• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    process for the production of microcapsules. The application describes a process for producing microcapsules which contain a coating made of polyurea and which surrounds a water-insoluble oil in which the coating is obtained by the reaction of two structurally different diisocyanates in emulsion form.
    公开号:BR112012032634B1
    申请号:R112012032634-1
    申请日:2011-03-05
    公开日:2018-12-26
    发明作者:Wolfgang Denuell；Jutta Hotz
    申请人:Cognis Ip Management Gmbh；
    IPC主号:
    专利说明:

    “PROCESS FOR THE PRODUCTION OF MICROCapsules”
    The application refers to a process for the production of microcapsules.
    Microcapsules are powders or particles that consist of a core and a barrier material that surrounds the core, where the core is a solid, liquid or gaseous substance that is surrounded by solid, generally polymeric barrier material. They can be solid, that is, consist of a single material. The microcapsules have an average diameter of 1 to 1000 pm.
    A large number of coating materials are known for the production of microcapsules. The coating can consist of natural, semi-synthetic or synthetic materials. Natural coating materials are, for example, gum arabic, agar agar, agarose, matodextrin, alginic acid and its salts, for example, sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, Shellac gum, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysates, sucrose and waxes. Semi-synthetic coating materials are modified celluloses, in particular cellulose esters and cellulose ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and also starch derivatives, in particular starch ethers and starch esters. Synthetic coating materials are, for example, polymers, such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
    Depending on the type of coating material and the production process, microcapsules are formed, in each case, with different properties with regard to diameter, size distribution, physical and / or chemical properties.
    There is, therefore, a constant need to develop new production processes in order to be able to supply microcapsules with properties
    2/41 predefined.
    A first theme of the present application is therefore directed to a process for the production of microcapsules that contains a coating and a core made of a water-insoluble liquid material, where an aqueous solution of a protective colloid and a solution of a mixture of at least two bifunctional isocyanates (A) and (B), structurally different, in a water insoluble liquid, are put together until an emulsion is formed, to which at least one bifunctional amine is then added, and which is then heated to temperatures of at least 60 ° C until the formation of microcapsules, where isocyanate (B) is selected from anionically modified isocyanates or from isocyanates containing polyethylene oxide or mixtures of these types and isocyanate (A) does not has a charge, but is not an isocyanate containing polyethylene.
    The advantage of the process is that microcapsules of predetermined size or size distribution can be produced in a targeted manner, being possible to produce, in particular, relatively small microcapsules, with diameters from 10 to 60 pm. In addition, capsules with greater mechanical stability are obtained. In the particular case of obtaining these capsules, the coatings have only a low permeability in relation to liquid ingredients. In principle, an aqueous solution of a protective colloid is always produced and for this reason the isocyanates (A) and (B) are dissolved in the water-insoluble liquid, which later forms the nucleus of the microcapsules; the amine components are then added and the mixture is heated until the formation of the emulsion. The temperature for the reaction of isocyanates with the components of the amine should be at least 60 ° C, even better 70 ° C, but preferably 75 to 90 ° C, and in particular 85 to 90 ° C, to ensure that the reaction progresses quickly enough.
    3/41
    At this point it may be preferable to increase the temperature in stages (for example, in each case by 10 ° C) until, then, after completion of the reaction, the dispersion is cooled to room temperature (21 ° C). The reaction time typically depends on the quantities and temperatures used. However, generally, the elevated temperature to form the microcapsules is established between about 60 minutes to 6 hours or up to 8 hours.
    According to the present teaching, the addition of the amine preferably also happens with the supply of energy, for example, using a stirring apparatus.
    In order to form an emulsion in the present process, the respective mixtures are emulsified by processes known to the person skilled in the art, for example, by introducing energy into the mixture by stirring using a suitable stirrer until the mixture emulsifies. Preferably, the pH is adjusted using aqueous bases, preferably using the sodium hydroxide solution (for example, 5% by weight).
    It is essential for the process that at least two structurally different isocyanates (A) and (B) are used. These can be added in the process as a mixture, or separately from each other, to the premix (1) containing the protective colloid and then are emulsified and reacted with the amine. It is also conceivable to introduce both options, the mixture of (A) and (B) or the individual isocyanates, separately, at different times.
    In a preferred customization, the process is performed as follows:
    (a) A premix (I) of water and a protective colloid are prepared;
    (b) This premixture is adjusted to a pH in the range of 5 to 12;
    (c) An additional premix (II) is prepared from the liquid material
    4/41 insoluble in water, together with isocyanates (A) and (B);
    (d) The two premixes (I) and (II) are combined until an emulsion is formed and (e) The bifunctional amine is then introduced into the emulsion from step (d) and (f) The emulsion is then heated at temperatures of at least 60 ° C until microcapsules form.
    It may be advantageous to adjust the pH in step (b) to values from 8 to 12. Aqueous bases are most suitable, preferably aqueous sodium hydroxide solution. The formation of the emulsion in step (d), but also in step (e), is preferably guaranteed using a suitable agitator.
    Another equally preferred customization provides that:
    (a) A premix (I) of water and a protective colloid are prepared;
    (b) This premixture is adjusted to a pH in the range of 5 to 12;
    (c) An additional premix (II) is prepared from the water-insoluble material, which is liquid at 21 ° C, together with the isocyanate (A);
    (d) An emulsion is formed from premixes (I) and (II) by stirring and for this (e) A second isocyanate (B) is added, and then the pH of the emulsion is adjusted to a value of 5 to 10;
    (f) And then, the bifunctional amine is introduced into the emulsion from step (e) and (g) Then, it is heated to temperatures of at least 60 ° C until the formation of the microcapsules.
    In this procedure, the isocyanates (A) and (B) are added separately to the protective colloid, before the addition of the amine, and the microcapsule production reaction takes place. The formation of the emulsion - just like the mixture in step (e) also
    5/41 preferably occurs by using a stirring apparatus.
    The pH in step (e) is preferably adjusted to values from 7.5 to 9.0. For step (b), the value can also be adjusted from 8 to 12. For this purpose, the aqueous bases are more suitable, preferably, the aqueous sodium hydroxide solution.
    Microcapsules
    In the context of the present teaching, microcapsules have a coating made of a reaction product of at least two different bifunctional isocyanates with amines, preferably with polyamines. The reaction is a polycondensation between isocyanates and amines, which leads to a polyurea derivative.
    The microcapsules are present in the form of aqueous dispersions, the fraction by weight of these dispersions in the capsules being preferably between 15 and 45% by weight and preferably between 20 and 40% by weight. The microcapsules have an average diameter in the range of 1 to 500 pm and, preferably, from 1 to 50 pm or from 5 to 25 pm.
    The microcapsules have contents of liquid insoluble in water or solid, for example, an oil. The fraction of this oil can vary in the range of 10 to 95% by weight, based on the weight of the capsules, where fractions of 70 to 90% by weight can be advantageous. As a result of the process, capsules are obtained which typically have core / coating fractions (weight / weight) from 20: 1 to 1:10, preferably from 5: 1 to 2: 1 and, in particular, from 4: 1 to 3: 1.
    The microcapsules that are produced by the present process are preferably free of formaldehyde.
    Protective Colloid
    A protective colloid must be present during the reaction between the isocyanates and the
    6/41 amines. This protective colloid is preferably a polyvinylpyrrolidone (PVP). Protective colloids are systems of polymers that, in suspensions or dispersions, prevent the agglutination (agglomeration, coagulation, flocculation) of emulsified, suspended or dispersed substances. During solvation, protective colloids 5 bind large amounts of water and in aqueous solutions produce high viscosities depending on the concentration. Within the context of the process described here, the protective colloid may also have emulsifying properties. The aqueous protective colloid solution is preferably also prepared with stirring.
    The protective colloid may be, but does not have to be, a constituent of the capsule coating 10, with amounts of 0.1 to 15%, at most, by weight, but preferably in the range of 1 to 5% by weight and, in particular, from 1.5 to 3% by weight, based on the weight of the capsules.
    Isocyanates
    Isocyanates are N substituted organic derivatives (R-N = C = O) of isocyanic acid (HNCO), tautomeric in the free state, with cyanic acid. Organic isocyanates are compounds in which the isocyanate group (-N = C = O) is attached to an organic radical. Polyfunctional isocyanates are those compounds with two or more isocyanate groups in the molecule.
    According to the invention, at least bifunctional, preferably polyfunctional isocyanates are used, that is, all aromatic, alicyclic and aliphatic isocyanates are suitable, provided that they have at least two reactive isocyanate groups.
    Suitable polyfunctional isocyanates preferably contain, on average, 2 to 4, at most, NCO groups. Preference is given to the use of diisocyanates, that is, isocyanic acid esters with the general structure O = C = N-R-N = C = O, where R '
    7/41 is an aliphatic, alicyclic or aromatic radical.
    Suitable isocyanates are, for example, naphthalene 1,5-diisocyanate, diphenylmethane 4,4'-diisocyanate (MOI), hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylol diisocyanate (TMXDI), 4, Diphenyl 4'-diisocyanate, 5 dimethylmethane, di- and tetraalkyl diphenylmentan diisocyanate, dibenzyl 4,4'-diisocyanate, phenylene 1,3-diisocyanate, phenylene 1,4-diisocyanate, tolylene diisocyanate (TDI) isomers, optionally in a mixture, 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanate-2,2,4-trimethylhexane, 1,6-diisocyanate-2,4,4 trimethylhexane, 1-isocyanatomethyl-3-isocyanate-1,5 , 5-trimethylcyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanate-phenylperfluoroethane, 1,4-diisocyanate tetramethoxybutane, 1,4-diisocyanate butane, 1,6-diisocyanate hexane (HDI), diisocyanate dicycles Cyclohexane 4-diisocyanate, ethylene diisocyanate, bis-isocyanatoethyl phthalic acid ester, also poly socianates with reactive halogen atoms, such as 1-chloromethylphenyl 2,415 diisocyanate, 1-bromomethylphenyl 2,6-diisocyanate, 3,3-bis-chloromethyl 4,4'diphenyldiisocyanate. Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxy-diexyl sulfide. Also suitable are diisocyanates, trimethylhexamethylene diisocyanate, 1,4-diisocyanate-butane, 1,2-diisocyanatododecane and the fatty acid diisocyanate dimers.
    An essential feature of the present invention is the mandatory use of two structurally different isocyanates, (A) and (B).
    Suitable isocyanates of type (A) are at least bifunctional compounds (i.e. compounds containing at least two isocyanate groups -N = C = O).
    Typical representatives are hexamethylene diisocyanate (HDI), or derivatives
    8/41 of these, for example HDI biuret (commercially available, for example, as Desmodur N3200), HDI trimers (commercially available as Desmodur N3300) or dicyclohexylmethane diisocyanates (commercially available as Desmodur W). Toluene 2,4-diisocyanate or diphenylmethane diisocyanate are also suitable.
    The second isocyanate of type (B) is structurally different from the isocyanate of type (A) and, specifically, the isocyanate of type (B) must be either an anionically modified isocyanate or an isocyanate containing polyethylene oxide (or any desired mixtures of these two types of isocyanates).
    Anionically modified isocyanates are known per se. Preferably, these type (B) isocyanates contain at least two isocyanate groups in the molecule. Preferably, one or more sulfonic acid radicals are present as anionic groups. Preferably, the selected type (B) isocyanates are oligomers, especially trimers, of the 1,6-diisocyanate hexane (HDI). Commercial products of these modified isocyanates are known, for example, under the brand name Bayhydur (Bayer), for example, Bayhydur XP.
    Isocyanates containing polyethylene oxide (with at least two isocyanate groups) are also known and are described, for example, in US 5, 342, 556. Some of these isocyanates are self-emulsifying in water, which can be advantageous within the context of the present process, since there may not be a need for a separate step to carry out the emulsification.
    The weight ratio of the two isocyanates (A) and (B) is preferably adjusted in the range of 10: 1 to 1:10, but in particular, in the range of 5: 1 to 1: 5 and in particular , in the range of 3: 1 to 1: 1.
    It is also possible to use mixtures of different isocyanates of types (A) and (B). Beyond
    9/41 of the isocyanates (A) and (B), other isocyanates can also be additionally used in the process according to the invention.
    Preferably, however, only anionically modified isocyanates are used as component (B) in the present process.
    Amines
    At least bifunctional amines are used, but preferably polyethyleneimines (PEI) are used as an additional component in the process according to the invention. Polyethyleneimines are generally polymers, in which in the main chains there are NH groups that are separated from each other by two methylene groups:
    Polyethyleneimines belong to polyelectrolyte and complexing polymers. Short-chain linear polyethyleneimines with a high fraction of primary amino groups, that is, products of the general formula H 2 N fCH 2 -CH 2 -NH} n H (n = 2: 15 diethylenetriamine; n = 3; triethylenetetramine ; n = 4: tetraethylenepentamine) are sometimes called polyethyleneamines or polyalkylene polyamines.
    In the process according to the invention, polyethyleneimines with a molecular weight of at least 500 g / mol, preferably from 600 to 30,000 or 650 to 25,000 g / mol and, in particular, from 700 to 5,000 g / are preferably used mol or 20,850 to 2,500 g / mol.
    Protective Colloids
    In the process in accordance with the invention, PVP is used as a protective colloid. PVP is short for polyvinylpyrrolidones (also known as polyvivone). According to Rõmpp Chemie Lexikon, online edition 3.6, 2010, they
    10/41 are [oly (1-vinyl pyrrolidin-2-ones)], that is, polymers (vinyl polymers) that follow the general formula:
    Commercial polyvinylpyrrolidones have molar masses in the range of approximately 2,500 - 750,000 g / mol, which are characterized by the fact that they establish K values and present - depending on the K value - glass transition temperatures of 130 to 175 ° C. They are supplied as white, hygroscopic powders or as an aqueous solution.
    In processes in accordance with the invention, preference is given to the use of high molecular weight PVPs, that is, more than 400,000 g / mol and, preferably, from 500,000 g / mol to 2,000,000 g / mol. It is even more preferable that polyvinylpyrrolidones have a K value greater than 60, preferably greater than 75 and, in particular, greater than 80. A preferred range for the K value is between 65 and 90.
    Water-insoluble liquid material
    The microcapsules produced using the process described above contain a material that is preferably insoluble in water and liquid at 21 ° C (that is, at 21 ° C, a maximum of 10 g of the material can be dissolved in 1 liter) of water). This includes all types of water-insoluble hydrophobic liquids and some mixtures of these. Fragrances and perfumes are excluded from these materials.
    From now on, this material will be referred to as “oil”. In order for these oils to be used in the present process they must preferably be able to
    11/41 without auxiliaries, to dissolve isocyanates. If an oil does not guarantee adequate solubility of isocyanates, there is an option to overcome this disadvantage using suitable solubility promoters.
    In addition to the oils mentioned, microcapsules may also have ingredients, optionally liquid or solid, that are dissolved, dispersed or emulsified in the oil in the microcapsules.
    The word "oil" in the context of the present invention encompasses all types of oil or oil components, in particular vegetable oils, such as canola oil, sunflower oil, soybean oil, olive oil and so on. , modified vegetable oils, for example, alkoxylated sunflower or soy oil, synthetic (tri) glycerides, such as technical mixtures of mono, di and triglycerides of C6-C22 fatty acids, alkyl esters of fatty acids, for example, methyl or ethyl esters of vegetable oils (Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 12C-F, Agnique® ME1270, all products from Cognis GmbH, Germany), fatty acid alkyl esters based on the aforementioned C6C22 fatty acids, mineral oils and their mixtures. Examples that illustrate the nature of these suitable hydrophobic carriers, without limiting the invention to these examples, are: Guerbet alcohols based on fatty alcohols that have 6 to 18, preferably 8 to 10, carbon atoms, esters of acids C6-C22 linear fatty acids with C6-C22 linear or branched fatty alcohols or C6-C13 branched carboxylic acid esters with c6-C22 linear or branched fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate , myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate,
    12/41 stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl oleate, oleyl myristate, oil palmitate, oil stearate, oil stearate, oil stearate, oil isearate , oleyl oleate, oleyl behenate, oleyl erucate, behenila myristate, behenila palmitate, behenila stearate, behenila isostearate, behenila oleate, behenila behenate, behenila erucate, erucila myristate, erucila palmitate, erucila palmitate erucila, erucila isostearate, erucila oleate, erucila behenate and erucila erucate. Also suitable are C6-C22 linear fatty acid esters with branched alcohols, in particular 2-ethylhexanol, C18-C38 alkylhydroxy carboxylic acid esters with C6-C22 linear or branched fatty alcohols, in particular Dioctyl Maleate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimer-diol or trimer-triol) and / or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mixtures of mono , di, triglycerides based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols have 22 carbon atoms or polyols that have 2 to 10 carbon atoms and 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, carbonates of linear or branched fatty alcohol C6-C22, such as, for example, Dicaprilil carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having from 6 to 18, preferably from 8 to 10, atoms carbon, esters of benzoic acid with linear and / or branched C6-C22 alcohols, linear or branched dialkyl ethers, symmetrical or asymmetrical, having from 6 to 22 carbon atoms per alkyl group, such as, for example, dicarprilyl ether,
    13/41 products with an open ring of fatty acid esters epoxidized with polyols, silicone oils (cyclomethicone, degrees of silicone methicone, etc.), aliphatic or naphthenic hydrocarbons, such as, for example, squalene, squalene or dialkylcyclohexanes, and / or mineral oils.
    In the context of the present invention, the preferred oils are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, C6-C22 linear fatty acid esters with C6 linear or branched fatty alcohols -C22 or esters of C6-C13 branched carboxylic acids with linear or branched C6-C22 fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate , myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl stearate, isostearate stearyl, stearyl behenate, stearyl erucate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, ole oleyl act, oleyl behenate, oleyl erucate, behenila myristate, behenila palmitate, behenila stearate, behenila isostearate, behenila oleate, behenila behenate, behenila erucate, erucila myristate, erucyl palmitate, erucyl palmitate erucila, erucila isostearate, erucila oleate, erucila behenate and erucila erucate.
    Also preferred are oils from C6-C22 linear fatty acid esters with branched alcohols, in particular 2-ethylhexanol, C18-C38 alkylhydroxycarboxylic acid esters with C6-C22 branched fatty alcohols, C6-C22 linear or branched fatty alcohols particular dioctyl maleate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example,
    14/41 example, propylene glycol, dimer-diol or trimer-triol) and / or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mixtures of mono, di, triglycerides based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols that have to 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, C6-C22 linear or branched fatty alcohol carbonates, such as, for example, Dicaprilil carbonate (Cetiol® CC), 10 Guerbet carbonates, based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms, benzoic acid esters with C6-C22 linear and / or branched alcohols, (for example, Finsolv TM TN ), dialkyl ethers linear or branched, symmetrical or asymmetric, having 6 to 22 carbon atoms per alkyl group, such as, for example, dicarprilil ether (Cetiol TM OE), 15 products with an open ring of fatty acid esters epoxidized with polyols, oils silicone (cyclomethicone, types of silicone methicone, etc.), and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalene, squalene or dialkylcyclohexanes.
    Other suitable oils or oil constituents can be UV filter substances.
    Typical oil-soluble UV-B filters or broad-spectrum UV A / B filters, for example 3-benzylidene camphor or 3-benzylidene camphor and derivatives thereof, for example 3- (4-methylbenzylidene) -phorph, 3- (4'-trimethylammonium) benzylidene-bornan-2-one (Mexoryl SO), 3,3 '- (1,4-phenylenedimethine) bis (7,7-dimethyl-2oxo-bicyclo- [2.2.1 ] heptane-1-metasulfonic acid) and salts (Mexoryl SX), 3- (4'25 sulfo) benzylidene-bornan-2-one and salts (Mexoryl SL), the polymer of N - {(2 and 4) - [ 2
    15/41 oxoborn-3-ylidene) methyl} benzyl] acrylamide (Mexoryl SW), 2- (2H-benzotriazol-2-yl) -4methyl-6- (2-methyl-3- (1,3,3,3 -tetramethyl-1- (trimethylsilyloxy) disyloxanil) propyl) -phenol (Mexoryl SL), derivatives of 4-aminobenzoic acid, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-cyano (octocrylene) 3-phenylcinnamate; esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomentyl salicylate; benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'10 methyl-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; benzalmalonic acid esters, preferably di-2-ethylhexyl 4-methoxybenzalmalonate; triazine derivatives, such as, for example 2,4,6-trianilino (p-carbo-2'-ethyl-1'hexyloxy) -1,3,5-triazine and 2,4,6-tris [- ( 2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (Uvinul T 150) or bis (2-ethylhexyl) 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] 15 1,3,5-triazine-2,4-diyl) diimino] bis-benzoate (Uvasorb® HEB); 2,2- (methylene-bis (6- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (Tinosorb M); 2,4-bis [4- (2ethylhexyloxy) - 2-hydroxyphenyl] -6- (4-methoxyphenyl) -1,3,54riazine (Tinosorb S); propane-1,3diones, such as, for example 1- (4-tert-butylphenyl) -3- (4'- methoxyphenyl) -propane-1,3dione; derivatives of ketotriciclo (5,2,1,0) decane, dimethodethyl benzylmalonate 20 (Parsol SLX).
    In addition, linear and / or branched and / or saturated or unsaturated liquid hydrocarbons or any desired mixtures thereof can be used as oils within the context of the present invention. These hydrocarbons can be, for example, alkanes having from 4 to 22, preferably from 6 to 18 carbon atoms, or any desired mixtures thereof. Also suitable are
    16/41 unsaturated hydrocarbons having 4 to 22 carbon atoms, or unsaturated hydrocarbons with identical carbon number and any mixtures of these hydrocarbons. Cyclic and aromatic hydrocarbons, for example, toluene and mixtures thereof, can also be oils within the context of the present invention. Silicone oils are also suitable. Any desired mixtures of all specified core materials are also suitable.
    It is also possible for other liquids, preferably water-insoluble materials, to be used and to be present in microcapsules, such as thickeners, silicone defoamers, oil-soluble corrosion inhibitors, and similar additives, such as extreme pressure additives, deactivators yellow metal and so on, oil-soluble dyes or drugs, emollients, odor-absorbing compounds, oil-phase cosmetics, film-forming additives, pearls, vitamins, dyes, biocides. Any mixtures of these materials can also be present in the microcapsules. In cases where such a material is not soluble in oil, additives can be used to disperse or emulsify it. Many actives, such as biocides or dyes, are generally available only as mixtures with an oily solvent. These compositions are also usable in the context of the present invention. The use of biocides, emollients, dyes and UV filters are most preferred in the microcapsules of the present invention.
    Biocides
    A biocide is a chemical substance capable of killing different forms of living organisms and which are used in areas such as medicine, agriculture, forestry and mosquito control. Biocides are generally divided into two
    17/41 subgroups:
    • Pesticides, which include fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides and rodenticides, and • Antimicrobials, which include germicides, antibiotics, antibacterials, 5 antivirals, antifungals, antiprotozoans and antiparasites.
    Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, some types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as algaecide, 10 protecting water from algae infestation and growth.
    Pesticides: The United States Environmental Protection Agency (EPA) defines a pesticide as "any substance or mixture of substances designed to prevent, destroy, repel or mitigate any pest." A pesticide can be a chemical or biological agent (such as a virus or bacterium) used against pests, 15 including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (worms) and competing microbes with humans for food, they destroy properties, spread disease or are a nuisance. In the following examples, pesticides suitable for agrochemical compositions according to the present invention are presented.
    Fungicides: A fungicide is one of the three main methods of pest control in this case chemical control of the fungus. Fungicides are chemical compounds used to prevent the spread of fungus in gardens and crops. Fungicides are also used to fight fungal infections. Fungicides can be contact or systemic. A contact fungicide kills the fungus when sprayed on its surface. A systemic fungicide needs to be absorbed by the
    18/41 fungus before his death. Examples of suitable fungicides according to the present invention include the following species: (3-ethoxypropyl) mercury bromide, (2-methoxyethyl) mercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercurioxy ~ <quinoline, acibenzolar , acylamino acid fungicides, acypetacs, aldimorf, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, benoxysil, zoxoxil M, benodanil, benomyl, benquinox, bentaluron, bentiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursors, benzimidazole, benzimidazole, fungicides binapacril, biphenyl, bitertanol, bitionol, blasticidinS, Bordeaux mixture, boscalid , biphenyl bridge fungicides, bromuconazole, bupyrimate, Burgundy mixture, butiobate, butylamine, calcium polysulfide, captafol, captan, carbamate fungicides, carbamorf, carbanylate fungicides, carbendazim, carboxin, carpropamid, carvone, chompone mixture, quinone, Cheshunt mixture cloraniformetan, chloranil, chlorphenazole, chlorodinitronaftaleno, çloroneb, cloropicrin, clorotalonil, clorquinox, clozolinato, ciclopirox, climbazol, clotrimazol, conazole fungicides, conazole fungicides (conazole fungicides) copper (ll), basic, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper (ll) sulfate, copper sulfate, basic, zinc copper chromate, cresol, cufraneb, cuprobam, cuprous oxide, ciazofamid, ciclafuramid, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamid, cymoxanil, cipendazole, cyproconazole, ciprodinil, dazomet, DBCP, debacarb, decaf ntin, dehydroacetic acid, dicarboximide fungicides,
    19/41 diclofluanid, diclone, dichlorophen, dichlorophenyl, dicarboximide fungicides, diclozoline, diclobutrazol, diclocimet, diclomezine, dicloran, dietofencarb, diethyl pyrocarbonate, diphenoconazole, diflumetorim, dinophobon, dinethobromine, dinethomimim, dimethirimol , dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimphos, ditianon, dithiocarbamate fungicides, DNOC, dodemorf, dodicin, dodine, DONATODINE, drazoxolon, edifenphos, epoxiconazole, ethoxy, ethoxy, ethoxy, ethoxy , 3-dihydroxypropyl mercaptide, ethyl mercury acetate, ethyl mercury bromide, ethyl mercury chloride, ethyl mercury phosphate, etridiazole, famoxadone, 10 fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazol, fenfucil, fenfil, fenamilan , fenpropidin, fenpropimorf, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, formaldehyde, fosetil, fuberidazole, furalaxil, furametpir, furamide fungicides, 15 furanilide, furcarfuran, furcaranil, furcaranil, furcarol, furcarolil, furcarolil, furcarolil, furcarolil , gliodin, griseofulvin, guazatine, halachrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiophos, hydrargafen, himexazole, imazalil, imibenconazole, imidazole, inorganic, inorganic, fungicides, fungicides, fungicides, fungicides, fungicides iprovalicarb, isoprothiolane, isovaledione, kasugamicin, cresoxim-methyl, sulfocalcic, mancopper, mancozeb, maneb, mebenyl, mecarbinzid, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercury chloride, methiloxane, methiloxane, , metconazole, metasulfocarb, metifuroxam, methyl bromide, methyl isocyanate, methylmercury benzoate, methylmercury diciandiamide, methylmercury pentachlorophenoxide, metomin, metominostrobin,
    20/41 metrafenone, metsulfovax, milneb, morpholine fungicides, myclobutanil, miclozolin, N- (ethylmercury) -p-toluenesulfonanilide, nabam, natamicin, nitrostirene, nitrotalisopropil, nuarimol, OCH, fungicides, fungicides, fungicides, fungicides, organotin, orisastrobin, oxadixil, oxatiin fungicides, 5 oxazole fungicides, copper oxin, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencicuron, pentachlorophenol, pentiopyrad, phenylmercuriurea, phenylmercury sulfate, phenylmercury chloride, phenylmercury chloride , phenylmercury salicylate, phenylsulfamide fungicides, fosdifen, phthalide, phthalamide fungicides, picoxystrobin, piperalin, polycarbamate, polymeric 10 dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide fungicides, potassium azassium potassium, potassium azide , prochloraz, procymidone, propamocarb, propiconazole, prop ineb, proquinazid, protiocarb, protioconazole, piracarbolid, piraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitrile, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, 15 pyroxyuridines, quinroazurol, pyrimoxychlorides, quinroazurol, , quinone fungicides, quinoxaline fungicides, quinoxifen, quintozena, rabenzazole, salicylanilide, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomicin, sulfuricide, strobilur fungicides, sulfuricides, strobilur fungicides, sulfuricides, strobilur fungicides, TCMTB, tebuconazole, keyboardoftalam, technazene, weave, tetraconazole, thiabendazole, tiadifluor, thiazole fungicides, ticiofen, tifluzamide, tiocarbamato fungicides, thiochlorfenphim, thiomersal, thiophil, thiophil, thiophio, thiophio, thiophio tolnaftate, tolylfluanid, tolylm acetate ercurium, triadimefon, triadimenol, 25 triamiphos, triarimol, triazbutyl, triazine fungicides, triazole fungicides, triazoxide,
    21/41 tributyltin oxide, triclamide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforin, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, urea fungicides, validamicin, valinamide fungicides, vinclozolin, zinc, zinc ziram, zoxamide and mixtures thereof.
    Herbicides: A herbicide is a pesticide used to kill unwanted plants. Selective herbicides kill specific targets while leaving the desired crop relatively unscathed. Some act by interfering with the growth of weeds and are often based on plant hormones. The herbicides used to clean wasteland are not selective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and on lawns. They are applied in programs of total vegetation control (TVC), for the maintenance of highways and railways. Smaller amounts are used in forestry, grazing systems and management of reserved areas as a natural habitat for wildlife. The following are a number of suitable herbicides:
    * 2,4-D, a latifolicide herbicide in the phenoxy group used in lawn and in the production of no-till crops. Now used mainly in a mixture with other herbicides that act as synergistic agents, it is the most widely used herbicide in the world, the third most used in the United States. It is an example of synthetic auxin (plant hormone).
    * Atrazine, a triazine herbicide used in corn and sorghum to control leafy weeds and grasses. It is also used because of its low cost and because it acts as a synergistic agent when used with other herbicides, it is an inhibitor of photosystem II.
    * Clopiralid, is a broadleaf herbicide in the pyridine group, used mainly
    22/41 on turf, pasture and for the control of harmful thistles. Famous for his ability to subsist on composting. It is another example of synthetic auxin.
    * Dicamba, a persistent latifolicidal herbicide active in the soil, used in lawn and planting corn. It is another example of synthetic auxin.
    * Glyphosate, a non-selective systemic herbicite (kills any type of plant) used in no-till management and for weed control in crops that are generally modified to resist its effects. It is an example of an EPSPs inhibitor.
    * Imazapir, a non-selective herbicide used to control a wide range of weeds including annual and recurring terrestrial grasses and leafy herbs, woody species and riparian and emerging aquatic species.
    * Imazapic, a selective herbicide for pre and post-emergence control of some annual and recurring grasses and some leafy weeds. Imazapic kills plants by inhibiting the production of branched-chain amino acids (valine, leucine and isoleucine), which are necessary for protein synthesis and cell growth.
    * Metoalachlor, a pre-emergent herbicide widely used to control annual grasses in corn and sorghum; has largely replaced atrazine in these uses.
    * Paraquat, a non-selective contact herbicide used for no-till management and aerial destruction of marijuana and cocaine plantations. More toxic to people than any other herbicide in commercial use.
    * Picloram, a pyridine herbicide used primarily to control unwanted trees on pastures and field margins. It is another synthetic auxin.
    * Triclopir.
    23/41
    Insecticides: An insecticide is a pesticide used against insects in all forms of development. They include ovicides and larvicides used against eggs and insect larvae. Insecticides are used in agriculture, medicine, industry and domestically. The following are suitable insecticides:
    * Chlorinated insecticides such as, for example, Canfecloro, DDT, Hexachlorocyclohexane, gamma-Hexachlorocyclohexane, Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane, Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex and mixtures thereof;
    * Organophosphate compounds such as, for example, Acephate, Azinfomethyl,
    Bensulide, Chlorethoxyphos, Chlorpyrifos, Chlorpyrifos-methyl, Diazinon, Dichlorvos (DDVP), Dicrotofos, Dimetoato, Disulfoton, Etoprop, Fenamifos, Fenitrotion, Fention, Fostiazato, Melation, Metamidofos, Metidation. Methyl-paration, Mevinfos, Naled, Ometóato, Oxidemeton-methyl, Paration, Forato, Fosalona, Fosmet, Fostebupirim, Pirimiphos-methyl, Profenofos, Terbufos, tetrachlorvinfos, Tribufós, Triclorfon and mixtures thereof;
    * Carbamates, such as, for example, Aldicarb, Carbofuran, carbaryl, Metomyl, 2- (1-methylpropyl) phenyl methylcarbamate and mixtures thereof;
    * Pyrethroids such as, for example, Alletrin, Bifentrin, deltametrin, Permetrin, Resmetrin, Sumitrin, Tetrametrin, Tralometrin, transflutrin and mixtures thereof;
    * Compounds derived from plant toxins such as, for example, Derris (rotenone), Piretrum, Neen (Azadirachtin), Nicotine, Caffeine and mixtures.
    Rodenticides: Rodenticides belong to the category of pest control chemicals intended to kill rodents. It is difficult to kill rodents with poisons because their eating habits reflect their position as a butcher. They eat a small piece of something and hope, if they don't get sick, they continue to eat. a
    24/41 effective rodenticide must be tasteless and odorless in lethal concentrations and have a delayed effect. The following are examples for suitable rodenticides:
    * Anticoagulants are defined as chronic (death occurs after 1-2 weeks after ingestion of the lethal dose, rarely occurs before this period), single dose (second generation) or multiple dose (first generation) of cumulative rodenticides. Fatal internal bleeding is caused by the lethal dose of anticoagulants, such as brodifacoum, coumatetralil or warfarin. These substances in effective doses are antivitamin K, blocking the enzymes K1-2.3 epoxide reductase (this enzyme is blocked, preferably, by the 4-hydroxycoumarin / 4-hydroxytycoumarine derivatives) and k1-quinone reductase (this enzyme is blocked, preferably by the derivatives of indandione), depriving the organism of its source of active vitamin k1. This leads to a disruption of the vitamin K cycle, resulting in an inability to produce essential blood clotting factors (mainly coagulation factors II (prothrombin), VII (proconvertin), IX (Christmas factor) and X (Christmas factor) In addition to this specific metabolic disruption, the toxic doses of the anticoagulants 4-hydroxycoumarin / 4hydroxytyacoumarin and indandione cause damage to small blood vessels (capillaries), increasing their permeability, causing diffuse internal bleeding (bleeding). they develop over the course of days and are not accompanied by any nociceptive perceptions, such as pain or agony. In the final stage of intoxication the exhausted rodent collapses into hypovolemic circulatory shock or severe anemia and dies calmly. Raticidal anticoagulants are first generation agents (4-hydroxycoumarin type: Warfarin, cumatetralil; indandione type: Pindone, difacinone, chlorofacin ona), generally require higher concentrations (usually between 0.005 and 0.1%),
    25/41 consecutive ingestion over days in order to accumulate the lethal dose, present poor or inactive active after single ingestion and are less toxic than the second generation agents, which are derived from 4-hydroxycoumarin (difenacum, brodifacum, bromadiolone and flocumafen) or 4-hydroxy-1-benzothiin-2-one (4-hydroxy-1-thiacoumarin, sometimes incorrectly referred to as 4-hydroxy-1-thiocoumarin, see the ratio in heterocyclic compounds), ie difetialone. Second generation agents are far more toxic than first generation agents, they are generally applied in lower concentrations in baits (usually in the range of 0.001 - 0.005%), and are lethal after a single ingestion of the bait and are also effective against rodent strains that became resistant to first generation anticoagulants; thus, second generation anticoagulants are sometimes referred to as “super warfarins. Sometimes, anticoagulant rodenticides are enhanced by an antibiotic, more commonly by sulfaquinoxaline. The purpose of this association (eg warfarin 0.05% + sulfaquinoxaline 0.02%, or diphenacum 0.005% + sulfaquinoxaline 0.02% etc.) is that the antibiotic / bacteriostatic agent suppresses the symbiotic intestinal microflora that represents a vitamin source K. Thus, symbiotic bacteria are killed or their metabolism is weakened and vitamin K production is reduced, an effect that obviously contributes to the action of anticoagulants. Antibiotic agents other than sulfaquinoxaline can be used, for example, co-trimoxazole, tetracycline, neomycin or metronidazole. Another synergism used in rodenticide baits is an association of an anticoagulant with a compound with vitamin D activity, that is, cholecalciferol or ergocalciferol (see below). A typical formula used is, for example, warfarin 0.025 - 0.05% + cholecalciferol 0.01%. In some countries there are three fixed component rodenticides, ie anticoagulant +
    26/41 antibiotic + vitamin D, for example, 0.005% diphenacum + 0.02% sulfaquinoxaline + 0.01% cholecalciferol. Combinations of a second generation coagulant with an antibiotic and / or vitamin D are considered effective even against the most resistant rodent strains, although some second generation anticoagulants (ie brodifacul and difetialone), in the concentrations of 0.0025 - 0.005%, being so toxic that there is no record of any rodent strain that is resistant and even rodents resistant to any of the other derivatives are safely exterminated by the application of these more toxic coagulants.
    Vitamin K1 has been suggested and used successfully as an antidote for animals or humans who were accidentally or intentionally (animal poisoning attempts, suicide attempts) exposed to anticoagulant poisons. In addition, since some of these poisons work by inhibiting liver function and, in advanced stages of poisoning, many blood coagulation factors and the total volume of blood circulating are impaired, a blood transfusion (optionally with the coagulation factors can save the life of a person who inadvertently ingested these poisons, which is an advantage over older poisons.
    * Metal phosphides have been used as a way to kill rodents and are considered to be fast-acting rodenticides in a single dose (death usually occurs within 1 to 3 days after ingesting a single bait). A bait consisting of food and a phosphide (usually zinc phosphide) is left where the rodents can eat it. The acid in the rodent's digestive system reacts with the phosphide to generate the toxic phosphine gas. This method of controlling unwanted animals has possible use in places where rodents are resistant to any of the
    27/41 anticoagulants, particularly for the control of mice at home and in the field; zinc phosphide baits are also cheaper than second generation anticoagulants, so that sometimes, in cases of large rodent infestation, their population is initially reduced by abundant amounts of zinc phosphide bait application and the rest of the population that survived the initial poison is then eradicated by prolonged feeding with anticoagulant bait. Conversely, individual rodents that survived anticoagulant bait poisoning (the remaining population) can be eradicated by offering them non-toxic baits for a week or two (this is important to overcome the fear of the bait and make the rodents get used to eating in specific areas by offering them specific foods, especially when rats are eradicated) and subsequently applying poisoned bait of the same type that was used previously without poison, until all the bait consumption ceases (usually between 2 -4 days). These rodenticide methods that alternate different modes of action provide a de facto or almost 100% eradication of the rodent population in the area if the bait's acceptance / palatability is good (ie, rodents quickly feed on it).
    * Phosphides are very fast acting as rat poison, resulting in the fact that mice usually die in open areas instead of the affected buildings. Typical examples are aluminum phosphide (fumigant only), calcium phosphide (fumigant only), magnesium phosphide (fumigant only) and zinc phosphide (in baits). Zinc phosphide is typically added to rodent baits in amounts of about 0.75-2%. The baits have a strong odor, burning like garlic, characteristic for the phosphine released by hydrolysis. The odor attracts (or at least
    28/41 less, does not repel) rodents, but has a repulsive effect on other mammals; however, birds (notably wild turkeys) are not sensitive to smell and feed on baits, resulting in collateral damage.
    * Hypercalcemia. Calciferols (vitamins D), cholecalciferol (vitamin D3) and ergocalciferol (vitamin D2) are used as rodenticides, which are toxic to rodents for the same reason that they are beneficial to mammals: they will affect the homeostasis of calcium and phosphate in the body. D vitamins are essential in minimal amounts (a few IU per kilogram of body weight daily, which is only a fraction of a milligram) and, like most fat-soluble vitamins, they are toxic in larger doses, since they quickly result in what is called hypervitaminosis, which is, to put it simply, vitamin poisoning. If the poisoning is severe enough (that is, if the dose of the toxicant is high enough), death eventually occurs. In rodents that consume rodenticide bait, hypercalcemia occurs due to an increase in the level of calcium, mainly by increasing the absorption of calcium from the food, mobilization of the calcium fixed in the bone matrix to the ionized form (mainly cation calcium monohydrogencarbonate, partially linked to plasma proteins , [CaHCO3] +), which circulates dissolved in the blood plasma, and after ingestion of a lethal dose, the levels of free calcium are elevated sufficiently so that the blood vessels, kidneys, stomach wall and lungs are mineralized / calcified (formation of calcified, salt crystals / calcium complexes in the tissues, damaging them), then cause heart problems (the myocardium is sensitive to variations in free calcium levels that will affect both myocardial contractility and the spread of excitation between atria and ventricles ) and bleeding (due to capillary damage) and possibly insufficiency
    Renal 29/41. It is considered to be a single, or cumulative, dose (depending on the concentration used; the common bait concentration of 0.075% is lethal for most rodents after a single ingestion of larger portions of the bait), sub-chronic (death usually occurs days or one week after taking the bait). The applied concentrations, when used alone, are 0.075% cholecalciferol and 0.1% ergocalciferol. There is an important feature of calciferol toxicology, which is that they are synergistic with toxic anticoagulant substances. This means that the mixtures of anticoagulants and calciferols in the same bait are more toxic than the sum of the toxicities of the anticoagulant and calciferol in the bait, so that a huge hypercalcemic effect can be achieved by significantly lower calciferol content in the bait and vice -version. The most pronounced ancient / hemorrhagic effects are seen if calciferol is present. This synergy is used mainly in baits with low calciferol content because the effective concentrations of calciferols are more expensive than the effective concentrations of most anticoagulants. The first application of a calciferol in rodenticide bait was, in fact, the product of Sorex Sorexa® D (with a formula different from today's Sorexa® D) in the early 1970s, containing warfarin 0.025% + ergocalciferol 0, 1%. Currently, Sorexa® CD contains a combination of 0.0025% diphenacum + 0.075% cholecalciferol. Several other brands of products containing 0.075 - 0.1% calciferols alone are marketed (eg Quintox®, containing 0.075% cholecalciferol), or a combination of 0.01 - 0.075% calciferol with an anticoagulant.
    Acaricides, molluscicides and nematicides: Acaricides are pesticides that kill mites. All antibiotic acaricides, carbamate acaricides, formamidine acaricides, mite growth regulators, organochlorine acaricides,
    30/41 permethrin and organophosphates belong to this category. Molluscicides are pesticides used to control mollusks, such as moths, slugs and snails. These substances include metaldehyde, metiocarb and aluminum sulfate. A nematicide is a type of chemical pesticide used to kill parasitic nematodes (a worm phylum). A nematicide is obtained from a piece of the armagozeira seed; which is the residue from the seeds of the armagozeira after oil extraction. Armagozeira is known worldwide by several names, but it was first cultivated in India since antiquity.
    Antimicrobials: In the examples that follow, antimicrobials suitable for agrochemical compositions according to the present invention are presented. Microbial disinfectants frequently used are those that employ * Active chlorine (ie, hypochlorites, chloramines, dichloroisocyanurate and trichloroisocyanurate, chlorine, chlorine dioxide, etc.), * Active oxygen (peroxides such as peracetic acid, sodium persulfate, perborate sodium, sodium percarbonate and urea perhydrate), * sludge (povidone-iodine (povidone-iodine, betadine), Lugol's solution, iodine tincture, non-ionic iodinated surfactants), * concentrated alcohols (mainly ethanol, 1-propanol, also called n-propanol and 2-propanol, called isopropanol and mixtures of these, 2-phenoxyethanol and 1- and 2-phenoxypropanols are still used.
    * Phenolic substances (such as phenol (also called carbolic acid ”), cresols (called“ Lysol ”in combination with liquid potassium soaps), halogenated (chlorinated, brominated), phenols, such as hexachlorophene, triclosan, trichlorophenol, tribromophenol , pentachlorophenol, Dibromol and salts thereof), * Cationic surfactants, such as some quaternary ammonium cations (such as
    31/41 such as benzalkonium chloride, cetyl trimethylammonium bromide or chloride, didecyldimethylammonium chloride, cetylpyridinium chloride, benzethonium chloride) and others, non-quaternary compounds, such as chlorhexidine, glucoprotamine, octenidine, dihydrochloride, etc.), * Oxidants such as ozone and permanganate solutions;
    * Heavy metals and their salts, such as colloidal silver, silver nitrate, mercury chloride, phenylmercury salts, copper sulfate, copper oxide-chloride, etc. Heavy metals and their salts are the most toxic and environmentally dangerous bactericides and therefore, its use is strongly suppressed or prohibited;
    in addition, also * Strongly appropriately concentrated strong acids (phosphoric, nitric, sulfuric, amidosulfuric, toluenesulfonic acids) and * Alkali (sodium, potassium and calcium hydroxides) with pH <1 or> 13, particularly at not elevated temperatures (above 60 ° C) kill bacteria.
    As antiseptics (that is, germicidal agents that can be used on the human or animal body, skin, mucous membranes, wounds and the like), a few of the disinfectants mentioned above can be used under suitable conditions (mainly concentration, pH, temperature and toxicity in relation to man / animal). Among them, are important:
    * Some properly diluted chlorine preparations (eg Daquin's solution, 0.5% sodium or potassium hypochlorite solution, pH adjusted to 7-8, or 0.5-1% sodium benzenesulfochloramide solution (chloramine B) ), some * Iodine preparations, such as povidone iodine in various galenic forms (ointments, solutions, plaster for wounds), in the past also
    32/41
    Lugol.
    * Peroxides such as urea perhydrate solutions and peracetic acid solutions in buffer pH 0.1-0.25%, * Alcohols with or without antiseptic additives, used mainly for skin antisepsis, * Weak organic acids, such as sorbic acid , benzoic acid, lactic acid and salicylic acid * Some phenolic compounds, such as hexachlorophene, triclosan and Dibromol, and * Active cation compounds, such as benzalkonium 0.05 - 0.5%, chlorhexidine 0.5 - 4%, solutions octenidine 0.1 - 2%.
    Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics only slow their growth or reproduction. Penicillin is a bactericide, as are cephalosporins. Aminoglycoside antibiotics can act in a bactericidal way (breaking the cell wall precursor leading to lysis) or in a bacteriostatic way (binding to the 30S ribosomal subunit and reducing translation fidelity, which leads to an inaccurate protein synthesis). Other bactericidal antibiotics according to the present invention include fluoroquinolones, nitrofurans, vancomycin, monobactans, cotrimoxazole and metronidazole. Preferred biocides are selected from the group consisting of oxyfluorfen, glyphosate, tebucanozole, demedipham, fenmedipham, etofumesate and mixtures thereof.
    Emollients
    Microcapsules can also contain emollients. An emollient is a material that softens, soothes, feeds, coats, lubricates, moisturizes or cleanses the skin. An emollient usually accomplishes many of these goals, such as soothing, moisturizing and lubricating the skin. Suitable emollients are generally selected from
    33/41 of the oils described above. The emollients useful in the present invention can be petroleum based, fatty acid ester type, alkyl ethoxylate type, fatty acid ester ethoxylates, fatty alcohol type, polysiloxane type, or a mixture of these emollients.
    Dyes
    The microcapsules can also contain dyes, preferably some dyes suitable and approved for cosmetic purposes. Examples include cochineal red A (Cl 16255), patent blue V (Cl 42051), indigotine (Cl 73015), chlorophyllin (Cl 75810), quinoline yellow (Cl 47005), titanium dioxide (Cl 77891), blue indantreno RS (Cl 69800) and madder lake (Cl 58000). These dyes are normally used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
    In addition to the compounds mentioned above, the microcapsules of the present invention may also contain any desired mixtures of oils, as well as mixtures of oil and water in emulsified form. Any type of emulsion is possible (water in oil or oil in water, or various emulsions).
    For this purpose, emulsifiers are required: Microcapsules according to the present invention can also contain one or more emulsifiers. Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups: Products of the addition of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide in fatty alcohols 6-22 of straight chain , in 12-22 chain fatty acids, in alkyl phenols containing from 8 to 15 carbon atoms in the alkyl group and in alkylamines containing from 8 to 22 carbon atoms in the alkyl group; alkyl oligoglycosides containing 8 to 22 carbon atoms in the alkyl group and ethoxylated analogues thereof; addition products from 1 to
    34/41 mol of ethylene oxide in castor oil and / or hydrogenated castor oil; products for the addition of 15 to 60 mol of ethylene oxide in castor oil and / or hydrogenated castor oil; partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids containing from 12 to 22 carbon atoms and / or hydroxycarboxylic acids containing from 3 to 18 carbon atoms and products of these in 1 to 30 mol of ethylene oxide; partial esters of polyglycol (average degree of self-condensation from 2 to 8), polyethylene glycol (molecular weight 400 to 5,000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glycosides (eg methyl glycoside, glycosides butyl, lauryl glycoside) and polyglycosides (for example cellulose) with saturated and / or unsaturated, linear or branched fatty acids containing from 12 to 22 carbon atoms and / or hydroxycarboxylic acids containing from 3 to 18 carbon atoms and addition products of these in 1 to 30 mol of ethylene oxide; mixtures of pentaerythritol esters, fatty acids, citric acid and fatty alcohol and / or mixture of fatty acid esters containing 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol, mono, di and trialkyl phosphates and phosphates of mono-, di- and / or tri-PEG-alkyl and salts thereof, wool wax alcohols, polysiloxane / polyalkyl / polyether copolymers and the corresponding derivatives, block copolymers, for example, polyethylene glycol-30-polyhydroxystearate; polymer emulsifiers, for example, of Goodrich Pemulen types (TR-1, TR-2); polyalkylene glycol and glycerol carbonate and ethylene oxide addition products.
    It is also possible for the ingredients to migrate from the core of the microcapsules (ie the oil and / or other materials present in the core) into the coating. The invention further provides aqueous dispersions which comprise from 5 to 50% by weight, based on the total weight of the dispersion, preferably from 15 to 40% by weight, of
    35/41 microcapsules that can be produced by the above process. A preferred range is between 20 and 35% by weight. These aqueous dispersions are preferably obtained directly from the process described above.
    The microcapsule dispersions that are obtained by the present process can be used in a large number of different applications, depending on the type of oil. Preference is given to using microcapsules to finish all types of nonwovens, such as wipes (for example, wet or dry wipes for cosmetic or cleaning purposes), but also for finishing papers (including wallpapers, toilet paper or paper for books and newspapers), for finishing diapers or toilet papers and similar toilet products or textiles, for example, to finish papers or textiles with a dye or an insecticide, or in cosmetic compositions, for example example, to produce sunscreen compositions that comprise UV filter in the form of microcapsules. Another use belongs to the finishing of diapers or toilet papers and similar hygienic products. In addition, microcapsules can be used in massage oils or creams or personal lubricants, and suppositories, for example, to provide this product with anti-inflammatory actives.
    The present invention further provides fragrance-free microcapsules, preferably without formaldehyde, which contain a liquid core of a water-insoluble liquid or a hydrophobic material and a coating of a reaction product of at least two at least bifunctional and different isocyanates (A ) and (B), where the isocyanate (B) must be an anionically modified isocyanate or an isocyanate containing polyethylene oxide or mixtures of these types, and an amine at least bifunctional with the proviso that during the production of the microcapsules the ratio in weight between isocyanates (A) and (B) is in the range of 10: 1 to 1:10. Preferably,
    36/41 mentioned weight ratios can be adjusted where the ratio of 3: 1 to 1: 1 can be of particular importance.
    These microcapsules are preferably 1 to 50 pm in diameter and preferably 2 to 45 pm in diameter. The microcapsules can be present in the form of aqueous dispersions, where the fraction of the capsules can be from 1 to 90% by weight but, preferably, from 5 to 50% by weight.
    Examples
    Six microcapsule dispersions were produced using the process according to the invention. For comparison, a dispersion of microcapsules was prepared without the addition of an anionically modified isocyanate (B) and in each case the particle size of the capsules was determined.
    Determination of particle size
    The particle size determinations in the examples were carried out by means of static laser diffraction. The established values d50 and d90 were based on the volume distribution of the particles.
    Comparative example (without isocyanate type (B) - without being in agreement with the invention)
    Microcapsules were produced, as described below, using only one type of isocyanate (A): a premix (I) was prepared from 50 g of PVP K90 and 1160 g of water and the pH was adjusted to 10.0 using a aqueous sodium hydroxide solution (5% by weight). A premix II was prepared from 500 g of Myritol® 318 (caprylic / capric triglyceride) and 90 g of Desmodur® W (dicyclohexylmethane diisocyanate). The two premixes were combined and emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The emulsion pH was adjusted to 8.5 using a solution
    37/41 aqueous sodium hydroxide (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 40 g of Lupasol® PR8515 (polyethyleneimine) in 160 g of water was added over a period of 1 minute. The reaction mixture was then subjected to the following temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 34% non-volatile components and a particle size distribution according to the following values: d50 = 26 pm and d90 = 53 pm.
    Example 1:
    The microcapsules were prepared using two isocyanates of different types (A) and (B), as follows: a premix (I) was prepared from 50 g of PVP K90 and 1169 g of water and the pH was adjusted to 10.0 using an aqueous sodium hydroxide solution (5% by weight). A premix II was prepared from 500 g of Myritol® 318 (caprylic / capric triglyceride) and 58 g of Desmodur® W (dicyclohexylmethane diisocyanate) and 39 g of Bayhydur® XP 2547 (anionic HDI). These two premixes were combined and emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The pH of the emulsion was adjusted to 8.5 using aqueous sodium hydroxide solution (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 37 g of Lupasol® PR8515 (polyethyleneimine) in 147 g of water was added over a period of 1 minute. The reaction mixture was then subjected to the following temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60
    38/41 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 34% non-volatile components and a particle size distribution according to the following values: d50 = 6 pm and d90 = 10 pm.
    Example 2:
    The microcapsules were prepared using two isocyanates of different types (A) and (B), as follows: a premix (I) was prepared from 50 g of PVP K90 and 1169 g of water and the pH was adjusted to 10.0 using an aqueous sodium hydroxide solution (5% by weight). A premix II was prepared from 500 g of Myritol® 318 (caprylic / capric triglyceride) and 58 g of Desmodur® W (dicyclohexylmethane diisocyanate). These two premixes were combined and pre-emulsified by stirring. Then, 39 g of Bayhydur® XP 2547 (anionic HDI anionic oligomer) was added to this pre-emulsion and the mixture was emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The pH of the emulsion was adjusted to 8.5 using aqueous sodium hydroxide solution (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 37 g of Lupasol® PR8515 (polyethyleneimine) in 147 g of water was added over a period of 1 minute. The reaction mixture was then subjected to the following temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 34% non-volatile components and a particle size distribution according to the following values: d50 = 9 pm and d90 = 16 pm.
    Example 3:
    39/41
    The microcapsules were prepared using two isocyanates of different types (A) and (B), as follows: a premix (I) was prepared from 40 g of PVP K90 and 1146 g of water and the pH was adjusted to 10.0 using an aqueous sodium hydroxide solution (5% by weight). A premix II was prepared from 500g g of Myritol® 318 (caprylic / capric triglyceride) and 94 g of Desmodur® W (dicyclohexylmethane diisocyanate). These two premixes were combined and preemulsified by stirring. Then, 20 g of Bayhydur® XP 2655 (anionic HDI anionic oligomer) was added to this pre-emulsion and the mixture was emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The pH of the emulsion was adjusted to 8.5 using aqueous sodium hydroxide solution (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 80 g of Lupasol® G100 (polyethyleneimine) in 120 g of water was added over a period of 1 minute. The reaction mixture was then subjected to the following temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 35% non-volatile components and a particle size distribution according to the following values: d50 = 4 pm and d90 = 8 pm.
    Example 4:
    The microcapsules were prepared using two isocyanates of different types (A) and (B), as follows: a premix (I) was prepared from 50 g of PVP K90 and 1134 g of water and the pH was adjusted to 10.5 using an aqueous sodium hydroxide solution (5% by weight). A premix II from 300 g was prepared
    40/41 Eutanol® G (octyldodecanol), 300 g of Fitoderm (squalene) and 45 g of Desmodur® N3300 (HDI trimer). These two premixes were combined and pre-emulsified by stirring. Then, 31 g of Bayhydur® XP 2547 (anionic oligomer HDI) was added to this pre-emulsion and the mixture was emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The pH of the emulsion was adjusted to 8.7 using aqueous sodium hydroxide solution (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 28 g of Lupasol® PR8515 (polyethyleneimine) in 112 g of water was added over a period of 1 minute. The reaction mixture was then subjected to the following temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 38% non-volatile components and a particle size distribution according to the following values: d50 = 8 pm and d90 = 20 pm.
    Example 5:
    The microcapsules were prepared using two isocyanates of type (A) and type (B), as follows: a premix (I) was prepared from 50 g of PVP K90 and 1130 g of water and the pH was adjusted to 10.0 using an aqueous sodium hydroxide solution (5% by weight). A premix II was prepared from 500g g of Myritol® 318 (caprylic / capric triglyceride) and 50 g of Desmodur® W (dicyclohexylmethane diisocyanate), 50 g of Desmodur® N 3300 (HDI trimer) and 30 g of Bayhydur® XP 2547 (HDI anionic oligomer). These two premixes were combined and emulsified with the aid of a Mig stirrer for 30 minutes at room temperature at a speed of 1000 rpm. The pH of the emulsion was adjusted
    41/41 to 8.5 using aqueous sodium hydroxide solution (5% by weight). Then, at room temperature and with stirring at 1000 rpm, a solution of 38 g of Lupasol® FG (polyethyleneimine) in 152 g of water was added over a period of one minute. The reaction mixture was then subjected to the following 5 temperature program: heating to 60 ° C in 60 minutes, maintaining this temperature for 60 minutes, then 60 minutes at 70 ° C, 60 minutes at 80 ° C and, finally, 60 minutes at 85 ° C. The mixture was then cooled to room temperature, providing the desired microcapsule dispersion with a fraction of 33% non-volatile components and a particle size distribution according to the following 10 values: d50 = 8 pm and d90 = 14 pm .
    Example 6:
    The microcapsules were produced in a manner analogous to example 1 using, instead of 500 g of Myritol® 318, an oil comprising 350 g of Eusolex 2292 (octylmethoxycinnamate) and 150 g of Eusolex 9020 (butyl methoxydibenzoylmethane). This provided a desired dispersion of microcapsules with a fraction of 34% non-volatile components and a particle size distribution according to the following values: d50 = 4 pm and d90 = 20 pm.
    权利要求:
    Claims (17)
    [1]
    1. Production process of microcapsules containing a coating and a core of a water-insoluble liquid material characterized by the fact that in an aqueous solution of a protective colloid and a solution of a mixture of at least two difunctional diisocyanates structurally (A) and (B) in a water-insoluble liquid are combined until an emulsion is formed, which is then added with a difunctional amine and which is then heated to temperatures of a minimum of 60 ° C until the microcapsules are formed, in which the isocyanate (B) is selected from the anionically modified isocyanates and the isocyanate (A) has no charge and does not contain polyethylene oxide, with the proviso that during the production of the microcapsules the weight ratio between isocyanates (A ) and (B) is in the range of 10: 1 to 1:10.
    [2]
    2. Process, according to claim 1, characterized by the fact that a polyvinylpyrrolidone is used as a protective colloid.
    [3]
    Process according to claim 1 or 2, characterized in that the isocyanate (A) is chosen from the group consisting of hexane 1, 6-diisocyanate, hexane 1, 6-diisocyanate biuret or hexanol oligomers, 6 di-isocyanate, in particular its trimers or dicyclohexanomethylene diisocyanate.
    [4]
    Process according to claim 1, 2 or 3, characterized in that the isocyanate (B) is selected from the group of anionically modified diisocyanates that contain a minimum of a sulfonic acid group, such as an aminosulfonic acid group, in the molecule.
    [5]
    Process according to claim 1, 2, 3 or 4, characterized in that the difunctional amine used is a polyethyleneimine.
    [6]
    6. Process according to claim 1, 2, 3, 4 or 5, characterized by the fact that the weight ratio between isocyanates (A) and (B) is selected from 5: 1 to 1: 5 and in particular from 3: 1 to 1: 1.
    Petition 870180125412, of 9/3/2018, p. 12/17
    2/4
    [7]
    7. Process according to claim 1, 2, 3, 4, 5 or 6, characterized in that the core-coating ratio (w / w) of the microcapsules is selected from 20: 1 to 1:10, preferably from 5 : 1 to 2: 1 and, in particular, 4: 1 to 3: 1.
    [8]
    8. Process according to claim 1, 2, 3, 4 5, 6 or 7, characterized by the fact that:
    (a) a premix (I) is prepared from water and a protective colloid;
    (b) this premixture is adjusted to a pH in the range of 5 to 12;
    (c) another premix (II) is prepared from the water-insoluble liquid material together with the isocyanates (A) and (B);
    (d) the two premixes (I) and (II) are combined until an emulsion is formed; and (e) at least the bifunctional amine is then introduced into the emulsion from step (d); and (f) the emulsion is then heated to temperatures of 60 ° C until microcapsules are formed.
    [9]
    Process according to claim 8, characterized in that the pH in the process step (b) is adjusted to 8 to 12.
    [10]
    10. Process according to any of claims 1, 2, 3, 4, 5, 6, 7, 8 or 9, characterized by the fact that:
    (a) a premix (I) is prepared from water and a protective colloid;
    (b) this premixture is adjusted to a pH in the range of 5 to 12;
    (c) another premixture (II) is prepared from a water-insoluble material that is liquid at 21 ° C together with the isocyanate (A);
    Petition 870180125412, of 9/3/2018, p. 13/17
    3/4 (d) an emulsion is formed from the premixes (I) and (II) by stirring and for that;
    (e) the second isocyanate (B) is added, and then the pH of the emulsion is adjusted to a value of 5 to 10;
    (f) and then the amine at least the bifunctional amine is added to the emulsion from step (e); and (g) then heated to temperatures of at least 60 ° C until microcapsules are formed.
    [11]
    11. Process according to claim 10, characterized in that the pH in step (e) is adjusted to 7.5 to 9.0.
    [12]
    12. Perfume-free microcapsule comprising a liquid core of a water-insoluble liquid and a coating of a reaction product of at least two different difunctional isocyanates (A) and (B), (A) is unloaded and is not an isocyanate containing a polyethylene oxide and in which the isocyanate (B) must be an anionically modified isocyanate and a bifunctional amine, with the proviso that during the production of the microcapsules the weight ratio between the isocyanates (A) and (B) is in the range of 10: 1 to 1:10.
    [13]
    13. Microcapsule according to claim 12, characterized in that it has a diameter of 1 to 50 pm.
    [14]
    14. Microcapsule according to claim 12 or 13, characterized in that it is present in the form of an aqueous dispersion.
    [15]
    15. Microcapsule according to claim 12, 13 or 14, characterized in that it is free of formaldehyde.
    [16]
    16. Use of microcapsules according to claim 12, 13, 14 or 15, characterized in that they are used for finishing fabrics, papers or materials other than fabric.
    Petition 870180125412, of 9/3/2018, p. 14/17
    4/4
    [17]
    17. Use of microcapsules according to claim 12, 13, 14 or 15, characterized by the fact that they are in cosmetic, pharmaceutical, laundry and cleaning compositions.
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2628087T3|2017-08-01|Procedure to produce microcapsules
    CA2678656C|2016-06-14|Biocide compositions |
    AU2008217246B2|2012-12-20|Biocide compositions comprising at least one dialkylamide based on oleic or linoleic acid
    BRPI1005345B1|2017-06-13|Strengthening composition of sun protection factor
    ES2746271T3|2020-03-05|Process for the preparation of microcapsules that have a polyurea coating and a lipophilic core material
    BRPI0920497B1|2021-05-11|agricultural compositions
    US20110124505A1|2011-05-26|Agricultural Compositions
    EP2218328B1|2016-04-13|Oil-based agrochemical compositions with increased viscosity
    US20110224084A1|2011-09-15|Agricultural Compositions
    ES2831355T3|2021-06-08|Microcapsules comprising hydroxyalkyl cellulose
    WO2017085033A1|2017-05-26|Improvements in or relating to organic compounds
    同族专利:
    公开号 | 公开日
    EP2399667B1|2017-03-08|
    US20130095158A1|2013-04-18|
    CA2803420A1|2011-12-29|
    JP5934703B2|2016-06-15|
    CN102958597A|2013-03-06|
    WO2011160733A1|2011-12-29|
    RU2572889C2|2016-01-20|
    BR112012032634A2|2018-01-23|
    KR101925269B1|2018-12-05|
    CN102958597B|2015-05-13|
    RU2013101538A|2014-07-27|
    MX341671B|2016-08-30|
    KR20130121697A|2013-11-06|
    MX2012015042A|2013-06-28|
    EP2399667A1|2011-12-28|
    CA2803420C|2018-05-01|
    ES2628087T3|2017-08-01|
    JP2013537472A|2013-10-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3886085A|1971-08-31|1975-05-27|Fuji Photo Film Co Ltd|Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby|
    DE2312059C2|1972-03-15|1987-04-02|Stauffer Chemical Co., Westport, Conn., Us|
    US4280833A|1979-03-26|1981-07-28|Monsanto Company|Encapsulation by interfacial polycondensation, and aqueous herbicidal composition containing microcapsules produced thereby|
    US4643764A|1984-01-09|1987-02-17|Stauffer Chemical Company|Multiple types of microcapsules and their production|
    DE3685920D1|1985-09-13|1992-08-13|Ciba Geigy Ag|METHOD FOR PRODUCING MICROCAPSULES.|
    FR2591124B1|1985-12-10|1988-02-12|Rhone Poulenc Spec Chim|POLYADDITION-INTERFACIAL MICROENCAPSULATION PROCESS.|
    DE3771446D1|1986-10-23|1991-08-22|Ciba Geigy Ag|FIGHTING EKTOPARASITES.|
    FR2610537A1|1987-02-11|1988-08-12|Rhone Poulenc Chimie|IMPROVED MICROENCAPSULATION METHOD BY INTERFACIAL POLYADDITION|
    JP2929294B2|1989-05-30|1999-08-03|大日本インキ化学工業株式会社|Pigmented polyurethane polyurea particles and method for producing the same|
    US5011885A|1989-10-27|1991-04-30|The Mead Corporation|Methods for the production of microcapsules using functionalized isocyanate|
    US5225118A|1990-08-15|1993-07-06|Boise Cascade Corporation|Process for manufacturing polyurea microcapsules and product therefrom|
    DE4130743A1|1991-09-16|1993-03-18|Bayer Ag|MICROCAPSULES MADE FROM ISOCYANATES WITH GROUPS CONTAINING POLYETHYLENE OXIDE|
    PL186226B1|1993-11-15|2003-12-31|Zeneca Ltd|Microcapsules containing suspensions of biological active compounds|
    US5925595A|1997-09-05|1999-07-20|Monsanto Company|Microcapsules with readily adjustable release rates|
    US6653256B1|1999-08-24|2003-11-25|Bayer Aktiengesellschaft|Microcapsule formulations|
    MXPA02011951A|2000-06-05|2003-07-14|Syngenta Ltd|Novel microcapsules.|
    CA2311192A1|2000-06-12|2001-12-12|Harald D. H. Stover|Encapsulation process using isocyanate moieties|
    DE10117784A1|2001-04-10|2002-10-17|Bayer Ag|Microcapsule, for containing core of active substance especially plant protection agent, has shell of polyurethane or polyurea and is free of liquid|
    US6992047B2|2001-04-11|2006-01-31|Monsanto Technology Llc|Method of microencapsulating an agricultural active having a high melting point and uses for such materials|
    DE10156672A1|2001-11-17|2003-05-28|Creavis Tech & Innovation Gmbh|Process for the production of microcapsules|
    US20050271735A1|2002-05-31|2005-12-08|Stover Harald D H|Method of encapsulating hydrophobic organic molecules in polyurea capsules|
    CA2525263A1|2003-05-11|2004-11-18|Ben Gurion University Of The Negev Research And Development Authority|Encapsulated essential oils|
    GB0319071D0|2003-08-14|2003-09-17|Avecia Ltd|Catalyst and process|
    GB0526416D0|2005-12-23|2006-02-08|Syngenta Ltd|Formulation|
    GB0603501D0|2006-02-22|2006-04-05|Reaxa Ltd|Catalyst|
    US8143345B2|2007-12-06|2012-03-27|Prc Desoto International, Inc.|Water dispersible, hydroxyl-terminated, fluorinated polyurethanes and method of preparing the same|WO2013006661A2|2011-07-06|2013-01-10|President And Fellows Of Harvard College|Multiple emulsions and techniques for the formation of multiple emulsions|
    WO2014032920A1|2012-08-28|2014-03-06|Basf Se|Carrier system for fragrances|
    JP6143078B2|2013-05-13|2017-06-07|清水建設株式会社|Simulated powder manufacturing method and powder scattering state evaluation method|
    JP2014221012A|2013-05-13|2014-11-27|清水建設株式会社|Simulated powder, method for evaluating scattered state of powder, and powder handling facility|
    CN103933014B|2013-12-31|2016-03-09|杭州师范大学|A kind of tumor cell target drug-carrying microcapsule|
    GB2509431B|2014-03-26|2016-09-14|Rotam Agrochem Int Co Ltd|Herbicidal composition, a method for its preparation and the use thereof|
    WO2015165836A1|2014-04-29|2015-11-05|Basf Se|Process for producing microcapsules|
    RU2619331C2|2014-10-10|2017-05-15|Александр Александрович Кролевец|Method of producing nanocapsules of umifenovirin sodium alginate|
    US20170224849A1|2014-10-14|2017-08-10|President And Fellows Of Harvard College|Microcapsules and uses thereof|
    RU2599885C2|2014-11-05|2016-10-20|Александр Александрович Кролевец|Method for producing nanocapsules of umifenovirin carrageenan|
    MX2017004532A|2014-11-07|2017-06-28|Givaudan Sa|Improvements in or relating to organic compounds.|
    JP6883514B2|2014-11-07|2021-06-09|ジボダン エス エー|Capsule composition|
    ES2746271T3|2014-11-07|2020-03-05|Basf Se|Process for the preparation of microcapsules that have a polyurea coating and a lipophilic core material|
    EP3215103B1|2014-11-07|2020-08-19|Basf Se|Microcapsules comprising hydroxyalkyl cellulose|
    CN108348783B|2015-11-17|2021-05-14|荷兰联合利华有限公司|Clomibazole microcapsules and hair care compositions comprising surfactants and climbazole|
    WO2017085033A1|2015-11-18|2017-05-26|Basf Se|Improvements in or relating to organic compounds|
    EP3170552A1|2015-11-23|2017-05-24|Basf Se|Microcapsule comprising a polymeric shell and a hydrophilic or hydrophobic core material|
    EP3295929A1|2016-09-19|2018-03-21|S.P.C.M. Sa|Use of an ampholyte copolymer as colloidal stabilizer in a process of encapsulating fragrance|
    GB201615905D0|2016-09-19|2016-11-02|Givaudan Sa|Improvements in or relating to organic compounds|
    CN110121535A|2016-12-27|2019-08-13|富士胶片株式会社|Water dispersion and its manufacturing method and image forming method|
    CN107698865B|2017-09-14|2020-04-03|陕西理工大学|Preparation method of injection molding machine screw cleaning material|
    GB201804038D0|2018-03-14|2018-04-25|Givaudan Sa|Improvements in or realating to organic compounds|
    CN111867719A|2018-03-23|2020-10-30|富士胶片株式会社|Method for producing hollow particles, method for producing pore-forming material, method for producing cosmetic particles, and method for producing lightweight material|
    BR112020021624A2|2018-04-24|2021-01-26|Symrise Ag|core-shell capsules, product, process for producing said capsules and use of them|
    CN109231400B|2018-10-08|2021-09-21|华南理工大学|Suspended lignin microcapsule for treating water eutrophication and preparation method thereof|
    EP3845304A1|2019-12-30|2021-07-07|Bayer AG|Capsule suspension concentrates based on polyisocyanates and biodegradable amine based cross-linker|
    CN111226923A|2020-03-09|2020-06-05|上海生农生化制品股份有限公司|Pyraclostrobin-oxine-copper microcapsule suspension-suspending agent and preparation method thereof|
    GB202003883D0|2020-03-18|2020-05-06|Givaudan Sa|Consumer product|
    WO2021260017A1|2020-06-26|2021-12-30|Bayer Aktiengesellschaft|Aqueous capsule suspension concentrates comprising biodegradable ester groups|
    WO2022025133A1|2020-07-31|2022-02-03|森下仁丹株式会社|Microcapsule production method|
    WO2022028705A1|2020-08-06|2022-02-10|Symrise Ag|Method for producing microcapsules|
    法律状态:
    2018-06-05| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2018-11-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-12-26| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10167305.1A|EP2399667B1|2010-06-25|2010-06-25|Process for producing microcapsules|
    GB10167305.1|2010-06-25|
    PCT/EP2011/001098|WO2011160733A1|2010-06-25|2011-03-05|Process for producing microcapsules|
    [返回顶部]