Method for encapsulation of dissolved component of colored reactions of colored reaction system, capsules obtained, and their use in color reaction paper

FIELD: self-copy papers.

SUBSTANCE: group of inventions relate to use of microcapsules containing color reaction component. Color reaction component is first dissolved in solvent, namely vegetal oil C1-C8-alkyl ester, and to thus obtained solution a non-solvent is admixed at rapid stirring, said non-solvent not dissolving or dissolving insignificantly color reaction component and being taken in amount as to form supersaturated solution. The latter is directly emulsified in water phase at rapid stirring and, immediately after that, resulting emulsion is processed so that encapsulation takes place therein. Microcapsules obtained in this way are further described as well as their employment in color reaction paper.

EFFECT: improved writing quality and economic and environmental advantages.

33 cl, 1 dwg, 4 ex

 

The invention relates to a method of encapsulation of a solution of the color components of the reaction systems of color reactions in water emulsion, through the conventional method of microencapsulation and component color reactions are first dissolved in a solvent and the resulting solution with rapid stirring, add herstorical, which, if necessary, slightly dissolves the component color reactions, in a quantity sufficient to obtain a supersaturated solution, supersaturated solution directly emuleret in the water phase with rapid stirring, and then immediately spend encapsulation.

The method of the above type is known from the patent DE 3442268 C2. This method consists in the fact that supersaturated solutions of system components, non-ferrous reactions with a particularly high share of cheap herstories can be encapsulated without compromising image quality of systems of color reactions when later writing process. This strongly supersaturated solution component color reactions can be encapsulated, if such a solution immediately after its receipt undergo the process of emulsification and encapsulation before starts impede premature crystallization of the dissolved component of color reactions. If you receive so is m follows capsules used in the systems of color reactions, then color reactions that occur during the printing process, usually are without prejudice, and it is as if the capsules do not have any supersaturated system, just pure unsaturated system. The solvent or herstorical used at the same time, are biodegradable non-biodegradable. It would therefore be desirable to use biodegradable solvents, at least in a certain proportion, without compromising considered beneficial effects.

In the prior art already described method, according to which use, for example, a complex alkalemia esters of vegetable oil, and the question of saturation plays no role. Thus, patent EP 0593192 B1 relates to sensitive printing material for records registration of devices, and the chromogenic material is dissolved in ether complex. In the case of this complex ether it comes to mono-, di - or trifunctional complex ester of non-aromatic monocarboxylic acid containing a saturated or unsaturated unbranched or branched hydrocarbon chain with at least 5 carbon atoms in the chain, in addition to the carboxyl atom of carbon. There is a limitation that (a) the ester is not in a mixture with vegetable oil, (b) in the case of complex diapir he is not in a mixture with hydrocarbon (oil) oil and (C), the EU and ester includes metrpolitan, chromogenic composition consists essentially entirely of complex(s) ether(s), as indicated, and a chromogenic material.

In the patent EP 0520639 B1 describes sensitive printing transfer paper, and the solvent used for ceskobratrska component includes vegetable oil. Additionally it contains a mono - or difunctional ester of non-aromatic monocarboxylic acid, characterized by saturated or unsaturated, unbranched or branched hydrocarbon chain with at least 3 carbon atoms in the chain.

Patent DE 69504612 T2 is concerned, among other things, microcapsules for sensitive printing paper to the image, while hydrophobic chromogenic agent is dissolved in an organic solvent. This solvent may contain the mixture, which was obtained by the transesterification of vegetable oil. Emphasized that chemical conversion of vegetable oil, although it does not exclude impurities original oils and does not modify the fatty acid composition of these oils makes possible the creation of synthetic esters. Thus the costs of production must be further reduced by the same synthetic esters. It is a known solution also includes along with contaminated products of interesterification of vegetable oil used for the use of mineral oils, but in number, yet provide the full solution ceskobratrska component.

The objective of the invention was to improve the above-described prior art, so that he could become more economical, and could be obtained microcapsules, which when used in sensitive printing systems for image met the necessary requirements and are environmentally beneficial by binding capable of splitting vegetable oils or their derivatives.

According to the invention the task is solved in that the solvent used complex1-C8-alkilany ester of vegetable oil.

In the case of this complex With1-C8-Olkiluoto ether we are talking about complex ester with the so-called lower alkyl group with 1-8 carbon atoms. In particular, we are talking about the lower linear or branched alkyl residue with the number of carbon atoms from 1 to 8. Preferred alkyl residue, which is1-C6-especially With1-C4-group. Alkyl residues, in particular, arise from the esterification or interesterification of the corresponding vegetable oil by methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, so-butanol, isomers of pentanol and hexanol and/or 2-this is hexanol. Methyl ester of vegetable oil is particularly preferred within the framework of the invention, in particular the methyl ester of rapeseed oil, particularly its purified form.

In respect of vegetable oils, preterition to complex With1-C8-Olkiluoto ether, according to the invention there are no significant restrictions. It can be, for example, the dwarf oil palm, rapeseed oil, soybean oil, linseed oil, corn oil, palm oil, sunflower oil, olive oil, peanut oil, cottonseed oil, coconut oil, palm kernel oil, rapeseed oil, castor oil and wood oil.

Preferably, in the framework of the invention use complex With1-C8-alkilany ester of rapeseed oil. The rapeseed oil, according to the current situation in the market, there are two special varieties of rapeseed oil. This distinguishing characteristic is the content of erucic acid. Thus, there is rapeseed oil with a high content of erucic acid ("higt eruca acid rapeseed, HEAR") with special fatty acids, the essential part is erucic acid, while the other main part is in the form of fatty acids C18:1, C18:2 and C18:3, while the sample fatty acids of rapeseed oil with a lower with the holding erucic acid shows in this respect a clear shift in the direction of sample fatty acids, therefore erucic acid content of only less than one percent, and the above fatty acids C18:1 along with C18:2 and C18:3 are the main part. Regarding this, it is possible to refer to Michael Bockisch "Nahrungsfette und -öle", Handbuch der Lebensmittel-Technologie, Verlag Eugen Ulmer, 1993, str/211. The cultivation of both these varieties of canola in previous years has led to the so-called double zero or zero-zero-varieties containing both erucic acid and toxic glucosinolate still only in traces, while they were enriched in oleic acid. So, both of rapeseed oil can be brought in as raw material for complex alilovic esters used according to the invention, and in some cases, rapeseed oil, high erucic acid is preferred because it provides superior record. In some cases it appeared that the desired effect is achieved in particular if rapeseed oil, high erucic acid praeteritorum to complex With1-C8-Olkiluoto ester of vegetable oil and, accordingly, the use according to the invention. The desired effect is achieved in particular if the product of the method is free from impurities that are also valid for all other complex1-C8-alilovic esters of vegetable oils according to ISO is retenu. When talking about complex1-C8-Akilova the ester of vegetable oil, it should be underlined certain chemical species, regardless of how he actually made or received. Fundamentally it is possible to obtain complex1-C8-alkilany ester of vegetable oils according to the invention by transesterification of vegetable oil, as well as through the preparation of a mixture of suitable fatty acids and their esterification with suitable alcohols.

In the framework of the invention mentioned system component color reaction was transferred to a solution containing the specified complex1-C8-alkilany ester of vegetable oil. It may be the only solvent. However, in various cases, particularly preferably the solution additionally contains a different solvent, which is mentioned component color reactions dissolves better than complex1-C8-alkilany ester of vegetable oil, and is referred to as "solvent with good solubility". If you talk about "solvent with good solubility, this dissolving ability applies to each encapsulated component color reactions. If the component color of the reaction is dissolved in such a solvent in an amount which leads to dostaticcompression solution, which can capsulitis, then say, in the absence of complex1-C8-Olkiluoto ester of vegetable oil, certainly used according to the invention, the "good dissolving ability. This is true only for the definition of "good dissolving ability, as in the framework of this invention, the solvent is a good solvent capacity is not used alone, but only in connection with the described complex1-C8-alkylbis ester of vegetable oil.

If as a consequence along with certainly used according to the invention complex1-C8-alkylbis ester of vegetable oil use a solvent with good solubility", we usually must take into account that its dissolving ability, at least about 10% higher than that of the corresponding complex1-C8-Olkiluoto ester of vegetable oil in case the same ceskobratrska component, in particular more than 20%, and particularly preferably more than 30% (ceteris paribus).

Needless to say that each solvent in the resulting supersaturated system should also be inert in nature, that is, it cannot itself be chemically modified or changed accordingly dissolved chemical compound that is also applies to used according to the invention complex 1-C8-alkilany ester of vegetable oil. Thus, if necessary, to neglect the detected changes.

"Herstorical"used for the purposes of the invention, although in the above sense, and is inert, but not independently formed would be no sufficiently concentrated solution of each component color reactions, which should be dissolved. On the contrary, it was dissolved component would only slightly, for example, from about 0.01 to 3%, particularly from 0.1 to 0.3% or less than that on the concentration intended for encapsulation solution component color reactions almost irrelevant. This means, for example, in the case of a large number of well-known the actual pigment components, and their acidic components of color reactions, which are usually particularly well soluble in aromatic systems that non-polar aliphatic compounds fall under the concept of "herstorical"that these components of color reactions from a practical standpoint, it does not dissolve. As a result of this concept of "herstorical"and "solvent" in the form of a complex With1-C8-Olkiluoto ester of vegetable oil and solvent with good solubility" always should be considered, taking into account their solvent capable of being the industry in relation to dissolved compounds in the form of named components of color reactions. In each case related dissolving ability varies so clearly that from this point of view used here, the definitions are valid.

For these good solvents it is, in particular, aromatic solvents and/or chlorinated paraffins. These include, in particular, alkylated biphenyls, partially hydrogenated terphenyls, allrounda xylenes, as, for example, Cilicia, alkylated naphthalenes and alkyl residue preferably contains 3-10 carbon atoms, and in particular we are talking about ISO-propyl, diisopropyl, botulinum, Amelina, hexillion and/or 2-ethylhexyl residue. Are suitable alkylphenate, especially octylphthalate, and simple aromatic compounds as benzene, alkyl benzenes (e.g., methylbenzol, ethylbenzene, propylbenzene, isopropylbenzene, Livenza and hexylbenzoyl)and halogenases as chlorobenzene. As a non-aromatic compounds, which in the context of the invention represent a solvent with good solubility, in particular note chlorinated paraffins. Of particular importance among them are chlorinated unbranched paraffins with 6-18 carbon atoms and a degree of chlorination of from 20 to 60%.

In the framework of the invention can be used b lsoe number of nerastvorimaya for the corresponding system components of color reactions. This involves, in particular, non-aromatic solvents, starting materials or which occur in nature in large quantities and therefore are cheap, or get simple and therefore economical. To them in particular include aliphatic and cycloaliphatic compounds. Aliphatic and cycloaliphatic oil components play a special role, particularly crude petrol (gasoline) or its partial fractions in the form of petroleum ether, light petrol, naphtha (varnish gasoline), heavy gasoline, light oil (kerosene), i.e. the second main fraction of oil subjected to fractionated distillation, paraffin hydrocarbons containing 9 up to 20 carbon atoms, and gas oil (diesel oil, fuel oil) as a third main fraction distillation, consisting of paraffins with 12-18 carbon atoms and used in diesel engines or heating purposes. Also suitable gasoline from natural gas, representing a portion of the gasoline present in natural gas and removed from the gas by compression or by the absorption of oil.

The above-mentioned aliphatic fractions of crude oil come from oil, which mainly contains unbranched paraffins. Along with this, there is also the oil (as Soviet oil, heavy naphtha), which is worth up to 80% of cyclic hydrocarbons (naphthenes). Liquid naphthenic fractions can also be used preferably. These include as the most important representatives of the cyclopentane and cyclohexane, and their alkyl derivatives. Next we are talking about oil fractions of this oil, which in respect of its composition occupies a middle position between paraffinic and naphthenic oil.

When selecting quantitative proportions of herstories to the solvent of the invention has no significant limitations. This allows a technician to easily install this weight ratio, which allows carrying out the method according to the invention and receive valuable material of the capsules, which provides the solution of the problem described above. It is preferred that the solvent or mixture of solvents and herstorical, particularly in the form of a non-aromatic solvent is used in a weight ratio in which 1 weight. part of the solvent or mixture of solvents accounts for about 0.5 to 4 weight. part, in particular approximately 1-2,5 weight. part of herstories. For case, if you use a "good" solvent for the component system of color reactions in addition to the complex With1-C8-Olkiluoto ester of vegetable oil used according to the invention, preferably, if the weight. part of the good solvent accounts for about 0.1 to 9 weight. parts, in particular about 0.25 to 2 weight. part of a complex With1-C8-Olkiluoto ester of vegetable oil. In each case receive, as already repeatedly mentioned, eventually called supersaturated system and further treated according to the invention. At room temperature should be set presidenet at least 5%, preferably at least about 30%, and especially preferably more than about 50 wt.%. In the framework of the invention when carrying out the method, a manually-operated, it is possible to achieve the degree of saturation of more than about 60 wt.%, and in some cases more than 85 wt.%.

The method according to the invention is particularly preferred for encapsulation ceskobratrska component systems of color reactions, in particular in the papers for color reactions, in which case krasnobryzhyy component and the acidic component of color reactions spatially separated from each other on the surface of two different contiguous securities, or on the surface of a separate paper (autogenic paper). As a component of color reactions in systems of color reactions are especially mean the main actual pigment components. In particular the spine we are talking about the following compounds: dierenfield, as 3,3-bis-(p-dimethylaminophenyl)-6-dimethylaminophenyl (crystal violet lactone) and 3,3-bis-(p-dimethylaminophenyl)phtalic (malachite green lactone), lacarmina, as, for example, N-(2,5-dichlorophenyl)lakarin, N-benzoylamino, N-acetylamine or N-veniliornis, rhodamine-B-lactam, N-(p-nitrophenyl)rhodamine-B-lactam, policristalina as bis-(p-dimethylaminophenyl)methanol, crystal violet carbinol. Special economic importance the actual pigment components group fluorenol, particularly 2,7-di-N-substituted fluorine, amino or N-heterocyclic group which is substituted by (for the sake of completeness, should have mentioned that in the literature 3,7-position fluorolog fragment on the occasion also known as 2,6-position, depending on the item). Such fluorenone the actual pigment components are widely described in the literature, for example, in patent applications EP-A-276980, GB-B-1269601, GB-B-1374049, GB-B-2002801, GB-B-1182743. Further significant actual pigment components selected from the group of 3,1-benzoxazines as, for example, 2-phenyl-4-(4-diethylaminophenyl)-4-(4-methoxy-phenyl)-6-methyl-7-dimethylamino-4H-Benz,1-oxazin or their isomeric compounds. Also important are the benzo - and naftopererobniy. In this case we are talking about the so-called primary the actual pigment components that when desire is s color reactions can form the paint almost instantly through reaction with the acidic component of color reactions. Additionally can be used as secondary the actual pigment components, which color reactions proceed relatively slowly, and are opposed to the rapid fading of the color formed by using primary ceskobratrska component. This is particularly suitable N-benzoylacetonate blue and/or derived N-alquilerbarcelona.

In the technique of color reactions, in particular the technique of color reactions of the paper, in some cases it is preferable to capsulerebel dissolved component color reactions ceskobratrska component. For normal acidic components of color reactions in particular using an aromatic solvent. The components of the color reactions are acidic phenolic resins, in particular phenolaldehyde resins as phenol-formaldehyde resin. In the framework of the invention can also be encapsulated so-called "chelated" or "modified by zinc phenolic resin whose phenolic protons replaced by zinc. These phenolic resins are described, for example, in the application US-A-3732120. Especially when referring to compounds with acidic carboxyl group (also in the form of anhydride) as: polymers of finalization, polymers of maleic acid, partially or completely hydrolyzed copolymers of styrene and anhydride Malinov the th acid and copolymers of ethylene and maleic anhydride, carboxypolymethylene, and fully or partially hydrolyzed copolymer simple phenylmethylene ether and maleic anhydride, p-halogenfrei-formaldehyde resin, and resin type bisphenol A. in Addition, suitable in particular also acidic monomers of phenolic compounds, such as bis-(p-hydroxyphenyl)propane, naphthol derivatives, esters of p-hydroxybenzoic acid and salicylic acid derivatives.

The above acid components of color reactions of actual pigment components in the framework of the invention is particularly preferably suitable for the following the actual pigment components: crystal violet lactone, fluoran reacting to orange, red and olive-green or black, and connections benzenepropanal.

Also when choosing the method of encapsulation, the invention has no significant limitations. Thus, there can be used known methods of encapsulation, which, in General, provide a sufficiently rapid encapsulation svezheubrannoy rich mud system ceskobratrska component or the acid component of color reactions in the form of an emulsion. However, in General, the formation of the capsule's shell, if liquid, is completed within a few seconds to several minutes. Encapsulation can be the ü completed only for about 2 minutes. Subsequent events, such as the hardening of the capsule, likewise do not have to invent the critical value and can be significantly longer reaction time. Especially preferred within the invention is a method koatservatsii on the basis of gelatin, as well as the way the melamine-formaldehyde condensation. Likewise also suitable such conventional methods that are not based on the principle koatservatsii or condensation.

Suitable methods of encapsulation are explained in detail next. When the method koatservatsii receive, for example, heated to about 50°With an aqueous solution of an ionisable hydrophilic colloidal material (especially gelatin, gum Arabic, CMC, alginate or casein), and choose at least two electrically diametrically oppositely charged colloid. When using gelatin, on the one hand, and, for example, gum Arabic, on the other hand, has the same name electronegative ions colloids above the isoelectric point of gelatin (e.g., pH 8). Exposed capsulerebel solution ceskobratrska component emuleret in this aqueous colloidal solution, and the formed emulsion of the type oil-in-water. Then lower the pH value to approximately 3,8 while diluting the emulsion with water, by adding the heated to 50° With emulsions of highly diluted aqueous acetic acid or hydrochloric acid. When this happens electrophoretically recharge molecules gelatin interconnected with the separation of liquid koatservatnyh complex, forming the wall of the capsule. Upon cooling the mixture from the 50°6-8°begins With the gelatinization or hardening of the walls of the capsules. Additional chemical curing of the walls of the capsules by crosslinking gelatin by formaldehyde or glutaraldehyde leads to stable dispersions of capsules. This method is among others described in the application US-A-2800457. It can be used for encapsulation of the acid components of color reactions ceskobratrska component.

As already mentioned, there are also ways in which microcapsules are obtained by solution of a system component color reactions without koatservatsii, only by mixing the oily material is not miscible with water, a solution of at least one thermoplastic polymer and water. The water causes release of polymer from solution in the form of solid particles around the nucleus of these oily material. This method is described in the application US-A-3418250. Following the current methods of encapsulation that can be used within the scope of the invention described in application DE-A-2940786 and 2652875.

According to the method, Izv the STN from the application DE-A-2940786, use the condensation of melamine-formaldehyde precondensation and/or their simple1-C4-alilovic ethers in water, dispersive mainly water-insoluble material which later forms the core of the microcapsules. Condensation occurs in the presence of dissolved polymers containing negatively charged ionic group, at a pH of from 3 to 6.5 and at a temperature of from 20 to 100°C. a Special feature of this method lies in the fact that the dissolved polymer is a Homo - or copolymer having sulfonic acid group, which is not phenyl and/or sulfophenyl groups, and which has value To Fikentscher from 100 to 170, and a viscosity of from 200 to 500 MPa when the shift gradient 489-1(measured at 20 wt.%-nom solution at 20° (C), and add the melamine-formaldehyde precondensed as condensation continuously or in portions. This method is easily adjustable. So, it can be installed easily by a simple series of tests required, the optimum amount of water-soluble polymers. Similar encapsulation method based on the condensation reaction of the melamine-formaldehyde precondensation resins and/or their simple1-C4-alilovic esters, described in the patent DE-C1-3743427.

With the advantage can also be used in the framework of the invention, the method described in patentees-In-016366, special use of which relates to the production of microcapsules containing a solution ceskobratrska component. The solution ceskobratrska component in an organic solvent enclosed in a capsule from the product polyaddition special diisocyanate and diamine. First, under heating and under stirring suitable diisocyanate are added to a solution ceskobratrska component in the aromatic solvent. This organic phase is then transferred to an aqueous solution of polyvinyl alcohol and emuleret in ultrasonic pipe. With stirring, to this emulsion is added a dilute aqueous solution of an amine. The number of amine and isocyanate are in stoichiometric ratio. After addition of the amine for some time was stirred at room temperature and then at an elevated temperature.

The method according to the invention may be subjected to modifications for purely practical reasons relating to certain goals without compromising the achieved advantages. For the purposes of the invention can also be suitable for other, not the methods above, because they guarantee that more or less fresh supersaturated solution component system, color reactions, in particular in the paper for color reactions, decapsuling or cover shell for such a short in EMA, that will be completely eliminated unwanted premature crystallization of the dissolved component of color reactions before kapsulirovaniem. Typically, the length of time between the production of a supersaturated solution and the formation of individual droplets decapsulating environment since the beginning of the wrapping may be approximately from 1 to 60 seconds. Under optimal holding of the way this time may even be reduced, which is an advantage. Short-term holding method facilitates that conduct the mixing of source materials, on the one hand, may be more highly concentrated solution of the corresponding component color reactions and, on the other hand, his herstories, high-speed mixer, for example a stationary tubular mixer, placed directly before the initial emulsifying apparatus. Determining the time stage just how then would depend solely on the methods of encapsulation. Conventional encapsulation naturally provide a rapid way.

Technologically this invention can be explained as follows. Because of the rapid emulsification and subsequent kapsulirovaniem freshly prepared saturated solution of component color reactions, especially Krasko the shedding component of the paper for color reactions with a high proportion of herstories expected extensive crystallization process is carried out inside the capsule unnoticed. This could occur, for example, because the degree of formation of nuclei of crystallization inside capsules or on the inner walls of the capsules is not sufficient. On the other hand, it is likely that all the same, at least to some extent, the crystallization processes occur in microform, but they lead to a particularly fine crystalline or colloidal disperse precipitation of crystals, which practically corresponds to the molecular dispersion, and this dispersion state at a later practical use, for example, capsules containing solution ceskobratrska component in the paper for color reactions in the recording process, there is a negative impact. The above possible mechanism of action should not be mandatory. This could be explained by other mechanisms.

A special advantage of the invention lies in the fact that the share of herstories can be extremely high, even in some cases up to about 85 wt.% or more of the total system solution. This means that the price of the common system of solvents essentially determined cheap aristotelem. If encapsulation is carried out such system solution, you get the kapsa is s, which in terms of their suitability in systems of color reactions are relatively well-known capsules, obtained from supersaturated systems, at least, are equivalent. Thanks mandatory introduction complex1-C8-alilovic esters of vegetable oils according to the invention found the following advantage. Especially hard it is manifested in complex With1-C8-alilovic esters of rapeseed oil, preferably complex methyl ester of rapeseed oil. So, it turned out that the result of the image than the one used until now, systems are clearly improving. This, among other things, can be explained by the fact that the obtained capsules on the curve of the Gaussian distribution, show unexpectedly narrow distribution of particle sizes, particularly narrow and modal distribution curve. Because this increases the color intensity of the corresponding fingerprint with the similar systems of the gauge reactions, hence, if achieve equal intensity of color, the possibility of lowering the mass of microcapsules/m2that means economic benefits. So it turned out that regardless of the method of application (painting rollers, paint squeegee or device for coating irrigation) for a comparable provision of the image may be sat the warning ceskobratrska component from about 20% to 30% and in some cases even more.

In addition, the modal distribution leads to other advantages. So, unexpectedly high susceptibility to abrasion established for known systems, is greatly reduced through the elimination of exceeding the natural size of the microcapsules. Ineffective microcapsules with too small a diameter, in the region of about 1 μm, largely excluded that also means cost advantage. Too small microcapsules in General are useless, while the large are too high, the surface effects due to friction and manipulation. Therefore, it is always desirable to have a capsule that, when a narrow distribution of particle size (for example, the average particle diameter of about 4±1 μm, in particular about 4±0.5 µm) are completely modal. In addition, the Biodegradability is positively influenced by the inclusion of complex alilovic esters of vegetable oil. A special advantage of this invention is very significant energy savings when subjected to emulsification capsulerebel solution. Thus, the number of revolutions of the device for emulsification, comprising, as a rule, with the same size capsules 3700 rpm, in General can be reduced to about 3100 rpm, This corresponds to energy savings of about 30%. In addition it turned out that there is a significant reduction "removal ceskobratrska component. This can be understood as follows. Middle leaves with a color developer to the CF (coated front) (side coated) after printing, printing inks by the way, dry or wetted offset printing susceptible to removal ceskobratrska component. In a few days, for example 1-2 days, due to involuntary damaging the capsules released krasnobryzhyy component enters the roll printed from the middle of the list-NE - to medium sheet-CF-hand side of the next layer. Thus, by this invention there is a very substantial reduction of such effects. Thanks already considered the possibility of reducing the number ceskobratrska component of this phenomenon pickup ceskobratrska component is even less noticeable.

Further, the invention should be explained through various examples and the drawing. The drawing schematically illustrates the carrying out of the method according to the invention. If this describes encapsulation ceskobratrska component of the paper for color reactions. Accordingly, it is also valid for the encapsulation of acidic component color reactions ceskobratrska component.

In the drawing in the tank 1 is the solution of crystal violet lactone in a mixture of 30 parts by weight of Xili the xylene and 15 parts by weight of complex methyl ester of rapeseed oil, while dearomatizing kerosene (aliphatic or non-aromatic solvent) is in the vessel 2. In the vessel 3 is aqueous colloidal solution of gelatin, which later forms the material of the capsules. In the vessel 4 is the second colloidal component in the form of a solution of gum Arabic. The solution ceskobratrska component of the tank 1 is supplied via line 6 into the pump 13 metering system 29 system (dosing pumps). The dosing system 29 in addition to the pump 13 has other pumps 14, 15 and 16. Herstorical from the tank is fed by a pump 14 through line 7. Of the pumps 13 or 14 mentioned materials of the containers 1 and 2 on the lines 17 or 18 are in a static tube mixer 19. Tubular mixer 19 is a flow pipe. The performance of the pumps 13 and 14 is regulated so that the ratio of the mixture solution ceskobratrska component containing 30 weight parts of silicicola and 15 weight parts of a complex methyl ester of rapeseed oil to kerosene in svezheubrannoy solvent mixture is 1:1,22.

This mixture is next in line 20 serves static tube mixer 21. At the same time static tube mixer 21 through line 19 is fueled by the material for the walls of the capsules through the pump 14 metering system 28. While we are talking about a mixture of solutions of gelatin and gum Arabic from emkosti the 3 and 4 served on lines 8 and 9 and homogeneous mixing in the vessel 10. After that, the mixture mentioned manner is served on. A coarse emulsion is formed in a high-speed mixer 21, line 22 send in the device for fine emulsification 23 and line 25 into the tank for koatservatsii 27. At the same time required to bring koatservatsii additive from the tank 5 through line 11, pump 15 metering system 28 and line 24 in capacity for koatservatsii 27. When it comes to an aqueous solution of acid, which begins the coacervation. In capacity for koatservatsii 27 with a stirrer 26, driven by a motor 29, first formed the system in which the material for the walls of the capsules still liquid, but already there is a liquid shell droplets exposed capsulerebel. The time of formation of liquid membrane capsules is only a few seconds, for example 15 seconds. After leaving capacity for koatservatsii 27 through outlet 30 unloaded mass is then cooled from 50°With up to approximately 6-8°C. the Material for the walls of the capsules due to this cooling solidifies. To the walls of the formed capsules with a diameter of about 3 to 10 μm to give irreversible hardness obtained dispersion capsules utverjdayut in a known manner, for example, by using formalin solution. The device used for this cooling and Oteri is to be placed, on the above drawing is not given. Devices of this kind are known.

The following examples show formulations encapsulated supersaturated solutions of system components, non-ferrous reactions according to the invention.

Example 1

Compounding oil for encapsulation
The crystal violet lactone1.9 wt.%
9-N-butyl-carbazolyl-(3)-4',4″-bis-(N-methyl-N-phenylamino)-difenilmetana0.7 wt.%
Monoisopropylamineto 17.4 wt.%
Methyl ester of rapeseed oil20.0 wt.%
Dearomatizing keroseneby 60.0 wt.%
100.0 wt.%

Example 2

Compounding oil for encapsulation
The crystal violet lactoneof 0.94 wt.%
6-(N-ethyl-N-p-tolylamino)-2-methyl-fluoran0.45 wt.%
1,3-dimethyl-6-diethylamino-fluoranof 0.56 wt.%
2 dibenzylamino-6-diethylamino-fluoran0.85 wt.%
2 phenylamino-3-methyl-6-diethylamino-fluoran2,Wes.%
Mix the actual pigment components that react to black4,80 wt.%
Chloroparaffin10,00 wt.%
Methyl ester of rapeseed oil30.2 wt.%
Dearomatizing kerosene, rich in naphthenes55,00 wt.%
100.0 wt.%

Example 3

Compounding oil for encapsulation
Mix the actual pigment components
reacting to the black color example 24,80 wt.%
Diisopropylnaphthalene15.0 wt.%
Methyl ester of rapeseed oil20.0 wt.%
Aliphatic hydrocarbon oil, purifieda 60.2 wt.%
100.0 wt.%

Example 4

Compounding oil for encapsulation
The crystal violet lactoneof 0.68 wt.%
6 diethylamino-2-carboxitherapy ester of fluorine0.40 wt.%
6-(N-ethyl-N-p-tolylamino)-2-methylfluorene 0.32 wt.%
6-dimethylamino-2-dibenzylamino-fluorento 0.60 wt.%
6 diethylamino-2-phenylamino-3-methyl-fluoranof 1.40 wt.%
Mix the actual pigment components that react to black3,40 wt.%
Methyl ester of rapeseed oil40.0 wt.%
Dearomatizing purified kerosene56,60 wt.%
Decapsulating solution ceskobratrska component100.0 wt.%

1. The method of encapsulation of a solution component color reaction system color reactions in water emulsion, by obtaining microcapsules, and the component of color reactions are first dissolved in a solvent and the resulting solution with rapid stirring, add herstorical, which in any case is slightly dissolves the component color reactions in number, forming a supersaturated solution, supersaturated solution directly with rapid stirring emuleret in the aqueous phase, and then immediately spend encapsulation, characterized in that the solvent used complex1-C8-alkilany ester of vegetable oil.

2. The method according to claim 1, characterized in that as the 1-C8-Olkiluoto ester of vegetable oil using methyl ester of vegetable oil.

3. The method according to claim 2, characterized in that as difficult methyl ester of vegetable oil using methyl ester of rapeseed oil, obtained in particular from rapeseed oil, enriched erucic acid.

4. The method according to claim 3, characterized in that the methyl ester of rapeseed oil used in purified form.

5. The method according to claim 1, characterized in that additionally they use a good solvent, which dissolves the color component of the reaction system of color reactions better than complex1-C8-alkilany ester of vegetable oil.

6. The method according to claim 5, characterized in that as a good solvent with the best dissolving capacity use of aromatic solvents and/or chlorinated paraffins.

7. The method according to claim 6, characterized in that the aromatic solvent used alkylated biphenyls, alkylated naphthalenes, alkylated terphenyls, allrounda xylenes and/or diarylamino connection.

8. The method according to claim 1, characterized in that as herstories use non-aromatic solvent.

9. The method according to claim 8, characterized in that as a non-aromatic solvent use alifaticheskii/or cycloaliphatic hydrocarbon.

10. The method according to claim 5, characterized in that at 1 weight. part of the solvent or mixture of solvents is approximately 0.5-4 parts, especially about 1-2,5 parts of herstories.

11. The method according to claim 6, characterized in that parts 1 good solvent accounts for about 0.1 to 9 parts, in particular about 0.25 to 2 parts of a complex With1-C8-Olkiluoto ester of vegetable oil.

12. The method according to claim 11, characterized in that as component of the system of color reactions capsulebuy main krasnobryzhyy component.

13. The method according to item 12, characterized in that as the main ceskobratrska use component derived lactone, derived fluorine, derived phthalide derived difenilmetana, derived triphenylmethane, derived oxazine and/or derived spiropyran.

14. The method according to item 12, characterized in that it further as ceskobratrska component using N-benzoylacetonate blue and/or derived N-alquilerbarcelona.

15. The method according to item 12, wherein capsulebuy acid component of the color reactions of the main ceskobratrska component.

16. The method according to item 15, characterized in that the acid component of color reactions capsulebuy acidic phenolic compound and/or a modified zinc derivative of salicylic acid and/or acid activated clay minerals.

17. The method according to claims 1 to 16, characterized in that the encapsulation used method koatservatsii.

18. Microcapsules for sensitive printing systems, color reactions, obtained by the method, at least one of the preceding claims 1 to 17, characterized in that the corresponding component color reactions is inside the microcapsules in a supersaturated system, containing, along with nerastvorim complex1-C8-alkilany ester of vegetable oil as a solvent.

19. Microcapsules according p, characterized in that one weight part of the solvent or mixture of solvents is approximately 0.5-4 parts, in particular of about 1-2,5 parts of herstories.

20. Microcapsules according p, characterized in that the complex With1-C8-alkilany ester of vegetable oil is a complex methyl ester of vegetable oil, in particular in the form of complex methyl ester of rapeseed oil.

21. Microcapsules according p, wherein the supersaturated system additionally contains a good solvent, which dissolves the component color reactions better than complex1-C8-alkilany ester of vegetable oil.

22. Microcapsules according to item 21, wherein the 1 parts of a good solvent accounts for about 0.1 to 9 parts, in particular about 0.25 to 2 parts of a complex With1-C8-alkylboron the Fira vegetable oil.

23. Microcapsules according to item 21, wherein the good solvent is present in the form of an aromatic solvent and/or chlorinated paraffin.

24. Microcapsules according to item 23, wherein the aromatic solvent is in the form of alkyl biphenyls, alkyl naftalina, alkyl terphenyls, ALLROUNDER of xylenes and/or diarylamino connections.

25. Microcapsules according p, characterized in that herstorical is in the form of a non-aromatic solvent, in particular in the form of aliphatic and/or cycloaliphatic hydrocarbon.

26. Microcapsules according p, characterized in that as component of color reactions encapsulated basically krasnobryzhyy component.

27. Microcapsules according p, characterized in that as the main ceskobratrska component encapsulated derived lactone, derived fluorine, derived phthalide derived difenilmetana, derived triphenylmethane, derived oxazine and/or derived spiropyran.

28. Microcapsules according p, characterized in that the encapsulated acid component reactions of the main ceskobratrska system component color reactions.

29. Microcapsules according p, characterized in that as the acid component reactions encapsulated: acidic phenolic compounds, Modific the automatic zinc derivative of salicylic acid, and/or acid activated clay minerals.

30. Microcapsules according p, characterized in that at room temperature (20° (C) degree of saturation encapsulated system is at least 5%, particularly at least about 30%.

31. Microcapsules according to item 30, wherein presidenet is more than 50 wt.%, in particular more than about 60 wt.%.

32. Microcapsules on one of p-31, characterized in that the average particle diameter of approximately from 3 to 5, particularly from about 3.5 to 4.5 microns.

33. Microcapsules of at least one of p-32, with dispersed microdisperse main ceskobratrska component, which by reaction with the acid component of the reaction to form the ink in the paper for color reactions.



 

Same patents:

FIELD: cattle breeding; methods of the fodder production.

SUBSTANCE: the invention is pertaining to microballs containing the derivative of pleuromutiline and the method of their production and also to production of the fodder granules containing the microballs and to the method of their production. The microballs have the average size from 1 micron up to 5000 microns and represent the polymeric matrix particles, where the polymeric compound is selected from the shellac, the polymeric compound on the basis of cellulose, the acrylic acid or the methacrylic acid, the maleic anhydride, polyvinyl pyrrolidone or polyvinyl alcohol, and which is highly dispersed in the solid or liquid form with the derivative of pleuromutiline of formula 1 or its physiologically tolerable acid-additive salts and quarternary ammonium salts: , where R1 means vinyl, between 1 and 2 carbonic atoms there is a single bond, and Ra and Rb mean each separately from each other hydrogenen or halogen, and Т represents -CH2-S-(CH2)K-N(R5)(R6), where "k" means the integer from 2 up to 5; R5 andR6 mean each separately from each other C1-C6-alkyl or Т represents -CH2-S-C(CH3)2-CH2-NH-C(O)-CH(NH2)-CH(CH3)2. The method of preparation of the microballs includes production the polymer solution selected from the shellac, the polymetric compound on the basis of cellulose, the acrylic acid or methacrylic acid, the maleic anhydride, polyvinyl pyrrolidone or polyvinyl alcohol, by dissolution of the shellac, the polymetric compound in the organic solvent, having the low affinity to the paraffinic oil or the organosilicic oil and with the dielectric constant from 10 up to 40, with addition of the water. Then the produced solution is introduced at intermixing with the derivative of the pleuromutiline and receive the first organic phase, which is not admixed with the paraffinic oil or the organosilicic oil. The first organic phase introduce at the intense intermixing into the second phase consisting of the paraffinic oil or the organosilicic oil, and prolong intermixing of the produced mixture until the microballs are formed at evaporation or the solvent removal. The microballs are separated, flushed and dried. The fodder granules for the livestock includes the effective number of the indicated above microballs, the milled dry fodder on the vegetable or animal base with or without the additives, such as proteins, vitamins and minerals. The method of preparation of the fodder granules includes the careful intermixing of the microballs with the organic, ground and homogenized components of the fodder. Then they add the water or the steam in the mixture in the amount from 5 up to 10 % of the total mass, press the mixture in the fodder rods at the heightened temperatures from 60 up to 80°С, and divide the rods into the fodder granules. The invention ensures stabilization of the pleuromutiline, which stays undamaged at the granules preparation and is kept safe for the rather long duration of storage.

EFFECT: the invention ensures stabilization of the pleuromutiline, which stays undamaged at the granules preparation and is kept safe for rather long duration of storage.

6 cl, 3 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to cross-linkable polymeric binders, in particular to microcapsulated binders and produce containing such microcapsulated binder, and discloses composition of microcapsulated binder characterized by that binder forms in situ in capsules and comprises: essentially water-insoluble binder-forming material of core, which core includes at least first addition-type prepolymer, vitrification temperature of homopolymer Tg being less than about 0°C, inflammation temperature at least 75°C, and boiling temperature at least 175°C (at atmospheric pressure); solvent for binder-forming material of core, said solvent being essentially water-soluble and not reacting with prepolymer material; essentially water-insoluble free-radical-initiating substance in amount high enough for efficient catalysis, said substance being, in particular, azo-type initiating substance with half-life period at least 1 h at 25°C, which is soluble in prepolymer material to be polymerized and in solvent. Microcapsules are prepared by composing aqueous mixture comprising colloidal dispersion of microcapsule wall-forming material. In order to obtain core material particles less than about 250 μm in size, aqueous solution is subjected to vigorous stirring. Stirring at a first temperature leads to formation of microcapsule wall from microcapsule wall-forming material, while heating to a second temperature provides polymerization of prepolymer material of the core to form binder in microcapsule. Formation of the binder in microcapsule as well as microcapsuled binder composition and substrate are also described.

EFFECT: simplified binding of microcapsuled material.

56 cl, 2 tbl, 18 ex

FIELD: colloid chemistry.

SUBSTANCE: method comprises dispersing water emulsion of hydrophobic polymer in a liquid immiscible with water containing emulsifier, producing the emulsion with enriched phase that comprises water dispersed phase containing the hydrophobic polymer, and inducing inter-phase reaction of polycondensation at least of one of the reagents of the inter-phase polycondensation to produce polymeric film around the hydrophobic polymer.

EFFECT: enhanced efficiency.

40 cl, 5 ex

The invention relates to the field of encapsulation of solids and can be used in construction, chemical and other industries

The invention relates to the field of chemical means of pest control, namely using insecticide

The invention relates to compositions containing at least one microencapsulated additive for rubber
Conductive filler // 2199556
The invention relates to electrically conductive filler for conductive synthetic material for use as a shielding seal

The invention relates to the field of medicine

The invention relates to the field of microencapsulation, in particular to the microencapsulation of lubricating and cooling technological tools studied in the shell, consisting of ferromagnetic substance

FIELD: colloid chemistry.

SUBSTANCE: method comprises dispersing water emulsion of hydrophobic polymer in a liquid immiscible with water containing emulsifier, producing the emulsion with enriched phase that comprises water dispersed phase containing the hydrophobic polymer, and inducing inter-phase reaction of polycondensation at least of one of the reagents of the inter-phase polycondensation to produce polymeric film around the hydrophobic polymer.

EFFECT: enhanced efficiency.

40 cl, 5 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to cross-linkable polymeric binders, in particular to microcapsulated binders and produce containing such microcapsulated binder, and discloses composition of microcapsulated binder characterized by that binder forms in situ in capsules and comprises: essentially water-insoluble binder-forming material of core, which core includes at least first addition-type prepolymer, vitrification temperature of homopolymer Tg being less than about 0°C, inflammation temperature at least 75°C, and boiling temperature at least 175°C (at atmospheric pressure); solvent for binder-forming material of core, said solvent being essentially water-soluble and not reacting with prepolymer material; essentially water-insoluble free-radical-initiating substance in amount high enough for efficient catalysis, said substance being, in particular, azo-type initiating substance with half-life period at least 1 h at 25°C, which is soluble in prepolymer material to be polymerized and in solvent. Microcapsules are prepared by composing aqueous mixture comprising colloidal dispersion of microcapsule wall-forming material. In order to obtain core material particles less than about 250 μm in size, aqueous solution is subjected to vigorous stirring. Stirring at a first temperature leads to formation of microcapsule wall from microcapsule wall-forming material, while heating to a second temperature provides polymerization of prepolymer material of the core to form binder in microcapsule. Formation of the binder in microcapsule as well as microcapsuled binder composition and substrate are also described.

EFFECT: simplified binding of microcapsuled material.

56 cl, 2 tbl, 18 ex

FIELD: cattle breeding; methods of the fodder production.

SUBSTANCE: the invention is pertaining to microballs containing the derivative of pleuromutiline and the method of their production and also to production of the fodder granules containing the microballs and to the method of their production. The microballs have the average size from 1 micron up to 5000 microns and represent the polymeric matrix particles, where the polymeric compound is selected from the shellac, the polymeric compound on the basis of cellulose, the acrylic acid or the methacrylic acid, the maleic anhydride, polyvinyl pyrrolidone or polyvinyl alcohol, and which is highly dispersed in the solid or liquid form with the derivative of pleuromutiline of formula 1 or its physiologically tolerable acid-additive salts and quarternary ammonium salts: , where R1 means vinyl, between 1 and 2 carbonic atoms there is a single bond, and Ra and Rb mean each separately from each other hydrogenen or halogen, and Т represents -CH2-S-(CH2)K-N(R5)(R6), where "k" means the integer from 2 up to 5; R5 andR6 mean each separately from each other C1-C6-alkyl or Т represents -CH2-S-C(CH3)2-CH2-NH-C(O)-CH(NH2)-CH(CH3)2. The method of preparation of the microballs includes production the polymer solution selected from the shellac, the polymetric compound on the basis of cellulose, the acrylic acid or methacrylic acid, the maleic anhydride, polyvinyl pyrrolidone or polyvinyl alcohol, by dissolution of the shellac, the polymetric compound in the organic solvent, having the low affinity to the paraffinic oil or the organosilicic oil and with the dielectric constant from 10 up to 40, with addition of the water. Then the produced solution is introduced at intermixing with the derivative of the pleuromutiline and receive the first organic phase, which is not admixed with the paraffinic oil or the organosilicic oil. The first organic phase introduce at the intense intermixing into the second phase consisting of the paraffinic oil or the organosilicic oil, and prolong intermixing of the produced mixture until the microballs are formed at evaporation or the solvent removal. The microballs are separated, flushed and dried. The fodder granules for the livestock includes the effective number of the indicated above microballs, the milled dry fodder on the vegetable or animal base with or without the additives, such as proteins, vitamins and minerals. The method of preparation of the fodder granules includes the careful intermixing of the microballs with the organic, ground and homogenized components of the fodder. Then they add the water or the steam in the mixture in the amount from 5 up to 10 % of the total mass, press the mixture in the fodder rods at the heightened temperatures from 60 up to 80°С, and divide the rods into the fodder granules. The invention ensures stabilization of the pleuromutiline, which stays undamaged at the granules preparation and is kept safe for the rather long duration of storage.

EFFECT: the invention ensures stabilization of the pleuromutiline, which stays undamaged at the granules preparation and is kept safe for rather long duration of storage.

6 cl, 3 tbl, 3 ex

FIELD: self-copy papers.

SUBSTANCE: group of inventions relate to use of microcapsules containing color reaction component. Color reaction component is first dissolved in solvent, namely vegetal oil C1-C8-alkyl ester, and to thus obtained solution a non-solvent is admixed at rapid stirring, said non-solvent not dissolving or dissolving insignificantly color reaction component and being taken in amount as to form supersaturated solution. The latter is directly emulsified in water phase at rapid stirring and, immediately after that, resulting emulsion is processed so that encapsulation takes place therein. Microcapsules obtained in this way are further described as well as their employment in color reaction paper.

EFFECT: improved writing quality and economic and environmental advantages.

33 cl, 1 dwg, 4 ex

FIELD: encapsulation of solid materials.

SUBSTANCE: method comprises forming a shell made of encapsulating material on the surface of the grain material when grain material and encapsulating material flow through the piping chamber. The material is transported and capsulated under the action of the spiral member rotating with a speed of 50-3000 rev/min. The length of the spiral member and piping chamber ranges from 5 to 100 of the lateral sizes of the chamber.

EFFECT: enhanced efficiency.

1 tbl, 3 ex

FIELD: food and pharmaceutical industries.

SUBSTANCE: object of invention is production of freely flowing alcohol-containing encapsulated products. Food fat and/or wax are melted in heated reactor at 55-65°C, after which required food additives or additive complexes are added, resulting mixture is stirred to achieve homogenous mass and alcoholic produce with alcohol content from 5 to 96.6% is added in amount 5 to 60 wt parts per 100 wt parts of the reactor charge. Emulsion obtained is supplied to atomization turbine wherein arising drops are solidified in air and collected in receiving device. Thus obtained powder is screened and tightly packaged. Granule size is controlled by turbine rotation speed and varied within a range of 0.1 to 1 mm.

EFFECT: enabled creation of fundamentally novel formulations and production technologies, improved quality, reduced expenses, and prolonged shelf time of produce.

3 cl, 6 ex

FIELD: derivatives of chitosan.

SUBSTANCE: invention relates to preparing biologically active chitosan substances and their derivatives. Invention describes a modified chitosan substance showing pH-neutral reaction and plastic structure of chitosan particles as fractal chitosan particles of size of nanofractals from 1 nm, not less, and to 5000 nm, not above, or as cross-linked net-shaped polymer having multiple cavities of size from 1 nm, not less, to 50 nm, not above. Invention describes methods for their preparing. Invention provides high transdermal penetration of chitosan substance and enhanced capacity for administration of medicinal or biologically active substances into chitosan substance. Invention can be used in manufacturing cosmetic, curative-cosmetic, pharmacological preparations, biologically active food supplements and foodstuffs.

EFFECT: improved and valuable properties of chitosan substances.

14 cl, 4 tbl, 7 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: group of invention covers the microcapsules consisting of at least one core which contains the rubber supplement, and the first polymeric coat of melamine-formaldehyde or phenol-formaldehyde resin; the second polymeric coat is applied upon the microcapsule and its content differs from that of the first one and consists of the low-molecular inorganic or organic compound as a sliding and wear layer to reduce the static friction.

EFFECT: method of preparation microcapsules and use in rubber vulcanisation.

20 cl, 14 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition is used for making hollow micro-spheres, which are used as a component of boring solutions when finding and producing oil, as low density filler in various composite materials, used in machine building, aviation and ship building, space technology, and when making heat insulation materials. The composition contains the following, in the given mass ratios: resol phenol-formaldehyde resin with relative viscosity of 5000-9000 cP - 100, porofor (5), polyether based on ethylene oxide copolymer and propylene oxide with molecular mass of 4000-6000 (2-3).

EFFECT: higher space factor of the boring solution micro-spheres, improved looseness of the micro-spheres, increased strength during hydrostatic compression.

1 tbl, 3 ex

FIELD: medicine; pharmacology.

SUBSTANCE: carrying out of treatment of disease, in particular, diabetes, by implantation of the encapsulated devices containing a covering and cells, thus density of cells makes 100000 cells/ml, and the covering contains acrylate polyethylene alcohol (PEG) high density with molecular mass from 900 to 3000 Dalton, and also a sulfonated comonomer.

EFFECT: minimisation of the tissue response, augmentation of concentration of cells and augmentation of time of viability of cells in the specified devices.

83 cl, 33 dwg, 8 tbl, 20 ex

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