups, by reaction of compounds reactive with these end groups and carrying ethylenically unsaturated radicals.
• Preferred ethylenically unsaturated groups of the polymeric crosslinkers are the methacrylic radical, acrylic radical, vinyl radical, allyl radical, maleyl radical, itaconyl radical, in particular the aryl radical, methacrylic radical and the allyl radical.
• the modification is carried out with ethylenically unsaturated groups by reacting with these end groups reactive compounds which carry ethylenically unsaturated radicals.
• polyesters, polycarbonates and polyurethanes having ethylenically unsaturated end and / or side groups are preferred as highly branched crosslinkers.
• Polycarbonates and polyurethanes with an acrylic radical are particularly preferred as crosslinkers according to the invention.
• hyperbranched polyesters which are obtained by reacting at least one dicarboxylic acid or its halides, in particular chlorides, their anhydrides or their esters, with at least one tri- or polyhydric alcohol are suitable.
• Tri- or polyhydric alcohols mean three or four or more OH radicals.
• Tri- or polyfunctional carboxylic acid is understood to mean three or four or more COOH radicals or the corresponding acid halide radicals -CO-Hal, anhydride radicals -CO-O-CO-R 'or ester radicals -CO-OR'.
• the ethylenically unsaturated groups are preferably introduced directly in the construction of the backbone. They can be introduced via the alcohol, the acid or its derivatives.
• the hyperbranched polyesters having ethylenically unsaturated radicals can be prepared by reaction
• the condensation products (K) have on average either an OH group and more than one carboxyl group or group derived therefrom, or preferably a carboxyl group or have derived therefrom group and more than one OH group.
• the polyesters are preferably polyesters having hydroxyl end groups.
• polymers which have both hydroxyl end groups and acid end groups or their derivatives are formed. Preference is given to hyperbranched polymers whose fraction of hydroxyl end groups is> 50%, based on the sum of the end groups.
• Ethylenically unsaturated di- and polycarboxylic acids which may be mentioned are ethylenically unsaturated C 4 -C 10 -di- or polycarboxylic acids, preferably monoethylenically unsaturated C 4 -C 10 -dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, metaconic acid. Also suitable are the halides, anhydrides and esters derived from these acids, for example maleic anhydride, dimethyl fumarate or diethyl fumarate.
• Preferred nonethylenically unsaturated dicarboxylic acids or their halides, anhydrides or esters are, for example, aliphatic linear or branched C 2 -C 24 -dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, adipic acid, octanedioic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid or dodecanedioic acid.
• aromatic C 5 -C 12 -dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid or naphthalenedicarboxylic acid.
• Suitable trifunctional and polyfunctional alcohols are the alcohols (B) mentioned below in the context of the preparation of the hyperbranched polycarbonates.
• Alcohol (B) is preferably selected from Cs-Cs triols which have been alkoxylated once or more than once with at least one C 2 -C 6 -alkylene oxide.
• difunctional alcohols (diols) (B ') are those mentioned below in the context of the preparation of hyperbranched polycarbonates.
• the hyperbranched polyesters having ethylenically unsaturated radicals can be prepared, for example, by reaction
• the quantitative ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (K) on average either an OH group and more than one carboxyl group or group derived therefrom or preferably a carboxyl group or group derived therefrom and have more than one OH group.
• Preferred polycarboxylic acids or their halides, anhydrides or esters are, for example, aconitic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) as well as mellitic acid and low molecular weight polyacrylic acids.
• Preferred ethylenically unsaturated difunctional or trifunctional or polyfunctional alcohols are divinyl glycol.
• hyper-branched polyesters may also be based on the branching monomer dimethylolpropionic acid are prepared, being chosen as a starting point location for the polymerization often a "core molecule" such as trimethylolpropane or pentaerythritol.
• core molecule such as trimethylolpropane or pentaerythritol.
• Such polyesters are available under the name Boltorn ® (Perstorp Specialty Chemicals). Your modification with ethylenically unsaturated radicals is described, for example, in WO 00/64975, to which reference is expressly made.
• Hyperbranched polycarbonates are obtainable by reacting at least one organic carbonate (A) with at least one trifunctional or polyhydric alcohol (B).
• Polyfunctional alcohol is understood as meaning four or more OH radicals.
• the hyperbranched polycarbonates will be prepared, for example
• the amount ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (K) on average either a Carbonate group and more than one OH group or preferably an OH group and more than one carbonate group.
• the polycarbonates are preferably polycarbonates with hydroxyl end groups.
• Step a) by reacting the hyperbranched polycarbonate obtained from b) with an ethylenically unsaturated compound reactive with hydroxyl groups or with carbonate groups, and / or according to further preferred embodiments d) by adding an ethylenically unsaturated compound reactive with hydroxyl groups or with carbonate groups, before or during Step a) and / or
• the organic carbonates used as starting material for the polycondensations include aliphatic, aromatic / aliphatic and aromatic carbonates (A), preferably of the general formula R a -O- (CO) -OR b , where R a and R b are each independently selected are among straight-chain or branched C1-C20-alkyl, arylalkyl, Cs-Cz-cycloalkyl and C ⁇ -Cio-aryl radicals, wherein R a and R b are also taken together with the group -O- (CO) -O- for a cyclic Carbonate can stand.
• the radicals R a and R b preferably have the same meaning.
• Carbonates (A) which may be mentioned by way of example are ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate , Dihexyl carbonate, di-cyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate, dialkyl dicarbonates, such as di (tert-butyl) dicarbonate or dialkyl tricarbonates, such as di (tert-butyl) tricarbonate.
• dialkyl dicarbonates such as di (tert-butyl) dicarbonate or dialkyl tricarbonates, such as di (
• Aliphatic carbonates (A) are preferably used, in particular those in which the radicals R a and R b comprise 1 to 5 C atoms, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.
• the organic carbonates are reacted with at least one tri- or polyhydric alcohol (B) or mixtures of these alcohols.
• the alcohols are aliphatic or aromatic alcohols.
• Examples of compounds having at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol rin, triglycerol, polyglycerols, bis (tri-methylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1 Tris (4'-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, sugars, such as, for example, glucose, sugar derivative
• glycerol trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, pentaerythritol, and their polyetherols based on ethylene oxide or propylene oxide are particularly preferred.
• polyhydric alcohols (B) can also be used in mixture with difunctional alcohols (B '), with the proviso that the mean OH functionality of all the alcohols used together is greater than 2.
• suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 and 1, 3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol,
• the amount of difunctional alcohol (s) (A) is 0 to 80 mol% with respect to the total amount of all alcohols (B) and (B ') together.
• the amount is preferably 0 to 50 mol%, particularly preferably 0 to 35 mol% and very particularly preferably 0 to 25 mol%.
• Ethylenically unsaturated compounds having groups which react with hydroxyl groups are unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, unsaturated carboxylic acid halides such as acryloyl chloride or methacrylic acid chloride and unsaturated carboxylic acid anhydrides such as maleic anhydride, acrylic anhydride or methacrylic anhydride.
• degrees of esterification of 5 to 90 mol%, preferably 10 to 50 mol%, based on the OH group number of the polycarbonates, are generally achieved.
• Ethylenically unsaturated compounds are also allyl halide, vinyl and Allylchloroformiate, ethylenically unsaturated isocyanates such as isocyanatoalkyl acrylates and methacrylates or dimethyl metaisopropenylbenzyl isocyanate (TMI) from. Cytec Industries. Ethylenically unsaturated groups can also be introduced by the addition of OH-containing unsaturated compounds before or during the polycondensation reaction.
• Monoesters of ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid, preferably acrylic acid and methacrylic acid, or vinyl ethers with diols or polyols, preferably 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol , Pentaethylene glycol, tripropylene glycol, 1, 2-, 1, 3- or 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-1, 5-pentan
• esters or amides of (meth) acrylic acid with amino alcohols eg.
• amino alcohols eg.
• polycarbonates with ethylenically unsaturated radicals can be prepared by the addition of ethylenically unsaturated alcohols such as isoprenol, allyl alcohol or divinylglycol during the polycondensation reaction.
• ethylenically unsaturated alcohols such as isoprenol, allyl alcohol or divinylglycol
• the polyurethanes are preferably polyurethanes whose end group modification takes place via the reaction of ethylenically unsaturated compound reactive with hydroxyl groups or with isocyanate groups.
• the basic structure is generally carried out by reacting a di-, tri- or polyfunctional isocyanate-reactive compound, preferably an alcohol and / or aminoalcohol, with a di- and / or polyisocyanate.
• a di-, tri- or polyfunctional isocyanate-reactive compound preferably an alcohol and / or aminoalcohol
• multifunctional reactive compound is meant a compound having four or more isocyanate-reactive groups.
• polyisocyanate is meant a compound having an average of more than two, usually with an average of 2.1 to five, especially with an average of three to four isocyanate groups.
• Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art.
• Diisocyanates are those isocyanates having a functionality of 2, i. two isocyanate groups per molecule.
• Polyisocyanates are those isocyanates which have on average more than 2, preferably on average at least 2.1 NCO groups per molecule.
• Preferred di- or polyisocyanates are 2,4- and 2,6-toluene diisocyanate or mixtures thereof, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI) or mixtures thereof, the mixtures of monomeric diphenylmethane diisocyanates and higher nuclear homologues of diphenylmethane diisocyanate ( Polymer MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate trimer, 2,4'- and 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate , Lysinalkylester diisocyanate, wherein alkyl is Ci to C10
• di- or polyisocyanates such as hexamethylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triiso cyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl 2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane 1, 3-diisocyanate.
• di- or polyisocyanates such as hexamethylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-dip
• oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or triisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide , Uretonimine, oxadiazinetrione or iminooxadiazinedione structures.
• 2,4'- and 4,4'-diphenylmethane diisocyanate mixtures of diphenylmethane diisocyanates and higher-nuclear homologues of diphenylmethane diisocyanate (polymeric MDI), 1, 3 and 1, 4-phenylene diisocyanate, 4-isocyanatomethyl-1,8-octa methylene diisocyanate, hexamethylene diisocyanate, isocyanurate, uretdione, urethane, allophanate, iminooxadiazinedione or biuret group-containing oligomers of hexamethylene diisocyanate or isophorone diisocyanate (IPDI), oligomers of MDI or urethane having urethane, allophanate, carbodiimide or uretonimine groups, Allophanate, carbodiimide or uretonimine group-containing oligomers from
• monomers known to the person skilled in the art such as phenyl isocyanate, o-, m- or p-tolyl isocyanate, naphthyl isocyanate, phenylsulfonyl isocyanate, toluenesulfonyl isocyanate, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, dodecyl isocyanate or stearyl isocyanate.
• phenyl isocyanate, toluenesulfonyl isocyanate, cyclohexyl isocyanate or stearyl isocyanate Preference is given to adding phenyl isocyanate, toluenesulfonyl isocyanate, cyclohexyl isocyanate or stearyl isocyanate.
• the isocyanate-reactive compounds have hydroxyl groups, mercapto groups and / or amino groups. Preference is given to hydroxyl and / or amino groups and more preferably hydroxy groups.
• Examples of compounds having at least three isocyanate-reactive groups are glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, 1, 2,7 -Heptanetriol, 1, 2,8-octanetriol, 1, 2,9-nonanetriol, 1, 2,10-decanetriol, tris (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, 2- Amino-1, 3-propanediol, 2-amino-2-methyl-1,3-propanediol, diethanolamine, dipropanolamine, diisopropanolamine, ethanolpropanolamine, bis (aminoethyl) amine, bis (aminopropyl) amine, tris (aminoethyl)
• Preferred compounds having at least three or more isocyanate-reactive
• Groups are tri- or polyfunctional alcohols.
• glycerol trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, 1, 2,6-hexanetriol, pentaerythritol
• polyetherols based on glycerol, trimethylolpropane and pentaerythritol are particularly preferred.
• Examples of compounds having two isocyanate-reactive groups are ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 and 1, 3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol , 1, 2-, 1, 3- and 1, 5-pentanediol, 1, 6-hexanediol, hydroxypivalate neopentyl glycol, propane-1, 2-dithiol, butane-1, 2-dithiol, mercaptoethanol, mercaptopropanol, mercaptobutanol, ethylenedione - min, toluenediamine, isophoronediamine, cysteamine, ethanolamine, N-methylethanolamine, 1, 2- or 1, 3-propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-a
• ethylene glycol, 1, 2- and 1, 3-propanediol, 1, 2, 1, 3 and 1, 4-butanediol, ethanolamine, 1, 2-propanolamine, mercaptoethanol, 4-hydroxypiperidine and 1-hydroxyethylpiperazine or polyetherols are particularly preferred.
• the modification with ethylenically unsaturated radicals takes place by reaction with ethylenically unsaturated radicals bearing isocyanate-reactive or hydroxyl-reactive compounds.
• ethylenically unsaturated radicals bearing isocyanate-reactive or hydroxyl-reactive compounds examples which may be mentioned are monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid, preferably acrylic acid or methacrylic acid, with diols or polyols, preferably 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, tri
• esters or amides of (meth) acrylic acid with amino alcohols z are also suitable.
• amides of ethylenically unsaturated carboxylic acids and amino alcohols are suitable.
• hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides, such as N-hydroxyethylmaleimide.
• Ethylenically unsaturated compounds having groups which react with hydroxyl groups are unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, unsaturated carboxylic acid halides such as acryloyl chloride or methacrylic acid chloride, and unsaturated carboxylic acid anhydrides such as maleic anhydride, acrylic anhydride or methacrylic anhydride.
• degrees of esterification of from 5 to 90 mol%, preferably from 10 to 50 mol%, based on the OH group number of the polyurethanes are generally achieved.
• Ethylenically unsaturated compounds are also allyl halide, vinyl and Allylchloroformiate, ethylenically unsaturated isocyanates such as isocyanatoalkyl acrylates and methacrylates or dimethyl metaisopropenylbenzyl isocyanate (TMI) from. Cytec Industries.
• 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1, 4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.
• hydroxyethyl acrylate hydroxymethyl acrylate, pentaerythritol triacrylate, allylamine and diallylamine, in particular diallylamine and hydroxyethyl acrylate.
• polyurethanes with acrylic or allyl radicals are preferred as crosslinkers according to the invention.
• low molecular weight crosslinkers bearing two or more ethylenically unsaturated radicals may be used in conjunction with the one or more highly branched polymeric crosslinkers.
• low molecular weight is to be understood as meaning molecular weights ⁇ 800 g / mol. Preference is given to using low molecular weight crosslinkers with vinyl, allyl, acrylic or methacrylic groups.
• Suitable low molecular weight crosslinkers are, for example, divinylbenzene and divinylcyclohexane and preferably the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols.
• Examples are ethanediol diacrylate, ethylene glycol dimethacrylate, 1, 3-Butylenglykoldimethacrylat, Diethylene glycol diacrylate, dipropylene glycol diacrylate, methallyl methacrylamide, allyl acrylate and allyl methacrylate.
• Particularly preferred are propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.
• polyesters of polyols with acrylic acid and / or methacrylic acid, and the polyallyl and polyvinyl ethers of these polyols are preferred as low molecular weight crosslinkers.
• crosslinkers having three and / or four free-radically polymerizable double bonds such as trimethylolpropane triacrylate and methacrylate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, pentaerythritol triacrylate and pentaerythritol tetraacrylate and their technical mixtures.
• Suitable monomers III are monounsaturated monomers such as vinyl acetate, vinyl propionate, vinylpyridine and styrene or ⁇ -methylstyrene, itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate, acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
• monounsaturated monomers (monomers IIIa) such as vinyl acetate, vinyl propionate, vinylpyridine and styrene or ⁇ -methylstyrene.
• the capsule wall is obtainable by a process comprising the radical polymerization of an oil-in-water emulsion which contains the hydrophobic core material and the monomers I, II and optionally III. It is assumed that the wall material is formed by copolymerization of the monomers. However, it is unclear to which extent the highly branched polymeric crosslinker used in accordance with the invention is copolymerized in. It is conceivable both the binding of one and several double bonds. In addition, it is conceivable that polymeric crosslinkers are non-covalently bound to the wall.
• the oil-in-water emulsion generally contains at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, and up to 90% by weight, preferably at most 85 wt .-% and in particular at most 80 wt .-% of at least one monomer selected from C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid, acrylic acid, methacrylic acid and maleic acid (monomers I), based on the total weight of used monomers.
• the oil-in-water emulsion contains at least 10% by weight, preferably at least 15% by weight, preferably at least 20% by weight, and generally at most 70% by weight, preferably at most 65% by weight. % and in a particularly preferred form at most 60% by weight of one or more ethylenically unsaturated crosslinking agents (monomers II), based on the total weight of the monomers, wherein at least at least 10 wt .-%, preferably at least 20 wt%, in particular at least 30 wt% and at most 70, preferably at most 60 and in particular at most 55 wt .-% based on the total weight of the monomers I, II and III, highly branched, in particular hyperbranched, polymeric crosslinkers.
• monomers II ethylenically unsaturated crosslinking agents
• oil-in-water emulsion up to 30 wt .-%, preferably up to
• Monomers (monomer III) which are different from the monomers I contain.
• the oil-in-water emulsion contains as monomers only those of groups I and II.
• microcapsules obtainable by a process comprising the radical polymerization of an oil-in-water emulsion which
• microcapsules still show good tightness, especially in the evaporation test at 180 ° C. In particular in the preparation of microcapsule dispersions with high solids contents, very good tightness of the microcapsules is observed.
• the microcapsules according to the invention can be prepared by a so-called in situ polymerization.
• the principle of microcapsule formation is based on the fact that the monomers, free-radical initiator, optionally protective colloid and the core material to be encapsulated are used to prepare an oil-in-water emulsion in which the monomers and the core material are in the form of a disperse phase. This is usually done by preparing the oil phase from the individual components and dispersing the oil phase in the water phase. Subsequently, the polymerization of the monomers is initiated, generally by heating, and optionally controlled by further Temperature increase, wherein the resulting polymers form the capsule wall, which encloses the core material.
• This general principle is described, for example, in DE-A-10 139 171, to the contents of which reference is expressly made.
• the microcapsules are prepared in the presence of at least one organic and / or inorganic protective colloid.
• organic and inorganic protective colloids may be ionic or neutral.
• Protective colloids can be used both individually and in mixtures of several identically or differently charged protective colloids.
• Inorganic protective colloids are inorganic solid particles called Pickering systems.
• Pickering systems can consist of the solid particles alone or in addition of auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
• auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
• the mode of action and its use is described in EP-A-1 029 018 and EP-A-1 321 182, to the contents of which reference is expressly made.
• the inorganic solid particles may be metal salts, such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
• metal salts such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
• These include magnesium hydroxide, magnesium carbonate, magnesium oxide, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, titanium dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide.
• Silicates, bentonite, hydroxyapatite and hydrotalcites are also mentioned. Particular preference is given to SiO 2 -based silicas, magnesium pyrophosphate and tricalcium phosphate.
• Suitable SiO 2 -based protective colloids are finely divided silicic acids. They can be dispersed as fine, solid particles in water.
• colloidal dispersions of silica in water.
• colloidal dispersions are alkaline, aqueous mixtures of silica. In the alkaline pH range, the particles are swollen and stable in water.
• the pH of the oil-in-water emulsion is adjusted to pH 2 to 7 with an acid.
• Preferred colloidal dispersions of silica at pH 9.3 have a specific surface area in the range of 70 to 90 m 2 / g.
• SiO 2 -based protective colloids preference is given to highly disperse silicas whose average particle sizes are in the range from 40 to 150 nm at pH values in the range from 8 to 11. Examples include Levasil® ® 50/50 (HC Starck), Köstrosol ® 3550 (CWK Bad Köstritz), and Bindzil ® mentioned 50/80 (Akzo Nobel Chemicals).
• Organic protective colloids are preferably water-soluble polymers which lower the surface tension of the water from 73 mN / m to a maximum of 45 to 70 mN / m and thus ensure the formation of closed capsule walls and microcapsules with preferred particle sizes in the range of 0.5 to 50 microns, preferably 0.5 to 30 microns, in particular 0.5 to 10 microns, form.
• Organic anionic protective colloids are sodium alginate, polymethacrylic acid and its copolymers, the copolymers of sulfoethyl acrylate and methacrylate, sulfopropyl acrylate and methacrylate, N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid and vinylsulfonic acid.
• Preferred organic anionic protective colloids are naphthalenesulfonic acid and naphthalenesulfonic acid-formaldehyde condensates and above all polyacrylic acids and phenolsulfonic acid-formaldehyde condensates.
• Organic neutral protective colloids are, for example, cellulose derivatives such as hydroxyethylcellulose, methylhydroxyethylcellulose, methylcellulose and carboxymethylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, gum arabic, xanthan, casein, polyethylene glycols, polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and also methylhydroxypropylcellulose.
• Preferred organic neutral protective colloids are polyvinyl alcohol, partially hydrolyzed polyvinyl acetates and methylhydroxy (C 1 -C 4) -alkylcellulose and also their mixtures.
• Methylhydroxy- (C 1 -C 4) -alkylcellulose is to be understood as meaning methylhydroxy- (C 1 -C 4) -alkylcellulose of very different degrees of methylation, as well as degrees of alkoxylation.
• Methylhydroxy- (C 1 -C 4) -alkylcelluloses are prepared in known manner by two reaction steps.
• the alkoxylation of cellulose with alkylene oxides takes place in one step.
• the second step the methylation of existing hydroxyl groups with a methyl halide takes place.
• These two reactions usually take place in succession, but can also be carried out simultaneously.
• the degree of substitution of the cellulose varies.
• the average degree of substitution (DS) indicates how many hydroxyl units have been etherified on a dehydroglucose unit on average and can be from 0 to 3.
• the molar degree of substitution (MS) indicates the average number of alkoxy units per dehydroglucose unit, and can also be greater than 3 by the construction of side chains during the alkoxylation.
• the preferred methylhydroxy (C 1 -C 4) -alkylcelluloses have an average degree of substitution DS of 1.1 to 2.5 and a molar degree of substitution MS of 0.03 to 0.9.
• Suitable methylhydroxy (C 1 -C 4) -alkylcelluloses are, for example, methylhydroxyethylcellulose or methylhydroxypropylcellulose. Particularly preferred is methylhydroxypropylcellulose.
• methylhydroxy- (Ci-C4) of the company Hercules / Aqualon are -alkylcelluloses for example available under the tradename Culminal ®.
• Polyvinyl alcohol is obtainable by polymerizing vinyl acetate, optionally in the presence of comonomers, and hydrolysis of the polyvinyl acetate with elimination of the acetyl groups to form hydroxyl groups.
• the degree of hydrolysis of the polymers can be, for example, from 1 to 100% and is preferably in the range from 50 to 100%, in particular from 65 to 95%.
• partially hydrolyzed polyvinyl acetates are to be understood as meaning a degree of hydrolysis of ⁇ 50% and polyvinyl alcohol of> 50 to 100%.
• the preparation of homo- and copolymers of vinyl acetate and the hydrolysis of these polymers to form polymers containing vinyl alcohol units are well known.
• Vinyl alcohol units-containing polymers are sold, for example as Mowiol ® brands from Kuraray Specialties Europe (KSE).
• the microcapsules according to the invention are preferably prepared only with polyvinyl alcohol and / or partially hydrolyzed polyvinyl acetate and without the addition of further protective colloids.
• the protective colloids are used in amounts of from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the water phase.
• Organic protective colloids are preferably used in amounts of from 0.1 to 10% by weight, based on the water phase of the emulsion.
• polyvinyl alcohol or partially hydrolyzed polyvinyl acetate is used in a total amount of at least 3% by weight, preferably from 6 to 8% by weight, based on the microcapsules (without protective colloid). It is possible to add conventional protective colloids as mentioned in WO 2005/1 16559 in addition to the amount of polyvinyl alcohol or partially hydrolyzed polyvinyl acetate which is preferred according to the invention.
• Radical initiators for the free-radical polymerization reaction which can be used are the customary oil-soluble peroxo and azo compounds, advantageously in amounts of from 0.2 to 5% by weight, based on the weight of the monomers.
• Oil-soluble means that the radical starter is part of the oil phase of the oil-in-water emulsion and initiates the polymerization there.
• it can be fed as such, but preferably as a solution, emulsion or suspension, as a result of which, in particular, small amounts of radical initiator can be metered more precisely.
• Preferred free-radical initiators are tert-butyl peroxoneodecanoate, tert-amyl peroxy pivalate, dilauroyl peroxide, tert-amyl peroxy-2-ethylhexanoate, 2,2'-azobis (2,4-dimethyl) valeronitrile, 2,2'-benzyl peroxide Azobis (2-methylbutyronitrile), dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and cumene hydroperoxide.
• radical initiators are di (3,5,5-trimethylhexanoyl) peroxide, 4,4'-azobisisobutyronitrile, tert-butyl perpivalate and dimethyl 2,2-azobisisobutyrate. These have a half-life of 10 hours in a temperature range of 30 to 100 0 C.
• the polymerization is carried out at 20 to 100 0 C, preferably at 40 to 95 ° C.
• the oil-in-water emulsion is to be formed at a temperature at which the core material is liquid / oily. Accordingly, a free-radical initiator must be selected, whose decomposition temperature are carried out above this temperature, and the polymerization is also 2 to 50 0 C above this temperature, so that one optionally selected free radical initiator whose decomposition temperature is above the melting point of the hydrophobic core material.
• a common process variant for hydrophobic core material having a melting point up to about 60 0 C is a reaction temperature starting at 60 0 C, which is increased in the course of the reaction to 85 ° C.
• Advantageous free radical initiators have a 10-hour half life in the range of 45 to 65 ° C, such as t-butyl perpivalate.
• a temperature program is selected which starts at correspondingly higher reaction temperatures.
• free radical initiators having a 10 hour half life in the range of 70 to 90 ° C are preferred, such as t-butylper-2-ethylhexanoate.
• the polymerization is carried out at atmospheric pressure, but it is also possible at reduced or slightly elevated pressure z.
• the reaction times of the polymerization are normally 1 to 10 hours, usually 2 to 5 hours.
• aqueous microcapsule dispersions substantially free of odor carriers, such as residual monomers and other volatile organic constituents.
• This can be achieved physically in a manner known per se by distillative removal (in particular via steam distillation) or by stripping with an inert gas.
• distillative removal in particular via steam distillation
• stripping with an inert gas.
• it can be carried out chemically, as described in WO 99/24525, advantageously by redox-initiated polymerization, as described in DE-A 44 35 423, DE-A 44 19 518 and DE-A 44 35 422.
• microcapsules having a mean particle size in the range from 0.5 to 100 ⁇ m it being possible to adjust the particle size in a manner known per se by means of the shearing force, the stirring speed and its concentration.
• microcapsules having an average particle size in the range of 5 to 20 microns are preferred.
• Suitable materials of the capsule core are water-insoluble to essentially insoluble in water substances, which are referred to in the context of this application as "hydrophobic core material".
• Substantially insoluble in water is understood to mean a solubility of the core material in water of ⁇ 25 g / l, preferably ⁇ 5 g / l at 25 ° C. If the core material is a mixture, it may be in the form of a solution or suspension.
• Core materials having the above water solubility are preferably selected from the group comprising aliphatic and aromatic hydrocarbon compounds, saturated or unsaturated C ⁇ -Cso fatty acids, fatty alcohols, C ⁇ -Cso-fatty amines, C4-C3o-mono-, C4-C3o-di- and C4 C3o-polyester, primary, sec. Or tert.
• C4-C3o-carboxylic acid amides fatty acid esters, natural and synthetic waxes, halogenated hydrocarbons, natural oils, C3-C2o-ketones, C3-C2o-aldehydes, crosslinking agents, tackifier resins and tackifying resins, fragrances and flavorings, active ingredients, dyes, color formers, catalysts and inhibitors.
• Examples include:
• aliphatic hydrocarbon compounds such as saturated or unsaturated C 6 -C 40 -hydrocarbons, which are branched or linear, for example, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-penta- cosane, n-hexacosane, n-heptacosane, n-octacosane,
• aromatic hydrocarbon compounds such as benzene, naphthalene, biphenyl, o- or m-terphenyl, C 1 -C 4 -alkyl-substituted aromatic hydrocarbons such as dodecylbenzene, tetradecylbenzene, hexadecylbenzene, hexylnaphthalene, decylnaphthalene and diisopropylnaphthalene;
• C ⁇ -Cso fatty acids such as lauric, stearic, oleic or behenic acid, preferably eutectic mixtures of decanoic acid with e.g.
• fatty alcohols such as lauryl, stearyl, oleyl, myristyl, cetyl alcohol, mixtures such as coconut fatty alcohol and the so-called oxo alcohols, which are obtained by hydroformylation of ⁇ -olefins and further reactions;
• C 6 -C 30 fatty amines such as decylamine, dodecylamine, tetradecylamine or hexadecylamine;
• C 1 -C 20 -carboxylic acids such as propyl palmitate, methyl stearate or methyl palmitate, and preferably their eutectic mixtures or methyl cinnamate and prim., Sec. Or tert. C4-C3o carboxylic acid amides, such as octanoic acid dimethylamide and decanedioic acid dimethylamide;
• natural and synthetic waxes such as montanic acid waxes, montan ester waxes, carnauba wax, polyethylene wax, oxidized waxes, polyvinyl ether wax, ethylene vinyl acetate wax or Fischer-Tropsch wax waxes;
• halogenated hydrocarbons such as chlorinated paraffin, bromoctadecane, bromopentadecane, bromononadecane, bromeicosane, bromodocosane;
• adhesive resins and tackifying resins optionally as a solution in the above-mentioned core materials of groups a) to i), such as epoxy resins, epoxy-acrylate resin, polyolefin resins; Polyurethane prepolymers, silicone resins, natural and synthetic resins, for example hydrocarbon resins, modified rosin resins, pinene and terpene resins;
• fragrances and flavorings optionally as a mixture in the abovementioned core materials of groups a) to i) and j), as in WO 01/49817, or in "Flavors and Fragrances", Ullmann's Encyclopedia of Industrial Chemistry, Whiley-VCH, 2002, to which reference is expressly made;
• active substances such as biocides, active substances against endo- and ectoparasites, herbicides, fungicides, algicides, active substances against animal pests, e.g. Insecticides, acaricides, nematicides, molluscicides and miticidal agents, and safeners, optionally as a solution or suspension in the abovementioned core materials of groups a) to i) and j), as described in WO 2006/092409.
• active substances such as biocides, active substances against endo- and ectoparasites, herbicides, fungicides, algicides, active substances against animal pests, e.g. Insecticides, acaricides, nematicides, molluscicides and miticidal agents, and safeners, optionally as a solution or suspension in the abovementioned core materials of groups a) to i) and j), as described in WO 2006/092409.
• the substances of groups a) to h) are preferably of group a), provided they undergo a phase change, preferably a solid / liquid phase change, in the temperature range from -20 to 120 ° C., as phase-change materials (PCM), also known as Latent heat storage materials, suitable.
• PCM phase-change materials
• the latent heat storage materials are selected, as set forth in WO 2006/018130, to which reference is expressly made.
• mixtures of these substances are suitable as long as there is no melting point depression outside the desired range or the heat of fusion of the mixture becomes too low for a sensible application.
• soluble compounds may be added to the core materials in order to prevent the crystallization delay which sometimes occurs with the non-polar substances. It is advantageous to use, as described in US Pat. No. 5,456,852, compounds as an additive which have a melting point 20 to 120 K higher than the actual core substance. Suitable compounds are the fatty acids, fatty alcohols, fatty amides and aliphatic hydrocarbon compounds mentioned above as core materials. They are added in amounts of from 0.1 to 10% by weight, based on the capsule core.
• Preferred latent heat storage materials are aliphatic hydrocarbons so-called paraffins, particularly preferably pure n-alkanes, n-alkanes having a purity of greater than 80% or alkane mixtures, as obtained as a technical distillate and as such are commercially available.
• paraffins particularly preferably pure n-alkanes, n-alkanes having a purity of greater than 80% or alkane mixtures, as obtained as a technical distillate and as such are commercially available.
• aliphatic hydrocarbons having 14 to 20 carbon atoms and mixtures thereof are preferred.
• core materials are tackifier resins for two-component adhesives, crosslinkers for two-component adhesives, fragrances and flavorings, active ingredients, dyes and / or color formers, in each case optionally as a solution in the abovementioned core materials of groups a) to i) and j).
• the core material is particularly preferably a crosslinker for two-component adhesives or an adhesive resin for two-component adhesives.
• Preferred adhesive resins are, for example, epoxy resins and epoxy acrylate resins which are starting materials for reactive adhesives.
• Epoxy adhesive resins are in the book of CA. May “Epoxy resins” second edition, Marcel Dekker, Ine.
• Resins in particular those with an average molecular weight ⁇ 5000 g / mol. They are e.g. available under the name Araldite® from Huntsman International LLC.
• epoxy acrylate resins Preference is given to resins based on
• Glycidyl acrylates and methacrylates Preferred starting monomers for this resin are glycidyl acrylate and / or glycidyl methacrylate, acrylic esters, styrene and hydroxyalkyl acrylates. Such products are available under the name Joncryl® ADR from BASF Corp. available.
• Preferred crosslinkers k) are di- and polyfunctional amines having primary, secondary or tertiary amino groups which have a water solubility ⁇ 5 g / l at a temperature of 20 ° C., preferably.
• crosslinked k are diepoxides.
• the microcapsules according to the invention are suitable for copying paper, in cosmetics, for the encapsulation of adhesives, adhesive components, catalysts or in crop protection or generally for the encapsulation of biocides.
• the microcapsules according to the invention are particularly suitable for latent heat storage materials.
• microcapsules according to the invention can be processed directly as an aqueous microcapsule dispersion or in the form of a powder.
• the microcapsules according to the invention can optionally subsequently be isolated by spray drying.
• the spray drying of the microcapsule dispersion can be carried out in the usual way.
• the procedure is such that the inlet temperature of the hot air flow in the range of 100 to 200 0 C, preferably 120 to 160 0 C, and the outlet temperature of the hot air flow in the range of 30 to 90 0 C, preferably 60 to 80 0 C.
• the spraying of the aqueous polymer dispersion in the stream of hot air can take place, for example, by means of single-fluid or multi-fluid nozzles or via a rotating disk.
• the deposition of the polymer powder is usually carried out using cyclones or filter separators.
• the sprayed aqueous polymer dispersion and the stream of hot air are preferably conducted in parallel.
• spray-auxiliaries are added to the spray-drying to facilitate spray-drying or to set certain powder properties, e.g. Low dust, free-flowing or improved redispersibility.
• spraying aids are familiar to the person skilled in the art. Examples of this can be found in
• Advantageous spraying aids are, for example, water-soluble polymers of the polyvinyl alcohol or partially hydrolyzed polyvinyl acetates, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose , Methylhydroxy- ethylcellulose and methylhydroxypropylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, preferably polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and methylhydroxypropylcellulose.
• microcapsule dispersions according to the invention can be prepared with a high solids content.
• solids contents 50% by weight, preferably>
• microcapsule dispersions according to the invention also show an advantageous rheology behavior. So even the flowability improves under the action of shear forces.
• microcapsules according to the invention containing catalysts and / or inhibitors are suitable as core material in chemical synthesis or in polymerization.
• the microcapsules according to the invention are suitable for copying paper, in cosmetics, for the encapsulation of adhesives, adhesive components, catalysts or in crop protection or generally for the encapsulation of biocides.
• Microcapsules with core materials of group p) are suitable as crosslinkers in adhesives, paints, varnishes, paper coating slips or other coating or impregnating agents.
• microcapsules of the invention are useful with a capsule core material of the groups a) to h), provided that it is in the range from -20 to 100 0 C a solid / liquid phase change passes (PCM) material as a latent heat store.
• PCM solid / liquid phase change passes
• the fields of use of microencapsulated phase change materials are well known.
• the microcapsules according to the invention can advantageously be used for modifying fibers and textile products, for example of textile fabrics and nonwovens (eg nonwovens), etc.
• Application forms here are, in particular, microcapsule coatings, foams with microcapsules and microcapsule-modified textile fibers to call.
• the microcapsules are applied to a fabric together with a polymeric binder and optionally other excipients, usually as a dispersion.
• Typical textile binders are film-forming polymers having a glass transition temperature in the range of -45 to 45 ° C, preferably -30 to 12 ° C.
• the preparation of microcapsule coatings is described, for example, in WO 95/34609, to which reference is expressly made.
• the modification of foams with microcapsules is carried out in a similar manner as described in DE 981576T and US 5,955,188.
• the prefoamed substrate preferably a polyurethane or polyether, is surface-treated with a binder-containing microcapsule dispersion. Then the binder
• Microcapsule mixture by applying a vacuum in the open-pore foam structure in which the binder cures and binds the microcapsules to the substrate.
• Another processing option is the modification of the textile fibers themselves, e.g. by spinning from a melt or an aqueous dispersion as described in US 2002/0054964. Melt-spinning processes are used for nylon, polyester, polypropylene fibers and similar fibers, while the wet-spinning process is primarily used to produce acrylic fibers.
• binding materials with mineral, silicate or polymeric binders.
• a mineral shaped body is understood as meaning a shaped body which is formed from a mixture of a mineral binder, water, additives and, if appropriate, auxiliaries after shaping, in that the mineral binder / water mixture as a function of time, optionally under the effect of elevated temperature, substantiated.
• Mineral binders are well known. These are finely divided inorganic substances such as lime, gypsum, clay, loam and / or cement, which are converted into their ready-to-use form by mixing with water, the latter being left to oneself, in the air or else under water, if necessary when exposed to elevated temperature, solidify as a function of time.
• the aggregates are usually made of granular or fibrous natural or artificial rock (gravel, sand, glass or mineral fibers), in special cases also of metals or organic aggregates or of mixtures of said aggregate, with grain sizes or fiber lengths corresponding to the respective Use are adapted in a conventional manner.
• Suitable auxiliaries are, in particular, those substances which accelerate or retard the hardening or which influence the elasticity or porosity of the solidified mineral shaped body.
• microcapsules according to the invention are suitable for the modification of mineral binders (mortar-like preparations) containing a mineral binder. th consisting of 70 to 100 wt .-% cement and O to 30 wt .-% gypsum. This is especially true when cement is the sole mineral binder, the effect being independent of the type of cement. For further details, reference is made to DE-A 196 23 413.
• the dry compositions of mineral binders based on the amount of mineral binder, contain from 0.1 to 20% by weight of microcapsules.
• microcapsules of the invention can be used as an additive in mineral coating materials such as interior or exterior plaster.
• a plaster for the interior is usually composed of gypsum as a binder.
• Exterior coatings such as exterior facades or damp rooms may contain cement (cementitious plasters), lime or waterglass (mineral or silicate plasters) or plastic dispersions (synthetic resin plasters) as binders together with fillers and optionally coloring pigments.
• microcapsules according to the invention are suitable with PCM materials for the modification of plasterboard.
• PCM microencapsulated latent heat storage materials
• They are usually prepared by placing aqueous gypsum slurry discontinuously, or preferably continuously, between two topcoats, such as cellulose based paperboard sheets, thereby forming sheets.
• topcoats such as cellulose based paperboard sheets
• fibrous structures preferably glass fibers
• the alternative materials can be used as fabric and as so-called “nonwovens", ie as nonwoven structures.
• Such structural panels are known for example from US 4,810,569, US 4,195,110 and US 4,394,411.
• microcapsules according to the invention with PCM materials are suitable as an additive in polymeric or lignocellulose-containing moldings, such as chipboard or for polymeric coating compositions.
• inventive microcapsule dispersions are suitable with PCM materials as a heat transfer fluid.
• auxiliaries can be added to the microcapsule dispersions according to the invention.
• Auxiliaries may be, for example, slip additives, adhesion promoters, leveling agents, film-forming auxiliaries, flame retardants, corrosion inhibitors, waxes, siccatives, matting agents, deaerating agents, thickeners and water-soluble biocides.
• Substrates coated with microcapsule dispersions of this type are storage-stable, ie even after several weeks of storage time, the coated substrate can be processed with unchanged good results.
• the following examples are intended to explain the invention in more detail. The percentages in the examples are by weight unless otherwise specified.
• EO ethylene oxide units (ethylene glycol units)
• TDI 2,4-tolylene diisocyanate
• HDI hexamethylene diisocyanate
• TMP x 5.2 PO is understood to mean the reaction product of 1 mol of trimethylolpropane with 5.2 mol of propylene oxide.
• TMP x 3.6 EO for the reaction product of 1 mole of trimethylolpropane with 3.6 moles of ethylene oxide
• the molecular weight determination was carried out by gel permeation chromatography (GPC) using a refractometer as detector.
• THF was used as the mobile phase and polymethyl methacrylate (PMMA) compositions having molecular weights in the range from 200 to 217000 g / mol were used as the standard for determining the molecular weight.
• PMMA polymethyl methacrylate
• dimethylacetamide as the mobile phase
• the double bond content is determined by the iodine value (according to Kaufmann).
• the OH number (mg KOH / g) was determined on the basis of DIN 53240, Part 2.
• TMP x 5.2 PO 250 g were dissolved in 100 g of toluene in a 1 l four-necked flask with stirrer, dropping device, nitrogen line and internal thermometer. At room temperature, 202.5 g of TDI (1.162 mol) were added over a period of 15 min. After the addition, the reaction solution was stirred at 30 0 C until an NCO content of 7.3 wt .-% was reached. Over a period of 60 minutes, 105 g of hydroxyethyl acrylate (0.905 mol) were added until an NCO content of 0 wt .-% was reached.
• the ethanol was collected, weighed and the percentage of sales so determined over the theoretically possible full turnover. After reaching a conversion of 80 wt .-%, the reaction mixture was cooled to 100 0 C and adjusted by the addition of 85% phosphoric acid to a pH of 6. Subsequently, the reaction mixture was reheated to 160 ° C. and passed through dry nitrogen at this temperature over a period of 3 hours in order to remove remaining amounts of monomers. Thereafter, the batch was cooled to room temperature.
• the hyperbranched polycarbonate had an OH number of 133 mg KOH / g.
• the ethanol was collected, weighed and the percentage of sales so determined over the theoretically possible full turnover. After reaching a conversion of 80% (283 g of ethanol), the reaction mixture was cooled to 100 0 C and adjusted by addition of 85% phosphoric acid to a pH of 6. Subsequently, the reaction mixture was reheated to 160 0 C and passed through at this temperature over a period of 3 hours dry nitrogen to remove residual amounts of monomers remaining. Thereafter, the batch was cooled to room temperature.
• the hyperbranched polycarbonate had an OH number of 183 mg KOH / g.
• Double bond content (calculated from the amount of maleic anhydride used per batch): 2.2 mol / kg of polymer
• the particle size of the microcapsule powder was determined with a Malvern Particle Sizer Type 3600E according to a standard measuring method documented in the literature.
• the D [v, 0,1] value indicates that 10% of the particles have a particle size (by volume) up to this value.
• D [v, 0.5] means that 50% of the particles and D [v, 0.9] means that 90% of the particles have a particle size (by volume) less than or equal to this value.
• the span value results from the quotient of the difference D [v, 0,9] - D [v, 0,1]) and D [v, 0,5].
• the rheological measurements were carried out using a cylinder measuring system (CC 27) on an automatic sample changer (ASC) with a DSR 301 measuring head from Anton Paar. Viscosity was recorded as a function of shear rate in the range of 25 S- 1 to 500 S- 1 . In order to be able to make a statement about the time-dependent flow behavior of the samples, measurements were carried out from low to high shear rates and back to low shear rates.
• ASC automatic sample changer
• Feed 3 0.55 g of a 75% strength by weight solution of tert-butyl perpivalate in aliphatic hydrocarbons
• VE deionized water
• Feed 3 0.66 g of a 75% strength by weight solution of tert-butyl perpivalate in aliphatic hydrocarbons
• Example 7 The procedure was as in Example 7, with the difference that, 128.02 g of deionized water in the water phase was used.
• crosslinker 1 hyperbranched polyurethane with acrylate end groups
• Example 19 The procedure was analogous to Example 7, weighed, emulsified and polymerized, with the difference that 146.02 g of deionized water in the water phase and that crosslinker 4 were used.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Epidemiology (AREA)
• Dispersion Chemistry (AREA)
• Birds (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Cosmetics (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paper (AREA)
• Catching Or Destruction (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (1)

Applications Claiming Priority (3)

Publications (1)

Family

ID=43217176

Family Applications (1)

Country Status (7)

Families Citing this family (39)

Family Cites Families (60)

• 2010
  • 2010-06-11 AU AU2010261875A patent/AU2010261875B2/en not_active Expired - Fee Related
  • 2010-06-11 KR KR1020127001006A patent/KR20120046166A/ko not_active Application Discontinuation
  • 2010-06-11 JP JP2012515440A patent/JP5730295B2/ja not_active Expired - Fee Related
  • 2010-06-11 CN CN201080036255.3A patent/CN102458641B/zh not_active Expired - Fee Related
  • 2010-06-11 WO PCT/EP2010/058201 patent/WO2010145993A2/de active Application Filing
  • 2010-06-11 US US13/376,226 patent/US9056302B2/en not_active Expired - Fee Related
  • 2010-06-11 EP EP10725133A patent/EP2442901A2/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events