MXPA01005404A - Hydrophobic epoxide resin system - Google Patents

Abstract

The invention relates to a composition containing (a) an epoxide resin, (b) an OH-terminated polysiloxane, (c) a cyclic polysiloxane and (d) a non-ionic, fluoroaliphatic surface-active reagent. The composition has excellent hydrophobicity properties and can be used as an electrical insulation material.

Description

HYDROPHOBIC SYSTEM OF EPOXY RESIN The present invention relates to a composition comprising an epoxy resin, various polysiloxanes and fluorinated compounds, to crosslinked products obtainable by hardening a composition such as this as well as to the use of this composition as electrical insulation material. Due to their good mechanical properties and their high specific resistance, epoxy resins are often used as electrical insulation material. Due to its high resistance to inclement weather, cycloaliphatic epoxy resins are especially suitable for outdoor use. However, especially in regions with high levels of precipitation with severe air pollution, the problem arises that a dirt / water conductive layer can be formed on the surface of the insulation, which produces leakage currents and arcs voltaicos and can have as a consequence a damage to the insulator until its total destruction. Also in the case of insulations based on epoxies with little dirt, an increase in surface conductivity can occur, when the surface erodes in the course of time due to inclement weather and water can better moisturize a rough layer as the that is formed. As disclosed in U.S. Patent 3,926,885, the hydrophobic characteristics can be provided to the epoxy resins by the addition of polysiloxane / polyether copolymers and OH-terminated polysiloxanes. However, the adhesion of this material to the metal is not sufficient for all applications. Japanese Patent JP-A 2-305454 discloses mixtures of epoxy resins with high moisture stability, which, in addition to an epoxinovolak and a phenolic resin, also contain small amounts of a cyclic dimethylsiloxane. Although in these compositions the corrosion produced by the bonding of water on the surface is largely avoided, this system does not achieve a sufficient hydrophobic effect for use as an insulator. In International Publication 098/32138 a resins system suitable as electrical insulation material is described, based on hardenable mixtures of epoxy resins and special silicone oligomers, which present final glycidyl groups. By hardening, the silicone oligomers become part of the cross-linked structure that is formed, the hardened material being able to provide the known properties of the silicones, such as hydrophobicity and good resistance to weathering. The disadvantage is the use of expensive silicone oligomers which can be obtained commercially and a poor hydrophobic transfer effect. It has now been found that compositions containing an epoxy resin, at least two specific polysiloxanes and a nonionic, fluoroaliphatic active surface reactant, can result in storage stable emulsions, which in the hardened state exhibit a marked hydrophobic transfer effect and recovery effects. The object of the present invention is a composition containing: (a) an epoxy resin, (b) an OH-terminated polysiloxane, (c) a cyclic polysiloxane, and (d) a non-ionic, fluoroaliphatic active surface reactant. In the compositions according to the invention, the amounts of the components (a) to (c) can vary within wide ranges. The compositions are preferred which, based on the total composition of (a), (b), (c) and (d), contain 77.0 to 97.99% by weight, in particular 86.0 to 96.95% by weight, of component (a) , 1.0 to 10.0% by weight, in particular 2.0 to 6.0% by weight, of component (b), 1.0 to 10.0% by weight, in particular 1.0 to 5.0% by weight, of component (c) and 0.01 to 3.0% by weight weight, in particular 0.05 to 3.0% by weight, of the subject (d), where the sum of the components (a), (b), (c) and (d) is 100% by weight. As component (a) of the compositions according to the invention, all types of epoxies containing at least one glycidyl or β-methylglycidyl group, a linear alkylene oxide group or a cycloalkylene oxide group are suitable. Examples of suitable epoxy resins are polyglycidyl and poly (β-methylglycidyl) ether, which can be obtained by the reaction of a compound containing at least two free alcoholic and / or phenolic hydroxyl groups per molecule, with epichlorohydrin or β -methylepicloridrine, under alkaline conditions or, also, in the presence of an acid catalyst with the subsequent alkaline treatment. Suitable starting compounds for the preparation of these glycidyl- or β-methyl glycidyl ethers are, for example, acyclic alcohols such as ethylene glycol, diethylene glycol and high molecular weight poly (oxyethylene) glycols, propan-1,2-diol and poly (oxypropylene) glycols, propan-l, 3-diol, butan-1,4-diol, poly (oxytetramethylene) -glycols, pentan-1,5-diol, hexane-1,6-diol, hexan-2, 4 , 6-triol, glycerin, 1,1-trimethylolpropane, pentaerythritol or sorbitol, cycloaliphatic alcohols such as resorcite, quinite, bis- (4-hydroxycyclohexyl) -methane, 2,2-bis- (4-hydroxycyclohexyl) -pyrropane and 1, 1-bis- (hydroxymethyl) -cyclohexen-3 and alcohols with aromatic nuclei, such as N, N-bis- (2-hydroxyethyl) -aniline and p, p '-bis- (2-n-hydroxyethylamino) -diphenylmethane. Other dihydroxyl compounds suitable for the preparation of glycidyl- or β-methylglycidyl ethers are monocyclic phenols such as resorcin and hydroquinone, polycyclic phenols, such as bis- (-hydroxyphenyl) -methane, 4,4-dihydroxydiphenyl, bis- (4) -hydroxyphenyl) -sulfone, 1,1,2,2-tetrakis- (4-hydroxyphenyl) -ethane, 2,2-bis- (4-hydroxy-phenyl) -propane (Bisphenol A) and 2, 2-bis- (3, 5-dibrom-4-hydroxyphenyl) -propane, as well as Novolak, for example, novolak of phenol and cresol. The polyglycidyl- and poly (β-methylglycidyl) -esters can be obtained by the reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerindichlorohydrin or β-methylepicloridrine in the presence of alkalis. These polyglycidyl esters can be derived from aliphatic polycarboxylic acids, for example, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid; sebacic acid or dimerized or trimerized linolic acid, of cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and methylmethylhydrophthalic acid, and of aromatic plicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. Other epoxies suitable as component (a) are poly (N-glycidyl) compounds, such as products obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms, such as aniline, n-butylamine, bis- (4-aminophenyl) -methane and bis- (4-methyl-aminophenyl) -methane. Among the above are also triglycidyl isocyanurate as well as N, N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethylene urea and 1,3-propylenic urea and hydantoins, such as 5,5-dimethylhydantoin. Also suitable are poly (S-glycidyl) compounds, such as for example the di-S-glycidyl derivatives of dithiols, such as ethane-1,2-dithiol and bis- (4-mercaptomethylphenyl) -ether. Preferably, the compositions contain as component (a) a cycloaliphatic epoxy resin or an epoxidation product of an unsaturated natural oil and a derivative thereof.

Within the framework of the present invention, the term "cycloaliphatic epoxy resin" encompasses all epoxy resins with cycloaliphatic structural units, that is, it includes both glycidyl cycloaliphatic compounds, ß-methylglycidyl compounds, and also epoxy resins based on oxides of cycloalkylene. Suitable glycidyl cycloaliphatic compounds and suitable β-methylglycidyl compounds are the glycidyl esters and β-methylglycidyl esters of cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid and 4-methylglycidic acid. methylhexahydrophthalic. Other suitable epoxy resins are the diglycidyl ethers and β-methylglycidyl ethers of cycloaliphatic alcohols, such as 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane and 1,4-dihydroxycyclohexane, 1,4-cyclohexanedimethanol, 1,1-bis (hydroxymethyl) cyclohex-3-ene, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane and bis (4-hydroxycyclohexyl) sulfone. Examples of epoxy resins with cycloalkylene oxide structures are bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidylether, 1,2-bis (2,3-epoxycyclopentyl) ethane, vinylcyclohexene dioxide, 3, 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate and bis (3) 4-epoxy-6-methylcyclohexylmethyl) adipate. Preferred cycloaliphatic epoxy resins are bLs (4-hydroxycyclohexyl) methan-diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propandiglycidyl ether, diglycidyl ester of tetrahydrophthalic acid, diglycidyl ester of 4-methyltetrahydrophthalic acid, diglycidyl ester of 4-methylhexahydrophthalic acid, and, in particular, diglycidyl ester of hexahydrophthalic acid and 3,4-epoxycyclohexylmethyl-3 '4'-epoxycyclohexanecarboxylate. As component (a), epoxidation products of unsaturated esters of fatty acids can also be used in the compositions according to the invention. Preference is given to using epoxy-containing compounds, which are derived from mono- and polyhydric acids having 12 to 22 carbon atoms and an iodine number between 30 and 400, such as, for example, lauroleinic acid, myristoleinic acid, palmitoleinic acid, oleic acid, gadoleinic acid, erucic acid, ricinoleic acid, linolic acid, linolenic acid, elaidinic acid, licánic acid, arachidonic acid and clupanodonic acid. Suitable are, for example, the epoxidation products of soybean oil, linseed oil, knob oil, tung oil, ocydic oil, safflower oil, poppy oil, hemp oil, cottonseed oil, oil. of sunflower, rapeseed oil, poly-unsaturated triglycerides, triglycerides of euphorbia plants, peanut oil, olive oil, olive oil, almond oil, ceiba oil, hazelnut oil, apricot kernel oil, beech oil, lupine oil, corn oil, sesame oil, grape bone oil, lalemancy oil, castor oil, herring oil, sardine oil, menhaden oil, whale oil, tallow and derivatives of the same. Also suitable are the high unsaturated derivatives, which can be obtained by further dehydrogenation reactions of these oils. The olefinic double bonds of the fatty acid radicals or the aforementioned compounds can be epoxidized according to known methods, for example by reaction with hydrogen peroxide, optionally in the presence of a catalyst, an alkyl hydroperoxide or a peracid, as for example, performic acid or peracetic acid. Within the framework of the invention, both the fully epoxidized and the partially epoxidized derivatives still containing free double bonds can be used as component (a). As the component (a), epoxidized soybean oil and linseed oil are especially preferred. The polysiloxanes terminated in OH according to component (b) can be obtained by known methods, for example, with the hydrolysis of the corresponding organophosilanes and the subsequent polycondensation of the silanols. In the foregoing, polysiloxane mixtures with molecular masses of 1'000-150'000 g / mol are usually obtained. A series of these OH-terminated polysiloxanes can be obtained in commerce. Liquid polysiloxanes are preferably used in the compositions according to the invention. Preferably, a polysiloxane of the formula I is used: wherein Ri and R, independently of one another, mean alkyl of 1 to 18 carbon atoms, aryl of 5 to 14 carbon atoms or aralkyl of 6 to 24 carbon atoms, and n means an average value of 3 to 60, in particular from 4 to 20. Alkyl may be, for example, methyl, ethyl, isopropyl, normal propyl, normal butyl, isobutyl, secondary butyl, tertiary butyl as well as various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl groups , undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Aryl as Ri or R2 preferably contains 6 to 14 carbon atoms. It can be, for example, phenyl, tolyl, pentalinyl, indenyl, naphthyl, blueinyl and anthryl. Aralkyl as R? or R2 preferably contains 7 a 12 carbon atoms and in particular 7 to 10 carbon atoms. It may be, for example, benzyl, phenylethyl, 3-phenylpropyl, α-methylbenzyl, 4-phenylbutyl or α, α-dimethylbenzyl. Especially preferred are the polysiloxanes of the formula I, in which Ri and R2, independently of one another, mean methyl, ethyl or phenyl. As component (b), polysiloxanes of the formula I are particularly preferred, in which Ri and R 2 represent methyl and n means 4 to 20. The polysiloxanes according to component (c) are also known to those skilled in the art and can be obtained in accordance with to known methods. Preferably, a cyclic polysiloxane of the formula II is used as component (c): wherein Ri and R, independently of one another, mean alkyl of 1 to 18 carbon atoms, aryl of 5 to 14 carbon atoms or aralkyl of 6 to 24 carbon atoms, and m means an integer of 3 to 12. Alkyl, aryl and aralkyl in the formula (II) have the same meaning as the corresponding groups of the formula (I). As component (c), cyclic polysiloxanes of the formula II are preferred, in which R x and R 2, independently of one another, mean methyl, ethyl or phenyl, and m means an integer from 3 to 8. In particular, R and R 2 represent methyl and m means an integer from 6 to 8. As described in J. Am. Chem. Soc. 6_8, 358 (1946), these cyclic polysiloxanes can be isolated from the product mixture that is generated in the hydrolysis of the corresponding dialkyl-, diaryl- or diaralkyldiclorsilanes. As component (c), the commercially available compounds octamethylcyclotetrasiloxane (m = 4), decamethylcyclopenta siloxane (m = 5) and, in particular, dodecamethylcyclohexasiloxane (m = 6), as well as the hydrolysates of dimethyldiclorsilane, in particular undistilled hydrolysates, since they have high portions of cyclic polysiloxanes with the preferred ring size m = 6 to 8, that is, in addition to dodecamethylcyclohexasiloxane also tetradecamethylcycloheptasiloxane (m = 7) and hexadecamethylcyclooctasiloxane (m = 8). As reagent of surface activity in the form of component (c) of the compositions according to the invention, perfluorinated nonionic polyalkylene derivatives, such as perfluorinated polyoxyalkylene, are suitable. Preference is given to compounds of a combination of a perfluorinated aliphatic alkyl unit Rf with a hydrocarbon unit R, wherein the latter contains at least one mono- or divalent polar functional group, which preferably contains oxygen, such as, for example, -OH, -COOH, -COOR, -COO-, -CO-, -0-. Suitable compounds are alkoxylated, especially ethoxylated, perfluorinated fatty acid derivatives, for example: Rf-COO- (CH2-CH20) mR (III) OR Rf- (CH2CH20) mR (IV) wherein m means 1 to 200, Rf means a perfluorinated alkyl, linear or branched, of 2 to 22 carbon atoms, and R means H, alkyl of 1 to 6 carbon atoms or Rf. Preferably, compounds of the formulas (III) or (IV) are used, in which the molar mass according to the theoretical additive formulait is only from 200 to 10'000, in particular from 300 to 8000. Preferred compounds are, for example, F3C- (CF2) 5- (CH2CH20) -H = 1, 2, 2-tetrahydroperfluoroctanol (according to formula (IV), wherein Rf = perfluorinated normal hexyl, m = 1 and R = H) or Rf-COO- (CH2CH20) mR, wherein Rf means linear alkyl perfluorinated with 16 to 18 carbon atoms, m = 110- 130 and R = H. These compounds can be obtained in part from several suppliers in commerce, for example, as ZONYL® Fluorochemical Intermediates (DuPont), for example, ZONYL® BA-L and BA fluoroalcohol, or FLUORAD® Fluorosurfactants (3M ), for example, FLUORAD® FC-431. Other surface-active compounds which can be used according to the invention can be found in the technical bulletins of the aforementioned manufacturers, for example, "Technical Information" 233592B (1/94) on ZONYL® Fluorochemical Intermediates (DuPont). In the compositions according to the invention, one or more compounds of the components (a) to (d) can be used respectively. In principle, the compositions according to the invention can be hardened by cationic polymerization of the epoxy resin system with an initiator system or with any usual epoxy hardener. However, anhydride hardeners are preferably used. Therefore, another object of the invention is constituted by a composition containing the above-mentioned components (a) to (d) and, additionally, as component (e), a polycarboxylic acid anhydride. They can be linear, aliphatic, polymeric anhydrides, such as, for example, polyanebic acid polyanhydride or polyazelaminic acid polyanhydride, or cyclic carboxylic acid anhydrides. Cyclic carboxylic acid anhydrides are preferred. Examples of cyclic carboxylic acid anhydrides are: succinic acid anhydride, citraconic anhydride, itaconic anhydride, succinic anhydrides substituted with alkenyl, dodecenylsuccinic anhydride, maleic acid anhydride and tricarballylic acid anhydride, adduct anhydride of maleic acid with cyclopentadiene or methylcyclopentadiene, adduct of lytic acid with maleic anhydride, alkylated anhydrides of endoalkylenetetrahydrophthalic acid, anhydride of methyltetrahydrophthalic acid and anhydride of trahydrofic acid, where mixtures of isomers of the latter two are especially suitable. . Hexahydrophthalic anhydride and methylhexahydrophthalic acid anhydride are particularly preferred. Other examples of cyclic carboxylic acid anhydrides are aromatic anhydrides, such as pyromellitic acid dianhydride, trimellitic acid anhydride and phthalic anhydride. Chlorinated or brominated anhydrides can also be used, such as, for example, tetrachlorophthalic acid anhydride, tetrabromphthalic acid anhydride, dichlormaleic acid anhydride and clorendic anhydride. Optionally, the compositions according to the invention may additionally contain a hardening accelerator (f). Suitable accelerators are known to the person skilled in the art. Examples which may be mentioned are: complexes of amines, especially tertiary amines, with boron trichloride or boron trifluoride; tertiary amines, such as benzyldimethylamine; urea derivatives, such as optionally substituted N-4-chlorophenyl-N ', N 1 -dimethylurea (monuron), imidazoles, such as imidazole or 2-phenylimidazole. For the aforementioned compositions containing epoxidized oils, the preferred accelerators are the tertiary amines, in particular benzyldimethylamine, and the imidazoles (for example, 1-methylimidazole). The components (e) and (f) are used in the amounts which are normally effective, ie sufficient for the hardening of the compositions according to the invention. The proportion of the components (a) and (e) and, optionally, (f), depends on the type of compound used, the required curing speed and the properties desired in the final product, and the person skilled in the art can determine it easily. In general, 0.4 to 1.6, preferably 0.8 to 1.2, equivalents of anhydride groups per equivalent of epoxy are employed. In general, the mixture of resins (a) to (d) and the hardener component (e), possibly together with the accelerator (f), are stored separately and mixed just before application. If the mixture of resins (a) to (d) must be stored before curing, it requires additional auxiliaries as an optional component (g), in order to keep the emulsion-forming mixture storable. As stabilizing aids of this type, both emulsifiers (surface activity and surface area compounds) and also thickeners (for example, silicic acids, bentonite, dibenzylidensorbitol, etc.) can be used. The above and their use are known to the person skilled in the art. Of the aforementioned auxiliaries, highly dispersed silicic acid is preferably used. Highly dispersed, hydrophilic, untreated silicic acids are especially suitable. You can get them in trade, for example, like Aerosil. The effective amounts of silicic acid are in the range of 0.01 to 3.5, preferably 0.05 to 3.0% by weight, based on the sum of the components (a) to (d), and the average size of the primary particles is conveniently around 12 nm. Therefore, the compositions stable to storage, which can be obtained by the addition of stabilizing aids, such as emulsifiers or thickeners, are also subject of the invention. Instead of the hardening component (e), optionally together with an accelerator (f), the mixture of resins (a) to (d) may contain as component (e) an initiator system for the cationic polymerization of the epoxy resin. As the initiator system for the cationic polymerization of the epoxy resins, for example, thermally activatable initiators are used, such as onium salts, oxonium salts, iodonium salts, sulfonium salts, phosphonium salts or quaternary ammonium salts, which do not They contain nucleophilic anions. These initiators and their application are known. For example, in U.S. Patent 4,336,363, in European Patent EP-A-0 379 464 or in European Patent EP-A-0580 552, specific sulfonium salts are disclosed as a hardener for epoxy resins. In U.S. Patent 4,058,401, in addition to the determined sulfonium salts, the corresponding tellurium and selenium salts are also described. The quaternary ammonium salts as thermally activatable initiators are disclosed, for example, in European Patent EP-A 0 066 543 and in European Patent EP-A-0 673 104. In this case, these are salts of nitrogen bases aromatic - heterocyclic, with non-nucleophilic halide anions, for example, complexes, such as BF4", PF6", SbFs (OH) "and AsF6". Preferably, N-benzylquinolium hexafluoroantimonate is used as the quaternary ammonium salt. In the use of the quaternary ammonium salts, it is also convenient to use a thermal radical former, such as, for example, pinacols and their ethers, esters or silyl derivatives. These compounds are known and can be obtained according to known procedures. As the thermal radical former, pinacols, such as acetophenonepinacols or, in particular, 1, 1, 2, 2-tetraphenyl-1,2-ethanediol (benzpinacol), are preferably used. In particular, N-benzylquinolium-hexafluoroantimonate is used as a thermally activatable initiator with 1,2,1-tetraphenyl-1,2-ethanediol, preferably in a molar ratio of 1: 1. In general, the activation temperature of the cationic initiators is located above room temperature, preferably in the range between 60 and 180 ° C, especially between 90 and 150 ° C. In general, the amount of the cationic initiator contained in the cationically hardenable epoxy resin is 0.05 to 30% by weight, preferably 0.5 to 15% by weight, based on the amount of the cationically polymerizable epoxy resin. Also, the hardenable mixtures may contain agents for toughness ("Toughener"), such as Core / Shell polymers or elastomers known to the person skilled in the art as "Rubber Toughener" or graft polymers containing elastomers. Suitable tenacity agents are described, for example, in European Patent EP-A-0 449 776.

They are preferably used in an amount of 1 to 20% by weight, based on the total amount of epoxy resin in the composition.

Likewise, hardenable mixtures, in addition to the aforementioned, may contain other fillers such as metal powder, wood dust, glass powder, glass spheres, semimetal and metal oxides, such as, for example, Si02 (quartz sand, quartz powder, silanized quartz powder, molten silicon powder, silanized molten silicon powder), aluminum oxide, titanium oxide and zirconium oxide, metal hydroxides, such as Mg (OH) 2, Al (OH) 3, Al (OH) 3 silanized and ALO (OH), nitrides of semimetals and metals, such as, for example, silicon nitride, boron nitride and aluminum nitride, semimetal and metal carbides (SiC and boron carbides), metal carbonates (dolomite, gis, CaCO3), metal sulphates (barite, gypsum), rock powders, such as hydromagnesite and huntite, and natural and synthetic minerals, mainly from the series of silicates, such as, for example, zeolites (especially molecular sieves), talc, mica, kaolin, wollastonite and others. Preferred fillers are quartz powder, silanized quartz powder, aluminum hydroxide or aluminum oxide. In addition to the aforementioned additives, the hardenable mixtures may contain other customary additives, such as, for example, antioxidants, photoresists, flame retardants, fillers containing water of crystallization, plasticizers, dyes, pigments, fungicides, thioxotropic agents, tenacity improvers, defoamers, antistatic agents, lubricants, antisease agents, humectants and mold release aids. The compositions according to the invention can be obtained according to known methods, with the aid of known mixing aggregates, such as, for example, stirrers (especially dispersers and Supraton® with high shear gradient), mixers, rollers or dry mixers.

In the case of solid epoxy resins, the dispersion can also be carried out in the melt. The curing of the mixtures according to the invention can be carried out, as is known, in one or more steps. In general, it is carried out by heating the mixtures at temperatures between 60 ° C and 200 ° C, in particular between 80 ° C and 180 ° C. The invention also relates to crosslinked products that can be obtained by hardening a composition according to the invention. Surprisingly, the addition of the two chemically different siloxane components and the surface activity reagent to the compositions according to the invention, in comparison with the corresponding unmodified systems (Comparative Example 1), produces practically no worsening, or only slight, of the mechanical and electrical properties of the products obtained from them. In general, the addition of silicones causes a worsening of the adhesive properties. Even so, the compositions according to the invention unexpectedly show a good adhesion to the metal, which is reflected in excellent values of bending break and tear force without modifications. In the same way, a behavior at comparatively very good temperature change of the encapsulated molding bodies with a system according to the invention is surprisingly observed. With respect to unmodified systems, the invention offers the advantage that traces of the siloxanes used according to the invention can migrate to the soils present in the hardened material. In this way, even an initially hydrophilic dirt layer becomes hydrophobic (hydrophobic transfer). This results in the water sliding more easily from the dirt and does not form, as in the case of the unmodified system, a continuous and conductive dirt / water layer, and thereby, harmful. Even, this effect is surprisingly marked. Water slides essentially better and faster. Surprisingly, also the durability of this effect is very good. That is to say, even in case of detachment several times and the dirt layer is deposited again, the marked hydrophobic transfer effect is maintained. Also in the case of lightly soiled insulators based on epoxy resin, a loss of the original hydrophobicity and, with it, an increase in surface conductivity can occur. The reason are micro-discharges that can be caused, for example, by certain drops of rain on the insulating surface. With respect to unmodified systems (Comparative Example 1), another advantage of the present invention is that with the present systems, surprisingly, after a forced loss like this, the recovery of the original hydrophobicity can take place. This implies that the original hydrophobia is restored within a period of hours to a few days (recovery effect). In this way, the systems according to the invention, with their excellent hydrophobic properties in the form of a very good and also permanent hydrophobic transfer effect in combination with a very good recovery effect and good properties at temperature changes , are predestined to be used as insulation material in outdoor applications in difficult climatic zones. The compositions according to the invention are especially suitable as molding resins, molding compounds ("structural casting"), rolling resins, compression molding materials ("epoxy molding compounds"), coating compositions, and special, as electrical insulation masses. The use of the compositions according to the invention as electrical insulation material is another object of the invention. The following commercial substances are used in the following examples: Epoxy resin 1: hexahydrophthalic acid diglycidyl ester; epoxy content: 5.6 to 6.2 val / kg ("CY 184", Ciba Spezialitáten Chemie). ESO: epoxidized soybean oil; Epoxy content: 4.10 to 4.20 val / kg; ("Reoplast", Witco). ELO: epoxidized linseed oil; Epoxy content: 5.50 to 5.65 val / kg; ("Merginat", Harburger Chemie). Hardener 1: hardener mixture of 70 parts by weight of hexahydrofonic acid anhydride and 30 parts by weight of methylhexahydrophthalic acid anhydride. W 12: untreated quartz powder (Quarzwerke Frechen). W 12 EST: quartz powder pretreated with epoxysilane (Quarzwerke Frechen). Polysiloxane 1: OH-terminated polydimethylsiloxane with a viscosity of 5 Pa. * S ("NG200-5000", Wacker).

Polysiloxane 2: mixture of linear polydimethylsiloxanes terminated in OH (< 40%) and cyclic dimethylsiloxanes (> 60%), with a viscosity of 5 to 20 Pa * s ("Dimethylmethanolysat", GE-Bayer AG). Fluorad: untreated perfluorinated aliphatic polymeric ester (perfluorinated ethoxylated fatty acid) ("Fluorad FC 431", 3M). BDMA: benzyldimethylamine. 1-M1: 1-methylimidazole. Aerosil: highly dispersed hydrophilic silicic acid ("Aerosil 200", Degussa).

Preparation examples Comparative Example 1: In a paddle mixer, 1000 g of epoxy resin 1, 900 g of hardener 1, 5.0 g of BDMA and 2700 g of quartz powder W are mixed at 60 ° C in a lapse of 30 minutes. 12 EST, and then, at approximately 10 mbar, it is degassed briefly. Subsequently, the composition hardens 6 hours at 80 ° C and 10 hours at 140 ° C. The properties of the hardened product are summarized in Table 1.

Example of conformity with the invention 1: In a mixer with dispersing discs they are mixed in 10 minutes at 3750 r.p.m. and at room temperature 9050 g of epoxy resin 1, 200 g of polysiloxane 1, 500 g of polysiloxane 2 and 100 g of Fluorad. Then add 150 g of Aerosil to the mixture and mix for one hour at 3750 r.p.m. and room temperature. In this way a white emulsion is obtained, stable to storage. 1000 g of the resin premix obtained in this way are mixed with a paddle mixer, at 60 ° C, in a lapse of 30 minutes, with 814.5 g of hardener 1, 4.5 g of BDMA and 2578.1 g of quartz powder W 12 EST, and then degas briefly to about 10 mbar. Subsequently, the composition hardens 6 hours at 80 ° C and 10 hours at 140 ° C. The properties of the hardened product are summarized in Table 1.

Example of conformity with the invention 2: In a mixer with dispersing discs they are mixed in 10 minutes at 3750 r.p.m. and at room temperature 6855 g of epoxy 1, 200 g of polysiloxane 1, 500 g of polysiloxane 2, 10 g of Fluorad, 1143 g of ESO and 1143 g of ELO. Then add 150 g of Aerosil to the mixture and mix for one hour at 3750 r.p.m. and room temperature. In this way a white emulsion is obtained, stable to storage. 1000 g of the resin premix obtained in this way are mixed with a paddle mixer, at 60 ° C, in a lapse of 30 minutes, with 806.6 g of hardener 1, 2.3 g of BDMA, 4.5 g of 1-MI and 2567.1 g of quartz powder W 12 EST, and then degas briefly to about 10 mbar. Subsequently, the composition hardens 6 hours at 80 ° C and 10 hours at 140 ° C. The properties of the hardened product are summarized in Table 1.

EXAMPLE OF COMPLIANCE WITH THE INVENTION 3: In a mixer with dispersing discs, at first 110 ° 50 g of dibenzylidene sorbitol are dissolved in 9100 g of epoxy resin 1, and then the mixture is cooled to room temperature. Then 200 g of polysiloxane 1, 500 g of polysiloxane 2 and 100 g of Fluorad are added, and the mixture is stirred for 15 minutes at 1500 r.p.m. and room temperature. Then, 50 g of Aerosil are added to the mixture and the whole mixture is stirred again for one hour at 1500 r.p.m. and room temperature. A white emulsion is obtained, stable to storage. 1000 g of the resin premix obtained in this way is mixed with a paddle mixer, at 60 ° C, in a lapse of 30 minutes, with 820 g of hardener 1, 4.5 g of BDMA and 3542 g of quartz powder W 12 EST, and then degas briefly to about 10 mbar.

Application Example 1: By means of the pressure gelation process, rigid insulators are manufactured. For this, the non-hardening mixtures obtained according to Example 1 and Comparative Example 1 analogously, but with a filling degree of 66% by weight, they are injected into a metal mold heated to 140 ° C, treated with release agents. After gelation (after approximately 20 minutes), the molded part is removed from the mold and further hardens 10 hours at 140 ° C. The insulator made with the composition according to the invention surprisingly has an equally high breaking strength by bending as that of the insulator made from the analogous composition without silicone additives, while a comparison of the tearing forces demonstrates that the material of conformity with the invention it remains very well adhered to the insertion (see Table 1).

Application Example 2: The following tests show the best performance of the insulators made with the modified system according to the invention, in atmospheres with a high air pollution, especially the best hydrophobic properties: 2A: Hydrophobic transfer effect examine samples of the examples according to the invention 1 to 3 to check the so-called "hydrophobic transfer effect". For this purpose, on four plates of the material obtained respectively with the product according to the examples according to the invention 1 to 3 and to Comparative Example 1 (obtained without using release agents containing silicone and cleaned with acetone after demolding), applies artificial dirt. For this purpose, quartz powder W 12 is applied to the plates by means of a vibrating device, in such quantities per surface, that subsequently, when flattening with a ruler or the like, a layer thickness of 0.5 mm can be achieved. In order to check whether the material transfers the hydrophobicity to the hydrophilic quartz layer itself, a drop of water of 30 μl is applied to the outer layer at regular intervals with a pipette, whose behavior is observed and classified according to the following scheme: Transfer level system (NT) Transfer level system: 500 μm quartz powder coating (W 12 quartz powder, Quarzwerke Frechen), 30 μl water drop application 2B: Checking the recovery effect by the plasma test To check the recovery effect, the state of the hydrophobicity is determined (see point 2B1). Subsequently, the hydrophilic state is forced by applying a plasma (see point 2B2). After the plasma treatment, which is intended to cause the loss of hydrophobicity, the state of the surface is again examined at various times (immediately, after one hour (h) and one day (d)). A recovery effect is observed when a sample passes from the hydrophilic state (approximately in class 5 to 7) to the hydrophobic state (approximately to class 1 to 4), that is, when it was restored to something before the plasma state. The results are shown in Table 1. 2B1: The state of momentary hydrophobicity of the samples is determined as follows: a sample surface of approximately 100 cm2, in vertical position, is sprayed with water 20 times (once per second) ) with a rolling bottle at a distance of about 25 ± 10 cm. After another 10 seconds, the sample is checked and the surface condition is classified according to the following scheme: Classification of the hydrophobic state in the spray test Class Properties Description of the effects CH 1 Excellent surface hydrophobia Only discrete drops, the wet angle of most drops is > 80 ° Very good surface hydrophobicity Only discrete drops, the wet angle of most drops is > 50 ° but < 80 ° Good surface hydrophobia Only discrete drops, the wet angle of the 2B2: A loss of hydrophobicity or hydrophilicity is forced by a plasma treatment. To do this, the 10 x 10 x 0.4 cm3 test plates are placed in a plasma chamber of type 440 (Technics Plasma GmbH) and are subjected to the following conditions: plasma application time: 2 minutes, pressure: 2 at 3 mbar, gas: oxygen, power: 200 Watts. This treatment produces the loss of hydrophobicity (see Table 1).

Comparative Application Examples: In principle analogously to the example according to the invention 1, three comparative examples are produced. Unlike Comparative Example 1, where the polysiloxanes 1 and 2 and a reagent of surface activity are simultaneously used, only one additive is used respectively. The compositions and the properties of the hardened products are summarized in Table 1. Table 1 Comparative examples and according to the invention EC 1 The 1 The 2 The 3 EC 2 EC 3 EC 4 Composition [parts by weight] Epoxy resin 1 100 90.5 68.55 91 97 94 99 ESO 11.43 ELO 11.43 Polysiloxane 1 2 2 2 Polysiloxane 2 5 5 5 Fluorad 1 0.1 1 1 BDMA 0.5 0.45 0.23 0.45 0.49 0.47 0.5 1-MI 0.45 Aerosil 1.5 1.5 0.5 Dibenzylidensorbitol 0.5 Hardener 1 90 81.45 80.66 82 87.3 84.6 89.1 W 12 EST 270 257.8 254.6 354.2 266.1 262.3 268.7 Stability of the emulsion A good phase good good bad bad One phase (resin + Aerosil components) TG (DSC) [° C1 110 110 109 110 tangent d (50 Hz) [% at 24 ° C 1 0.5 0.2 at 100 ° C 2 1.6 1.7 Temperature with a loss of 8% [° C] 125 127 123 Tensile strength [MPa] 90 86 75 Elongation at break [%] 1.4 1.4 1.3 Resistance to bending [MPa] 125 137 127 Elongation of fiber edge [%] 1.3 1.6 1.7 Elastic bending module [MPa] 10500 9785 8813 Critical voltage factor K1C [MPa * (m) 1/2] 2.25 2.24 2.12 DSC (Differential Scanning Calorimetry) made with the TA 4000 device Mettier) Electrical values (tangent d) in accordance with DIN 53483, measuring frequency 50 Hz Tensile strength and breaking strength conforming to ISO R527 Flexural strength, edge fiber elongation and elastic flexural modulus conforming to ISO 178 K1C and G1C: Double torsion test Table 1 shows: 1) The properties of a reference material without modification: no hydrophobic transfer is observed, but a good surface hydrophobicity is observed. However, after its loss (by plasma), surface hydrophobia is not restored. 2) The properties of the compositions according to the invention: Example 1 very quickly shows a good hydrophobic transfer effect, also in the second application of the outer layer. In the initial state, the material is quite hydrophobic and returns to recover very quickly the hydrophobicity after the forced loss by plasma, and with it, has an excellent recovery effect. The second example shows practically the same hydrophobic transfer effect as Example 1, but a less good surface hydrophobicity. After its loss (by plasma), it is restored, although less quickly than in Example 1. The third example has a very good and rapid action of hydrophobic transfer effect. 3) The other Comparative Examples show that the effect of recovery can not be influenced simply by the various additives. In none of the cases is hydrophobic reestablishment after forced loss.

Application Example 3 (comparative fissure test): Molded steel bodies are respectively encapsulated with the molding resin system 3, according to the invention (see example according to the invention 3) and a molding resin system without modifications and the resin hardens. The molded bodies are then subjected to a cycle with defined time units, at certain intervals of constant lack of temperature, and after each interval they are examined as to the eventual occurrence of fissures. Preparation of the comparative mixture without modifications (analogously to Comparative Example 1): in a mixer with paddles, 1000 g of epoxy resin 1, 900 g of hardener 1, 5.0 g of water are mixed in a lapse of 30 minutes at 60 ° C. BDMA and 3780 g of W 12 EST quartz powder, and then degas briefly to about 10 mbar. The molded bodies are subjected to the following crack test: Crack test In an aluminum mold with depressions, 20 sample bodies of steel are produced respectively from the molding resin systems to be compared, by applying the APG (Automatic Pressure Gelation) process. In this process, the liquid resin mixture is heated to 40-60 ° C and stirred under vacuum. The resin mixture is then injected under light pressure of 2-5 bar into the mold heated to 140 -150 ° C. Maintaining the pressure, the resin system is allowed to gel in the mold for a few minutes. In the foregoing, each sample body is manufactured with an internal steel body. After gelation, the sample bodies are removed from the mold and further hardened for 10 hours at 140 ° C. Then, the sample bodies are subjected to a certain temperature profile. The temperature profile consists of a series of cycles that have an upper temperature limit of 25 ° C, in which the inspection is also carried out as regards the appearance of cracks. In contrast, the lower limit of the temperature becomes lower with each cycle. In each of them, the samples are quickly taken to the lower temperature limit, respectively, higher and are maintained each time a few hours at the corresponding limit temperature. The cycle in which the sample shows the first fissures is noted. The average crack temperature of a resin system is determined from the frequency distribution of crack formation per cycle. The results of the comparative fissure test of Application Example 3 are presented in the following table: For the comparative system, an average crack temperature of -12 ° C results, however, for the system according to the invention, of -66 ° C. Thus, the systems according to the invention, in comparison with an unmodified system, in addition to their hydrophobic behavior, surprisingly show an obviously better behavior at temperature changes.

Claims (22)

1. A composition characterized in that it contains: (a) an epoxy resin,? (b) an OH-terminated polysiloxane, (c) a cyclic polysiloxane, and (d) a non-ionic, fluoroaliphatic active surface reactant.

2. A composition according to claim 1, characterized in that, based on the total composition of (a), (b), (c) and (d), it contains 77.0 to 97.99% by weight of component (a), 1.0 to 10.0% by weight of component (b), 1.0 to 10.0% by weight of component (c) and 0.01 to 3.0% by weight of component (d), where the sum of components (a), (b), (c) and (d) is 100% by weight.

3. A composition according to claim 1, characterized in that it contains as component (a) a cycloaliphatic epoxy resin or an epoxidation product of an unsaturated natural oil or a derivative thereof.

4. A composition according to claim 1, characterized in that it contains as component (a) diglycidyl ester of hexahydrophthalic acid and 3,4-epoxycyclohexylmethyl-3 '4'-epoxycyclohexanecarboxylate, as well as epoxidized soybean oil or epoxidized linseed oil.

5. A composition according to claim 1, characterized in that it contains as component (b) a polysiloxane of the formula I: wherein Ri and 2, independently of one another, mean alkyl of 1 to 18 carbon atoms, aryl of 5 to 14 carbon atoms or aralkyl of 6 to 24 carbon atoms, and n means an average value of 3 to 60.

6. A composition according to claim 5, characterized in that it contains as component (b) a polysiloxane of the formula I, in which Ri and R, independently of one another, mean methyl, ethyl or phenyl.

7. A composition according to claim 5, characterized in that it contains as component (b) a polysiloxane of the formula I, in which Ri and R2 signify methyl.

8. A composition according to claim 1, characterized in that it contains as component (c) a cyclic polysiloxane of the formula II: wherein Ri and R2, independently of one another, mean alkyl of 1 to 18 carbon atoms, aryl of 5 to 14 carbon atoms or aralkyl of 6 to 24 carbon atoms, and m means an integer of 3 to 12.

9. A composition according to claim 8, characterized in that it contains as component (c) a cyclic polysiloxane of the formula II, in which Ri and R, independently of one another, mean methyl, ethyl or phenyl, and m means a number whole from 3 to 8.

A composition according to claim 8, characterized in that it contains as component (c) octamethylcyclotetrasiloxane, decamethylcyclo-pentasiloxane, dodecamethylcyclohexasiloxane or a dimethylclorsilane hydrolyzate.

11. A composition according to claim 11, characterized in that it contains as component (d) a non-ionic, fluoraliphatic reagent of surface activity of the formula: Rf-COO- (CH2-CH20) m -R (III) Rf- (CH2CH20) m -R (IV) wherein ra means 1 to 200, Rf means a perfluorinated alkyl, linear or branched, of 2 to 22 carbon atoms, and R means H, alkyl of 1 to 6 carbon atoms or Rf.

12. A composition according to claim 11, characterized in that it contains as component (d) compounds of the formula (III) or (IV), in which the molar mass conforms to the theoretical additive formula, is from 300 to 8000.

13. A composition according to claim 12, characterized in that it contains as component (d) 1, 1, 2, 2-tetrahydroperfluoroctanol or Rf-COO- (CH2CH20) mR, wherein Rf means a linear perfluorinated alkyl with 16-18 carbon atoms, m = 110-130 and R = H.

14. A composition according to claim 1, characterized in that it additionally contains as another component (g) emulsifiers or, also, thickeners.

15. A composition according to claim 14, characterized in that it contains as component (g) 0.01 to 3.5% by weight, referred to the sum of components (a) to (d), hydrophilic silicic acid, highly dispersed, untreated.

16. A composition according to claim 1 or 14 or 15, characterized in that it additionally contains a hardener.

17. A composition according to claim 16, characterized in that the hardener is selected from a polycarboxylic acid anhydride (e) or a polycarboxylic acid anhydride (e) together with an accelerator (f).

18. A composition according to claim 16, characterized in that the hardener is an initiator system for cationic polymerization.

19. A composition according to any of claims 1 or 14 to 18, characterized in that it contains fillers.

20. A composition according to claim 19, characterized in that quartz powder, silanized quartz powder, aluminum hydroxide or, alternatively, aluminum dioxide are contained as fillers.

21. Cross-linked products characterized in that they can be obtained by hardening a composition according to any of claims 1 to 20.

22. Electrical insulation material according to claim 21.