DE1957357A1 - Radiation curable paints based on siloxane and products coated therewith - Google Patents

Description

Radiation-curable paints based on siloxane and herewith Coated Products The invention relates to ionizing radiation curable products Siloxane-based paints and products coated therewith.

The subject of the invention is a radiation-curable, film-forming film Paint binder, which in combination of (a) an olefinically unsaturated in a, ß-position Diurethane and / or an epoxy resin which is olefinically unsaturated in a, ß-position and (B) consists of a siloxane which is olefinically unsaturated in a, ß-position, the unsaturated Siloxane by reacting an ester bearing hydroxyl groups in a, ß-position olefinically unsaturated carboxylic acid with a siloxane with at least two functional Groups, namely hydroxyl groups and / or hydrocarbonoxy groups, obtained became. The unsaturated diurethane is made by reacting an organic diisocyanate with an ester containing hydroxyl groups of an ester which is olefinically unsaturated in the α, β-position Carboxylic acid obtained. The preferred hydroxyl group-containing esters are Monohydroxylester of acrylic acid or methacrylic acid, while also cinnamates and Orotonates can be used.

The combinations listed above are in most cases of a suitable viscosity to be applied undiluted to a substrate will. In further embodiments, the combinations come together in solution with vinyl monomers and / or olefinically unsaturated organic resins and / or volatile solvents that can be evaporated off before curing is applied. In a preferred embodiment, the binder solution also contains vinyl monomers, The binder solution is applied to a base in the form of a liquid pile and then by ionizing radiation, especially with an electron beam, networked and hardened.

The invention is concerned with the field of coatings and paints, as well as coated articles of daily use where the painted surface is both a high resistance to abrasion as well as resistance to the influences the weather shows together. The invention particularly relates to objects of daily use with external surfaces made of wood, metal or synthetic polymer solids, the polymerization product formed in situ with one on these surfaces ionizing radiation crosslinked, radiation-curable instriohsbinder <ibertogen, the paint consisting of a film-forming solution of (a) a in a, -position olefinically unsaturated organic diurethane and / or an in a, B-position olefinically unsaturated epoxy resin and (b) one in a, B-position olefinic unsaturated siloxane. The siloxane component is made by implementing a Siloxane with at least two functional groups, namely hydroxyl groups and / or Hydrocarbyl oxy groups, with one hydroxyl group exhibiting Ester of a carboxylic acid which is olefinically unsaturated in a, ß-position, preferably through Implementation of at least two molar proportions of the ester with one molar proportion of the siloxane. The diurethane monomer is obtained by reacting these hydroxyl groups Esters with an organic diisocyanate, preferably by reacting two molar ones Proportions of the ester made with a molar proportion of the diisocyanate. In a In a preferred embodiment, the film-forming solution additionally contains vinyl monomers.

The basis of the invention are therefore paint binders that, in combination (A) a diurethane which is olefinically unsaturated in the α, β-position and / or one in the α-β-position olefinically unsaturated epoxy resin and (b) one which is olefinically unsaturated in the α-13 position Contain siloxane. These materials are ionizing radiation, in particular an electron beam, copolymerizable and give abrasion-resistant paints of great resistance to atmospheric agents, with the siloxane component is responsible for weather resistance. The copolymerization with ionizing Radiation, especially an electron beam, is a far easier way to incorporate it this material as the chemical association with the resin before curing and results in much greater flexibility in terms of the amount of material to be used Siloxane. The application of these ingredients with ionizing radiation, in particular an electron beam, can therefore be copolymerized, allows wide ranges the concentration ratios with regard to the individual components. The combinations can also be used together with vinyl monomers and together with all known, by ionizing radiation curable paint binder resins can be used.

The term "paint" also includes the inclusion of pigment and / or finely ground filler in the binder solution, the binder solution without such a pigment and / or filler or only with one very low content of it, the binder solution being colored if desired can. Thus, the binder solution, which ultimately turns into a permanent, opposite Abrasion and weathering resistant film is transferred from the All or practically all of that used to form the film Material or it can be used as a carrier material for pigment and / or particulate Filler material are present.

The siloxanes used to produce the binder are reactive Hydroxyl groups and / or hydrocarbyl oxy groups attached to at least two of the 5ilIciumatome are bound on. The expression "5iloxan't denotes compounds, which contain a bond - Si - 0 - Si - or a - 0 - Si, the remaining Valences through a hydrocarbon radical, a hydrocarbonoxy group, hydrogen atoms, Hydroxyl groups or oxygen atoms which have such a valence Connect silicon atom with another silicon atom, are saturated.

Both cyclic and acyclic siloxane molecules can be used for production be used.

The acyclic siloxane molecules which can be used to produce the paint binder components according to the invention advantageously contain from about 3 to about 18 silicon atoms per molecule with the corresponding oxygen bonds. The preferred siloxanes are represented by the following general formula: where n has a value of at least 1 and X either (a) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical with t to 8 carbon atoms, preferably an alkoxy radical with 1 up to 4 carbon atoms, or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the groups X separated by a bond X - Si - O - Si - X are either (b) or (c).

The cyclic siloxanes which can be used to produce the paint binder component in the context of the invention contain at least 3, preferably 6 to 12, and usually not more than 18 silicon atoms per molecule with the corresponding oxygen bonds. The cyclic polysiloxanes which can be used can be used in the form of one of the following typical formulas: I.) Xn, SinOn ", where n is an odd positive number of at least 3, n 'the value of - and n" the value n, X either (a ) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms or (c) a hydroxyl group or (d ) denote a hydrogen atom, where at least two of the groupings X separated by a bond X - Si - 0 -Si - X either have the meaning tb) or (c), an example of which is given by the following formula: II.) Xn'SinOn ", where n is an odd positive number of at least 5, n 'the value n + 3 and n" the numbers 6, 6 + 3 or 6 * a multiple of 3, X either (a) a monovalent Hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom , where at least two of the groupings X separated by a bond X - Si - 0 - Si - X have either the meaning (b) or (c), an example of which is given by the following structural formula: III.) Xn'SinOn ", where n is the number 6 or a multiple of 6, nt is the number 8, 8 + 6 or 8 + a multiple of 6, n" is the number 8, 8 + 9 or 8 + a multiple of 9, X either (a) a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical having 1 to 8 carbon atoms, preferably an alkoxy radical having 1 to 4 carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the groups X separated by a bond X-51-0-Si-X have either the meaning (b) or (c), an example of which is given by the following structural formula : - or a dimer, trimer and the like thereof formed by condensation with loss of water or alcohol, IV.) Xn'SinOn ", where n is an even positive number of at least 4, n 'is the value of n + 4 and n" is the Number 4, 4 + 3 or 4 + a multiple of 3, X either (a) a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical having 1 to 8 carbon atoms or (c) denotes a hydroxyl group or (d) denotes a hydrogen atom, where at least two of the groupings X separated by a bond X - Si - O - Si - X have either the meaning (b) or (c), an example of which is given by the following Structural formula is given: where m is the number or a positive integer.

V.) Xn'SinOn ", where n is an even positive integer of at least 8, n 'the value of n + 2 and n" the numbers 11, 11 + 3 or 11 + a multiple of 3, X either (a) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy radical with 1 to 8 carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the Bond x - Si - 0 - Si - X separate groupings X either have the meaning (b) or (c), an example of which is given by the following structural formula: where m is a positive integer.

A large number of processes are known for producing the siloxanes. This includes the regulated hydrolysis of silanes and the polymerisation of a siloxane of low molecular weight, the reaction of silicon tetrachloride with a Alcohol, etc. The manufacture of siloxanes and their incorporation into organic ones Resins is described in U.S. Patents 3,154,597; 3,074,904; 3,044,980; 5,044,979; 3,015,637; 2,996,479; 2,973,287; 2 937 230 and 2 909 549.

The ester having hydroxyl groups is preferably composed of one Monohydroxyalkyl ester of a monocarboxylic acid which is olefinically unsaturated in α, β-position. The preferred esters containing hydroxyl groups are acrylates and methacrylates, as they are the olefinic unsaturation between the terminal carbon atoms included and easily at relatively low doses of ionizing radiation are polymerizable. Examples of such acrylates and methacrylates are given below listed: 2-hydroxyethyl acrylate or methacrylate 2-hydroxypropyl acrylate or methacrylate 2-hydroxybutyl acrylate or methacrylate 2-hydroxyoctyl acrylate or methacrylate 2-hydroxydodecanyl acrylate or methacrylate 2-hydroxy-3-chloropropyl acrylate or methacrylate, 2-hydroxy-3-acryloxypropyl acrylate or methacrylate, 2-hydroxy-3-methacryloxypropyl acrylate or methacrylate, 2-hydroxy-D-allyloxypropyl acrylate or methacrylate, 2-hydroxy-3-cinnamyl propyl acrylate or methacrylate 2-hydroxy-3-phenoxypropyl acrylate or methacrylate 2-hydroxy-3- (o-chlorophenoxy) propyl acrylate or methacrylate 2-hydroxy-3- (p-chlorophenoxy) propyl acrylate or methacrylate 2-hydroxy-3- (2,4-dichlorophenoxy) propyl acrylate or methacrylate, 2-hydroxy-3-acetozypropyl acrylate or methacrylate, 2-hydroxy-3-propionoxypropyl acrylate or methacrylate 2-hydroxy-3-chloroacetoxypropyl acrylate or methacrylate 2-hydroxy-3-dichloroacetoxypropyl acrylate or methacrylate 2-hydroxy-3-trichloroacetoxypropyl acrylate or methacrylate, 2-hydroxy-3-benzoxypropyl acrylate or methacrylate, 2-hydroxy-3- (o-chlorobenzoxy) propyl acrylate or methacrylate, 2-hydroxy-3- (p-chlorobenzoxy) propyl acrylate or methacrylate 2-hydroxy-3- (2,4-dichlorobenzoxy) propyl acrylate or methacrylate, 2-hydroxy-3- (3,4-dichlorobenzoxy) propyl acrylate or methacrylate 2-hydroxy-3- (2,4,6-trichlorophenoxy) propyl acrylate or methacrylate 2-Hydroxy-3- (2,4,5-trichlorophenoxy) propyl aerylate or methacrylate, 2-Hydroxy-3- (o-chlorophenoxyacetoxy) propyl acrylate or methacrylate, 2-hydroxy-3-phenoxyacetoxypropyl acrylate or methacrylate, 2-hydroxy-3- (p-chlorophenoxyacetoxy) propyl acrylate or methacrylate 2-hydroxy-3- (2,4-dichlorophenoxyacetoxy) propyl acrylate or methacrylate 2-hydroxy-3- (2,4,5-trichlorophenoxyacetoxy) propyl acrylate or methacrylate 2-hydroxy-3-crotonoxypropyl acrylst or methacrylate 2-hydroxy-3-cinnamyloxypropyl acrylate or methacrylate 3-acryloxy-2-hydroxypropyl acrylate or methacrylate 3-allyloxy-2-hydroxypropyl acrylate or methacrylate 3-chloro-2-hydroxypropyl acrylate or methacrylate 3-crotonoxy-2-hydroxypropyl acrylate or methacrylate.

In addition to these acrylates or methaerylates, one can also use oinnamates, Use orotonates and the like.

The a, -position unsaturated dialkenyl-diurethanes are by Reaction of an organic diisocyanate with an ester containing hydroxyl groups the same way he used to Manufacture of the above in a, ß-position olefinically unsaturated siloxane was used, produced, which includes the esters listed above.

Further information on such reaction products can be found in U.S. Patent 3,297,745.

The diisocyanates that can be used include: 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl diiocyanate, 4,4'-biphenylene diisocyanate, 3,3) -Dimethoxy-4,4'-dimethy1-4,4'-biphenylene diisocyanate, durene diisocyanate, 1-phenoxy-2,4'-phenylene diisocyanate, 1-tert-butyl-2,4-phenylene diisocyanate and the like.

For special areas of application, it can be advantageous to use a halogenated Diisocyanate, for example 1-chloro-2,4-phenylene diisocyanate 1 to be used.

The ester which is olefinically unsaturated in α, β-position is preferred added to the diisocyanate in part with continued stirring. The ester can be in solution with an inert solvent and the reaction mixture is preferably carried out under an inert atmosphere, for example nitrogen, held while the reaction is in progress. The addition is preferably made at such a rate that the exothermic heat generated is one Does not exceed a value of about 320 C. There is a conversion between the OCN groups of the diisocyanate and the HO groups of the hydroxyl esters, with those in a, I3-position existing unsaturation remains unreacted. The reaction is exothermic and self sustaining. The use of an excess of the ester is advisable or beneficial.

Epoxy resins are used in commercially available coating compounds used, which have good chemical resistance to alkalis, excellent adhesion properties and have both good hardness and flexibility. On the other hand, they have a pronounced. Tendency to "limescale" outdoors and their water resistance is mostly not good. Such coating masses are usually by means of polyamines, organic acids or anhydrides cross-linked. The curing times are between a few minutes and several hours. In contrast to this, according to the invention the, ß-position olefinically unsaturated epoxy resins with the other used in, B-position olefinically unsaturated materials within a few seconds Room temperature in the presence of ionizing radiation, especially electron beams, be networked.

According to a preferred embodiment of the invention, the in a, ß-position olefinically unsaturated epoxy resins by reaction of a diepoxide with a carboxylic acid which is olefinically unsaturated in a, ß-position. According to In further embodiments, the unsaturation is achieved by reacting the diepoxide with an anhydride of a carboxylic acid which is olefinically unsaturated in a, ß-position or a monohydroxy ester of such an acid, this advantageously in excess is used. The manufacture of the for use in the manufacture Diepoxides suitable for the resins used here are detailed in Modern Surface Coatings, Paul Nylen and Edward Sunderland, 1965, Interscience Publishers, John Wiley & Sons Ltd., London - New York - Sydney, Library of Oongress Catalog, Card Number 65-28344, pages 197 to 208. This as the starting material Serving polymers or prepolymers can either be of the epichlorohydrin-bisphenol type or epichlorohydrin - be dolyalcohol-type. A large number of such polymers are commercially available The manufacture of usable epoxy resins is also in the US Patents 2,467,171; 2,538,072, 2,558,969 and 2,694,694 and in many other places in the literature.

The starting polymer advantageously has a molecular weight of at least about 320 and below about 10,000, preferably between about 380 and about 3800. The epoxy resins used in the context of the invention with terminal Unsaturation advantageously have molecular weights above about 370, preferably in the range of about 500 to about 4000, and contain about 0.5 to about 5, preferably about 1 to about 3.5 olefinic ones present in the α, β-position Unsaturations per 1000 units of molecular weight.

As used herein, the term "vinyl monomers" denotes monomeric compounds having a terminal group allyl compounds are excluded. The preferred vinyl monomers are esters of monohydric alcohols having 1 to 8 carbon atoms with acrylic acid or methacrylic acid, for example ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, 2-ethylhexyl acrylate and the like. Alcohols with a higher carbon number, for example with 9 to 15 carbon atoms, can can also be used for the production of such acrylates and methacrylates and are used according to the invention. Vinyl hydrocarbon monomers such as styrene and alkylated styrenes such as vinyl toluene, α-methyl styrene and the like can be used individually or in combination with acrylates and / or methacrylates. Furthermore, in combination with acrylates and / or methacrylates and / or vinyl hydrocarbon monomers, smaller amounts of other vinyl monomers, for example nitriles, such as

Acrylonitrile, acrylamide, N-methylol-acrylonitrile, vinyl halides, for example vinyl chloride, or vinyl carboxylates, for example vinyl acetate, be used.

The expression "ionizing radiation" means radiation here of sufficient energy to make the polymerisatton the one described here Effecting paint films, d. H.

an energy equivalent to about 5000 e-volts or greater.

The preferred method of curing films made from the present Coating compounds on substrates to which they have been applied consist of: that these films have a beam of electrons causing polymerization exposed to average energy in the range of about 100,000 to about 500,000 e-volts will. When using such a beam, a minimum of 25 is preferred 000 e-volts per 2.5 cm distance between the radiation emitting source and the workpiece to be used if the space is filled with air. A setting can be made in the With regard to the relative resistance of the gas in between, which preferably consists of an oxygen-free inert gas such as nitrogen or helium, consists. An electron beam is preferably used as the ionizing radiation, that at the source have an average energy in the range of about 150,000 to has about 500,000 e-volts.

The films formed from the paint compositions according to the invention are advantageous at relatively low temperatures, for example between room temperature (20 to 25O C) and the temperature at which there is significant evaporation of the most volatile Components begins, usually between 20 and 700 a crosslinked and hardened. the Radiant energy is provided in dosage levels from about 0.1 to about 100 Mrads per second applied to a preferably moving workpiece, the amount being a total dosage in the range of about 0.5 bts about 100, usually between about 1 and about 25, and best takes up between about 5 and about 15 Mrad.

The electron irradiation turns the films into sight-bound, Wear-resistant and weather-resistant coatings overflows The abbreviation "Mrad" denotes here 1 000 000 Rnd. The term "wheel" here denotes such a radiation dose, the the absorption of 100 ergs of energy per gram of absorbent, e.g. coating film, results. The electron emitting device can consist of a linear electron accelerator, that for supplying a direct current potential in the range listed above is suitable to exist.

In such a device, the electrons are usually from a hot wire and emitted by a uniform voltage gradient accelerated. The electron beam, which has a diameter of about 3.2 mm at this May have place, is then dragged, so that a funnel-shaped beam results, and then through a metal window, for example made of a magnesium-thorium alloy, Aluminum, an alloy of aluminum and a smaller amount of copper, and the like. Like. From a thickness of about 0.0075 cm on the coating.

The film-forming material should have a sufficiently low application viscosity, in order to achieve a quick application to the substrate in a practically even depth allow, and a sufficiently high application viscosity so that a film of Maintained at least 25 p depth on the vertical surface without drop formation The coating films are usually average in depth from about 2.5 to 100 P with suitable adjustment of the viscosity and the method of application upset. Of course, by choosing the siloxane and the preparation of the a, β-olefinically unsaturated siloxane constituent of the binder solution Hydroxyl ester used, the viscosity of the siloxane component can be varied. In the same way, the choice of the diisocyanate and the one reacted with it Ester the viscosity of the diurethane and thus the binder solution and in the same way by choosing the epoxy resin, its viscosity and thus also the binder solution can be varied and adjusted. Also the type and amount of that in the binder solution Vinyl monomers used in a preferred embodiment can be so chosen be that the viscosity of the binder solution with the formation of a suitable consistency for application according to normal parabelling methods, For example, spraying, rolling, coating and the like can be set. In the case of other application options, the use of in a, ß-position influences olefinically unsaturated resins in the binder, for example of polyesters such as Vinyl resins, epoxy resins and the like, the viscosity of the binder. Within the scope of the invention it is also the viscosity of the polymerizable binder by volatile solvents, for example xylene, toluene, methyl ethyl ketone and the like, which are driven off before curing can be to decrease.

The in cr, ß-position olefinically unsaturated product of siloxane and unsaturated ester and the α, β-olefinically unsaturated product Diisocyanate and unsaturated ester or that which is olefinically unsaturated in a, ß-position Epoxies are both homopolymerizable and with each other, with vinyl monomers and copolymerizable with α, β-olefinically unsaturated organic resins.

In a first embodiment, the only ones are polymerizable Components of the binder the product of siloxane and unsaturated ester and that Product made from diisocyanate and unsaturated ester. In this embodiment contains the binder, excluding solvents, from about 20 to about 80, preferably about 30 to about 70 parts by weight of the siloxane-unsaturated ester product and correspondingly from about 80 to about 20, preferably from about 70 to about 30 parts by weight of the product of diisocyanate and unsaturated ester.

In a second embodiment, the binder solution contains as polymerizable Components vinyl monomers in addition to the polymerizable components of the first embodiment. In this embodiment, the binder solution contains about 10 to about 200, preferably about 20 to about 80 parts by weight of vinyl monomers, about 20 to about 80, preferably about 30 to about 70 parts by weight of the product of siloxane and unsaturated ester and from about 20 to about 80, preferably about 30 to about 70 parts by weight of the diisocyanate-unsaturated ester product.

In a third embodiment of the invention, the binder solution contains as polymerizable constituents an organic unsaturated in α, β-position Resin in addition to the a, ß-olefinically unsaturated siloxane and the diurethane which is olefinically unsaturated in a, ß-position and / or olefinically in a, ß-position unsaturated epoxy. In this embodiment the olefinically unsaturated one consists Resin consists essentially of carbon, hydrogen and oxygen and has an average molecular weight above about 500 and below about 25,000 with molecular weight preferred ranges from about 1,000 to about 15,000. In this embodiment contains the binder about 20 to about 80, preferably about 70 to about 70 parts by weight of the in α, β-position of olefinically unsaturated resin, about 20 to about 80, preferably about 30 to about 70 parts by weight of the siloxane-unsaturated ester product and about 20 to about 80, preferably about 30 to about 70 parts by weight of the product from diisocyanate and unsaturated ester or from the unsaturated epoxide.

In a fourth embodiment, the binder solution contains all of them four or five of the polymerizable ingredients listed above. At this In the embodiment, the binder solution contains from about 10 to about 300, preferably about 20 to about 200 parts by weight of vinyl monomers, about 20 to about 80, preferably about 30 to about 70 parts by weight of the in aß - '; position olefinically unsaturated organic Resins, about 2 () to about 80, preferably about 30 to about 70 parts by weight of the product of siloxane and unsaturated ester and about 20 to about 80, preferably about 30 up to about 70 parts by weight; leel product made from diisocyanate and unsaturated Ester and / or the unsaturated epoxy. Smaller amounts of other polymerizable Monomers, for example allyl compounds, can be used and form the rest.

Furthermore, it is within the scope of the invention to use a binder solution, wherein the unsaturated epoxy resin and the product of siloxane and unsaturated ester are the only polymerizable components and this coating material in Solution, optionally together with a volatile solvent, for example apply the above, which can be evaporated before curing would have.

Palls the binder is essentially olefinic in the a, ß-position unsaturated epoxy resin and the α9ß-unsaturated polysiloxane consists, the binder preferably contains about 20 to about 80, advantageously about 50 to about 70 parts by weight of the epoxy resin and correspondingly about 80 to about 20, advantageously about 70 to about 30 parts by weight of the siloxane.

If the binder involves significant amounts of additional vinyl monomers contains, the binder advantageously contains about 10 to about 200, preferably about 20 to about 100 parts by weight of vinyl monomers and the resinous ingredient which about 20 to 80, preferably about 30 to 70 parts by weight of the unsaturated siloxane and about 20 to about 80, preferably about 30 to about 70 parts by weight of the epoxy resin matters. Smaller proportions of other polymerizable monomers, for example Allyl compounds can optionally be used and make up the remainder.

In particular, however, the invention is concerned with such coatings in which the film-forming solution, apart from the vinyl monomers, essentially from the diurethane which is olefinically unsaturated in the α, β-position and / or in the α, β-position olefinisoh unsaturated epoxy resin as a binder resin and the product consist of siloxane and unsaturated ester, d. H.

Coating compositions in which these ingredients contain at least 85% by weight of the make up film-forming binder material. The paints obtainable according to the invention have such weatherability and abrasion resistance that they can even be used on floors that are outdoors, or even passable by hard wheels Roller shoe tracks and the like can be used excellently.

The following examples serve to further illustrate the invention.

Example 1 A radiation curable paint was made up of the following Components manufactured in the following ways: (a) Manufacture of the unsaturated siloxane ester component: reactants parts by weight of acyclic Siloxane with (1 functional methoxy groups 178 hydroxyethyl methacrylate 118 tetraisopropyl titanate 0.32 hydroquinone 0.06 (1) Commercially available methoxylated partial hydrolyzate of monophenyl and phenylmethylsilanes (largely condensed dimethyltriphenyltrimethoxytrisiloxane) with the following properties: average molecular weight 750 - 850 average Number of silicon atoms per molecule 5 - 6 Average number of methoxy groups 3 - 4 per molecule Process The siloxane, the methacrylate monomer and hydroquinone as a polymerization inhibitor were heated to 1000 C in one with one Distillation receiver of the Barrett-type equipped flask heated. The titanate was added as a catalyst and the temperature to 1500 C for 3 hours increased, during which time the methanol was removed by distillation became. The cooled reaction product had a viscosity of 0.6 Stoke at 250 C.

(b) Preparation of the unsaturated diisocyanate ester component: Reactant parts by weight of 2-hydroxyethyl methacrylate 44.08 Tolylen-diisocyt (Monomer Mixture (1) 27.00 (1) 80% 2,4-tolylene diisocyanate 20% 2,6-tolylene diisocyanate Procedure The diisocyanate was added dropwise to the methacrylate while stirring added to a nitrogen gas atmosphere, the rate of addition being so controlled was that the value of 32 C was not exceeded by the 0 exotherm. That Stirring was continued for 1 hour after the addition was complete, and then the mixture left to stand for 16 hours at room temperature.

(c) Preparation of the paint binder solution: copolymerizable components Parts by weight Unsaturated Silox, an ester product nadh (a) 25 Unsaturated diisocyanate ester product according to (b) 75 The polymerizable reactants became in solution with xylene on a metal base to an average depth of about 25 ji applied. The xylene was evaporated and the coating on the surface of the Crosslinked the substrate by exposing the coating to an electron beam.

The irradiation conditions were as follows: electron beam potential 295 KV electron beam current intensity 25 ma dosage 15 Mrad atmosphere N2 There were excellently coated sheets preserved.

Example 2 The procedure of Example 1 was repeated, however 75 parts by weight of the unsaturated siloxane ester product and 25 parts by weight of the unsaturated Diisocyanate ester product used.

Example 3 The procedure of Example 1 was repeated, however 50 parts by weight of the unsaturated siloxane ester product, 25 parts by weight of the unsaturated Diisocyanate ester product and 50 parts by weight of an equimolar mixture of styrene and methyl methacrylate were used, the xylene being omitted. The movie was applied to substrates made of metal, wood and synthetic polymers, for example ABS, an acrylonitrile-butadiene-styrene copolymer, the film turned out to be an average Depth of about 30 µ is applied and taken by exposure to an electron beam Applying ler conditions cured according to Example 1, with the irradiation continued until a tack-free film was formed.

Example 4 The procedure of Example 1 was repeated, however 25 parts by weight of the unsaturated siloxane ester product, 50 parts by weight of the unsaturated Diisocyanate ester product and 50 Ges parts of a vinyl monomer mixture of α-methylstyrene, Ethyl acrylate and butyl methacrylate were used, the xylene being omitted. The film was made on substrates made of metal, wood and synthetic polymers, for example ABS, an aryl nitrile butadiene styrene copolymer, is applied. The movie became too Applied to an average depth of about 30 and exposed to one Electron beam cured using the conditions of Example 1, wherein irradiation was continued until a non-tacky film was formed.

Example 5 The procedure of Example 1 was repeated, however 50 parts by weight of the unsaturated siloxane ester product, 50 parts by weight of the unsaturated Diisocyanate ester product and 50 parts by weight of a vinyl monomer mixture of methyl methacrylate, Butyl acrylate and 2-ethylhexyl acrylate were used, the xylene being omitted. The film was made into one using the same base as in the previous example average depth of about 20 f and applied by exposure to one Electron beam cured using the conditions of Example 1, wherein irradiation was continued until a non-tacky film was formed.

The products of Examples 2 to 5 were excellent coated Documents.

Example 6 The procedure of Example 1 was repeated, however 50 parts by weight of the unsaturated siloxane ester product, 50 parts by weight of the unsaturated Diisocyanate ester product, 50 parts by weight of methyl methacrylate and 50 parts by weight of one used in a, ß-position olefinically unsaturated polyester resin, the xylene was omitted. The film-forming solution was based on those listed above Underlays applied to an average depth of about 38 P and on top by exposing the film to an electron beam using the conditions crosslinked according to example 1, the irradiation being continued until a non-tacky one Film was formed.

The α, β-olefinically unsaturated resin used here was prepared in the following manner: Parts by weight of maleic anhydride from the materials 147 Phthalic anhydride 429 Neopentyl glycol 503 Process All reactants were placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and a 25 cm high Vigreux column with a Barrett trap to remove the Was equipped with condensation water, introduced. The respondents were slowly heated to 165 ° C, where the distillation of the condensation water began. Nitrogen was bubbled through the reaction mixture during the reaction. the The reaction temperature rose as the water continuously removed until a maximum temperature of 2250 C was reached. The column then became removed from the system, 3 wt.% xylene added for azeotropic water removal and heating continued until the acid number reached 30. The product was cooled to 1000 ° C. and 0.03% by weight hydroquinone as an inhibitor added and the polymer to a non-volatile content of 80% thinned with styrene.

Excellent coated documents were obtained.

Example 7 The procedure of Example 6 was repeated, however as a resin which is olefinically unsaturated in a, ß-position, a copolymer of vinyl monomers used. The resin was prepared in the following manner: starting materials parts by weight Xylene 600 methyl methacrylate 196 ethyl acrylate 333 glycidyl methacrylate 71 azobisisobutyronitrile 6 hydroquinone 0.12 methacrylic acid 42 triethylamine 0.96 process The for implementation The solvent, xylene, was added to a flask equipped with a stir bar, addition funnel, Thermometer, nitrogen inlet tube, and condenser were placed. the The amount of xylene was equal to the total weight of the vinyl monomers to be added. The xylene was heated to reflux, nitrogen through the solution while heating and blown during implementation. The mixed monomers and the initiator (Azobisisobutyronitrile) became uniform to the refluxed solution during a period of 2 hours added. The initiator weight was 10 parts by weight per 1,000 parts by weight of the vinyl monomers. The reaction solution became held at reflux until the conversion of the monomers to the polymer is greater than 97% (8 to 16 hours).

In a second stage, the hydroquinone was added as an inhibitor and then methacrylic acid added to the remaining epoxy groups of the polymer responded. Triethylamine was used as a catalyst. This esterification conversion was carried out at reflux temperature until 80% esterification was achieved was determined by the remaining acid number. The xylene was then vacuum distilled removed and the polymer dissolved in methyl methacrylate so that the weight ratio from polymers to solvents the ert was two.

Example 8 The procedure of Example 6 was repeated, however an epoxy resin is used as a resin which is olefinically unsaturated in the α, ß-position, which was prepared in the following manner: Into a 2,000 ml three-neck flask, the was equipped with a stirrer, dropping funnel, thermometer and nitrogen inlet, 1 mole of 2,3-butanediol (91.12 parts by weight) and 4 moles of epichlorohydrin (570 parts by weight) brought in. The temperature was maintained at 110 ° C while adding 2 moles of sodium hydroxide (80 parts by weight) were added dropwise as a 30% aqueous solution. I) the rate of addition was regulated so that the reaction mixture remained neutral. After about 3 hours the organic layer was separated, dried, distilled and the polymer obtained, To 210 g of diene polymers were 6 parts by weight of methacrylic acid, the 0.1 part by weight flydroquinone was added. While stirring under a nitrogen atmosphere was the mixture to 1400 a for 20 minutes heated and then on Room temperature, d. H. 260 a, cooled.

Example 9 The procedure of Example 8 was repeated, however an epoxy resin is used, which is obtained by reacting an epichlorohydrin bisphenol epoxide with acrylic acid.

The products of Examples 7 to 9 also had excellent coatings on.

Example 10 The procedures of the preceding examples were repeated, however, as a polysiloxane for the preparation of the unsaturated siloxane reaction product a methoxylated partial hydrolyzate of monophenyl and phenylmethylsilanes is used, which consisted essentially of dimethyltriphenyltr imethoxytrisiloxane and the following typical properties: average molecular weight 470 compound weight 155 Specific weight at 250 a 1.105 Viscosity at 250 a, Centistokes 13 Example 11 The procedures of Examples 1 to 10 were repeated, but as the polysiloxane for the preparation of the unsaturated siloxane ester reaction product dibutoxytetramethyldisiloxane used.

Example 12 The procedures of Examples 1 to 10 were repeated, je dooh as a polysiloxane to produce the unsaturated siloxane ester reaction product Dipropoxytetramethylcyclotrisiloxane is used.

Example 13 The procedures of Examples 1 to 10 were repeated, but in a, ß-position olefinically unsaturated siloxane composed of the following components produced in the following manner: Reactants Ges. share Cyclic siloxane with functional hydroxyl groups (1) 200 hydroxyethyl methacrylate 71 Hydroquinone 0.1 xylene (solvent) 116 (1) Commercially available cyclic polysiloxane with functional hydroxyl groups and the following typical properties: hydroxyl content, Dean Stark Percent Condensable 5.5 Percent Free 0.5 Average Molecular Weight 1600 compound weight 400 refractive index 1.531 to 1.539 softening point mercury method Durran, C 93 at 60% solids in xylene specific gravity at 25 ° C 1, ß75 viscosity at 250 C, Centipoises 33 Gardner-Hoidt A - 1 A three-necked flask with a stirrer, Thermometer, nitrogen inlet and Barrett's trap was fitted with the siloxane, the methacrylate, the xylene and the ITydroquinone charged. This solution was heated to reflux, 1380 ° C., for 30 minutes. Nitrogen was through the reaction mixture was blown throughout the process. That as a by-product The water formed was slowly removed and the temperature gradually rose to 1460 C. After 5 hours, 8.5 ml of water was collected, indicating almost complete conversion. The xylene was removed by distillation under reduced pressure and the product then diluted to a non-volatile content of 70 ff with methyl methacrylate Example 14 The procedures of Examples 1 to 13 were repeated, but for preparation of the unsaturated siloxane ester product, an equivalent amount of 2-hydroxyethyl acrylate used instead of hydroxyethyl methacrylate.

Example 15 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated siloxane ester product Amount of 2-hydroxypropyl methacrylate used instead of the Ifydroxyäthylmethacrylats.

Example 16 The procedures of Examples 1 to 13 were repeated, However, in the production of the unsaturated SiAoxane ester product, an equivalent one Amount of 2-Hydroxybuytlacrylat used instead of Hydroxyäthylmethacrylat.

Example 17 The procedures of Examples 1 to 13 were repeated, However in the manufacture of the unsaturated siloxane ester product an equivalent amount of 2-hydroxyoctyl acrylate in place of the hydroxyethyl methacrylate used.

Example 18 I) The procedures of Examples -1 to 13 were repeated, however, an equivalent in the preparation of the unsaturated siloxane ester product Amount of 2-hydroxydodecanyl methacrylate used instead of the hydroxyethyl methacrylate Example 19 The procedures of Examples 1 to 13 were repeated, but with the Prepare unsaturated siloxane ester product an equivalent amount of 3-chloro-3-hydroxypropyl acrylate used instead of hydroxyethyl methacrylate.

Example 20 The procedures of Examples 1 through 13 were repeated, however, an equivalent in making the unsaturated siloxane ester product Amount of 3-acryloxy-2-hydroxypropyl methacrylate instead of the hydroxyethyl methacrylate used.

Example 21 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated siloxa ester product Amount of 3-acryloxy-2-hydroxypropylyacrylate instead of the hydroxyethyl methacrylate calibrated.

Example 22 The procedures of Examples 1 to 13 were repeated, ever but in making the unsaturated siloxane ester product an equivalent amount of 3-cronoptoxy-2-hydroxypropyl acrylate in place of the hydroxyethyl methacrylate used.

Example 23 The procedures of Examples 1 to 13 were repeated, however, one equivalent in making the unsaturated siloxane ester product Amount of 3-acryloxy-2-hydroxypropyl cinnamate instead of hydroxyethyl methacrylate used.

Example 24 I) The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated siloxane ester product Amount of 3-acryloxy-2-hydroxypropyl crotonate instead of the hydroxyethyl methacrylate used.

Example 25 The procedures of Examples 1 to 13 were repeated, however, an equivalent product is used in the production of the unsaturated diisocyanate product Amount of 2-Ilydroxyä thylacrylat used instead of Hydroxy # thylmethacrylats.

Example 26 The procedures of Examples 1 to 13 were repeated, however, an equivalent in the preparation of the unsaturated di-isoynate ester product Amount of 2-Ilydroxypropylmethacrylat used instead of Hydroxyäthylmethacrylat.

Example 27 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 2-hydroxybutyl acrylate used instead of the hydroxyethyl methacrylate.

Example 28 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 2-hydroxy-octyl acrylate used instead of the hydroxyethyl methacrylate.

Example 29 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 2-Hydroxydodecanylmethacrylat used instead of Hydroxyätliylmethacrylats.

Example 30 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 3-chloro-2-hydroxypropyl acrylate used instead of the hydroxyethyl methacrylate.

Example 31 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the viisocyanate ester unsaturated product Amount of 3-acryloxy-2-hydroxypropyl methacrylate instead of I! Ydroxyäthylmetllacrylats used.

Example 32 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 3-crotonoxy-2-hydroxypropyl acrylate instead of the hydroxyethyl methacrylate used.

Example 33 The procedures of Examples 1 to 13 were repeated, however, an equivalent in making the unsaturated diisocyanate ester product Amount of 3-acryloxy-2-hydroxypropylcinnamate instead of hydroxyethyl methacrylate used.

Example 34 The procedures of Examples 1 to 13 were repeated, however, an equivalent is used in the manufacture of the unsaturated isocyanate ester product Amount of 3-acryloxy-2-hydroxypropyl crotonate instead of the hydroxyethyl methacrylate used.

Example 75 The procedures of Examples 1 to 13 were repeated, however, hexamethylene diisocyanate is used instead of tolylene diisocyanate.

Example 36 The procedures of Examples 1 to 13 were repeated, however, 1,3-xylylene diisocyanate is used instead of tolylene diisocyanate.

Example 37 The procedures of Examples 1 to 13 were repeated, however, in the preparation of the α, β-olefinically unsaturated siloxane such an amount of the monohydroxy ester used to react with at least a functional hydroxyl or hydrocarbonoxy group of the siloxane was sufficient however, for reaction with all such functional groups of the siloxane molecules Was insufficient in the reaction mixture.

Example 38 I) The procedures of Examples # through 13 were repeated, however, in the preparation of the α, β-olefinically unsaturated siloxane an amount of the monohydroxy ester used in excess of that used for Reaction with all functional hydroxyl and hydrocarbonoxy groups of the siloxane molecule in the reaction mixture was required.

Example 39 1 procedure of Examples 1 to 13 were repeated; however the fIart1ltlg with t; a Stranhlpotentil - carried out by 175,000 volts, with the workpiece three inches from the emitter, and from 400,000 Volts carried out at a distance of 25 cm, each in a nitrogen atomic sphere was worked, which contained a small amount of carbon dioxide.

The products of Examples 10 to 39 also had excellent coatings on.

Example 40 A paint was made by mixing 80 parts by weight of the unsaturated siloxane ester product according to Example 1, 80 parts by weight of the unsaturated Diisocyanate ester product according to Example 1, 80 parts by weight of that from vinyl monomers existing resin according to Example 7 and about 300 parts by weight of methyl methacrylate produced, The resulting film-forming solution was applied to a metal base and then cross-linked with an electron beam according to the previous example.

Example 41 A paint was made by mixing 20 parts by weight of the unsaturated siloxane ester product according to Example 1, 20 parts by weight of the unsaturated Diisocyanate ester product according to Example 1, 20 parts by weight of the polyester resin Example 6 and about 10 parts by weight of methyl methacrylate. The obtained film-forming Solution was applied to a metal base and then applied with an electron beam In accordance with the examples above, crosslinked.

The products of Examples 40 and 41 also had excellent coatings.

Example 42 A paint comprising an unsaturated siloxane ester product and vinyl monomers was made from the following ingredients in the following listed way: (a) Preparation of the siloxane component Reactant parts by weight of acyclic siloxane with 8 functional methoxy groups (178 Hydroxyethyl methacrylate 118 Tetraisopropyl titanate 0.32 II Hydroquinone 0.06 (1) See example 1.

The siloxane, the methacrylate monomer and hydroquinone as a polymerization inhibitor were heated to 1000 C in one with a Barrett-type still equipped flask heated. The titanate was added as a catalyst and the Temperature increased to 1500 C over 3 hours, during which time the Methanol was removed by distillation. The cooled reaction product had a viscosity of 0.6 stoke at 250 C.

(b) Preparation of the α, β-olefinically unsaturated epoxy resins: An epoxy polymer was prepared in the following manner: 1 mol of 2,3 were added to a three-necked flask of 2000 ml, which was equipped with a stirrer, dropping funnel, thermometer and nitrogen inlet -Butanediol (91.12 g) and 4 moles of epichlorohydrin (370.0 g) were introduced. The temperature was maintained at 1100 ° C. while 2 moles of sodium hydroxide (80 g) were added dropwise as a 30% aqueous solution. The rate of addition was adjusted so that the reaction mixture remained neutral. After about 3 hours the organic layer was separated, dried, distilled and the polymer recovered. This polymeric product is represented by the following structural formula: To 210 g of this polymer, 86 g of methacrylic acid containing 0.1 g of hydroquinone were added. While stirring in a nitrogen atmosphere, the mixture was heated to 1400.degree. C. for 20 minutes and then cooled to room temperature, ie 260.degree. The resulting unsaturated polyepoxide polymer is represented by the following structural formula: Two coatings were produced and applied as films of about 50 P thickness from metal plates of about 7.5 x 12.5 cm made of phosphatized sheet steel and cured thereon by ionizing radiation in a nitrogen atmosphere.

(c) Preparation of the paint: components parts by weight of siloxane ester product according to (a) 10 epoxy resin of formula (2) 15 methyl methacrylate 5 This paint was applied to a metal base to a depth of about 25 »in average and cured to a hard film using the following irradiation conditions: Electron beam potential 270 KV electron beam current intensity 25 ma dosage 15 Mrad atmosphere nitrogen Distance, workpiece to emitting point 25 cm The products possessed excellent Coatings.

Example 43 The process of Example 42 was repeated, but instead of the epoxy resin used there, a number of commercially available epoxy resins of the bisphenol-A-epichlorohydrin-2 type were used, each of which is represented by the following formula 3: The resins used have the following typical properties: Be Melt viscosity Epoxy equivalent average average drawing range (Poisen at equivalent weight molecular value for n in (1) (2) 25 ° C) (2) (3) lar weight formula 3 Epon 828 liquid 100-150 175-210 85 380-Epon 834 liquid 3.8-9.0 (4) 225-290 105 470 0.5 Epon 1001 64-76 0.8-1.7 (5) 450 -525 130 900 2.0 Epon 1004 95-105 4.3-6.3 (5) 870-1025 175 1400 3.7 Epon 1007 125-132 17.5-27.0 (5) 1650-2050 190 2900 8.8 Epon 1009 140-155 36.2-98.5 (5) 2400-4000 200 3750 12.0 (1) Shell Chemical Co; in Europe it is called "Epikote" (2) grams of resin containing 1 g-equivalent of epoxide (3) Necessary number of grams of resin for complete esterification of 1 mole of a monobasic acid, e.g. 280 g of a C18 fatty acid (4) Obtained as 70% solution in butyl carbitol (5) Obtained as a 40% solution in butyl carbitol. Example 44 The process according to Example 43 was repeated, but using methacrylic acid instead of acrylic acid for the reaction with the epoxy resins listed.

The products of Examples 43 and 44 also showed excellent coatings.

Example 45 The procedures of Examples 42 to 44 were repeated, however, the siloxane component from the following components in the specified Ways to prepare: reactants parts by weight of cyclic siloxane with functional Hydroxyl groups (1 200 hydroxyethyl methacrylate 71 hydroquinone 0.1 xylene (solvent) 116 (1) xylene, see example 13.

Procedure One with a stirrer, thermometer, nitrogen inlet and Three-necked flask equipped with Barrett's trap was filled with the siloxane, methacrylate, charged to the xylene and the hydroquinone. This solution was brought to reflux, 1380 C, heated for 30 minutes. Nitrogen was added to the reaction mixture during blown in throughout the process. The water formed as a by-product became slowly decreased and the temperature rose gradually to 1460 0. After two hours 8.5 ml of water were collected, indicating almost complete conversion. That Xylene was removed by distillation under reduced pressure.

The products showed excellent coatings.

Example 46 The procedure of Example 42 was repeated, however as a polysiloxane for the preparation of the α, β-olefinically unsaturated siloxane a methoxylated partial hydrolyzate of monophenyl and phenylmethylsilanes is used, consisting essentially of dimethyltriphenyltrimethoxytrisiloxanes and the following typical properties: Average molecular weight 470 compound weight 155 Specific gravity at 250 C 1.105 Viscosity at 250 a, Centistokes 17 Example 47 The procedures of Examples 42, 44 and 46 were repeated except for the vinyl monomer content adjusted so that it was 10% by weight of the binder solution.

Example 48 The procedures of Examples 42, 45 and 46 were repeated, However, the content of vinyl monomers is set so that it is 25% by weight of the binder solution and the vinyl monomers used were a mixture of styrene and methyl methacrylate used.

Example 49 The procedures of Examples 42, 45 and 46 were repeated, However, the content of vinyl monomers is set so that it is 50% by weight of the binder solution and the vinyl monomers used was an equimolar mixture of methyl methacrylate, Butyl acrylate and octyl acrylate are used.

Example 50 The procedures of Examples 42, 45 and 46 were repeated, However, the content of vinyl monomers is set so that it is 60% by weight of the binder solution and the vinyl monomers used was an equimolar mixture of vinyl toluene and butyl methacrylate and 2-ethylhexyl acrylate are used.

Example 51 The procedures of Examples 42, 45 and 46 were repeated, however, a solution free of vinyl monomers is used if necessary Spray consistency diluted with an equimolar mixture of toluene and methyl ethyl ketone became.

Example 52 The procedures of Examples 42, 45 and 46 were repeated, but 1 part by weight of the epoxy resin and 4 parts by weight of the unsaturated siloxane resin product used.

Example 53 The procedures of Examples 42, 45 and 46 were repeated, but 1 part by weight of the unsaturated siloxane resin product and 4 parts by weight of the epoxy resin used.

Example 54 The procedures of Examples 42, 45 and 46 were repeated, but 30 parts by weight of the unsaturated siloxane resin product and 70 parts by weight of the Epoxy resin used.

Example 55 The procedures of Examples 42, 45 and 46 were repeated, However 70 parts by weight of the unsaturated siloxane resin product and 30 parts by weight of the epoxy resin used.

Example 56 The procedure of Example 42 was repeated, however as a polysiloxane for the preparation of the α, β-olefinically unsaturated siloxane Dipropoxytetramethylcyclotrisloxane is used.

Example 57 The procedure of Example 42 was repeated, however as a polysiloxane for the preparation of the α, β-olefinically unsaturated siloxane Dibutoxytetramethyldisiloxane is used.

Example 58 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 2-hydroxyethyl acrylate instead of the hydroxyethyl methacrylate used in the production of the a, ß-olefinically unsaturated siloxane, Example 59 The procedures of Examples 42 to 46 were repeated but one equivalent amount of 2-hydroxypropyl methacrylate instead of hydroxyethyl methacrylate used in the production of the α, β-olefinically unsaturated siloxane.

Example 60 The procedures of Examples 42 to 46 were repeated, However, an equivalent amount of 2-hydroxybutyl aylate instead of Hydroxyethyl methacrylate in the production of the α, ß-unsaturated olefin Siloxane used.

Example 61 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 2-hydroxydodecanyl methacrylate instead of the hydroxyethyl methacrylate used in the production of the a, B-position olefinically unsaturated siloxane.

Example 62 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 3-chloro-2-hydroxypropyl acrylate instead of the hydroxyethyl methacrylate used in the production of the a, B-position olefinically unsaturated siloxane.

Example 63 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropyl methacrylate instead of hydroxyethyl methacrylate in the production of the olefinic in a, B-position unsaturated siloxane used.

Example 64 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 3-crotonoxy-2-hydroxypropyl acrylate in place of the Hydroxyethyl methacrylate in the production of the α, β-olefinically unsaturated Siloxane used.

Example 65 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropylcinnamate in place of the Hydroxyethyl methacrylate in the production of the α, ß-unsaturated olefin Siloxane used.

Example 66 The procedures of Examples 42 to 46 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropyl crotonate in place of the Hydroxyethyl methacrylate in the production of the α, ß-unsaturated olefin Siloxane used.

Example 67 The procedures of Examples 42 to 46 were repeated, however, in the preparation of the α, β-olefinically unsaturated siloxane such an amount of the monohydroxy ester used to react with at least a functional hydroxyl or hydrocarbonoxy group of the siloxane was sufficient, however, to react with all such functional groups of the siloxane molecules was insufficient in the reaction mixture.

Example 68 The procedures of Examples 42 to 46 were repeated, However, in the production of the α, β-olefinically unsaturated siloxane such an amount of the monohydroxy ester used, which is in excess over the for Reaction with all functional hydroxyl and hydrocarbonoxy groups the required amount of siloxane molecules was present in the reaction mixture.

The products obtained according to Examples 46 to 68 also showed excellent coatings.

Example 69 A pigmented paint was prepared by using 75 Parts by weight of the unsaturated siloxane ester product according to Example 45 with 150 parts by weight a commercial titanium dioxide pigment and 20 parts by weight of methyl methacrylate premixed became. The mixture was shaken with an equal amount of glass beads in ground in a conventional paint shaker for 30 minutes. The premix was diluted with a further 75 parts by weight of the unsaturated siloxane ester product and 65 parts by weight of the mixture obtained were with 35 parts by weight of an equimolar Diluted mixture of styrene and methyl methacrylate. This mixture became 75 Parts by weight of methyl methacrylate and 65 parts by weight of that which is olefinically unsaturated in a, ß-position Spoxy ester according to Example 42 was added.

The paint was applied to substrates made of metal, wood and polymers (ABS, d. H. Acrylonitrile-butadiene-styrene copolymers) to an average depth of about 38 P applied and then with an electron beam corresponding to the Method of the preceding examples cured.

Products with excellent coatings were obtained.

Example 70 The procedures of Examples 42 to 46 were repeated, however, curing with a beam potential of 175,000 volts at a distance of the workpiece from the emitting source of about 7.5 cm and 400,000 volts carried out a distance of 25 cm, each in a nitrogen atmosphere was worked, which contained small amounts of carbon dioxide.

The products thus obtained had excellent coatings.

Example 71 Anetrichsmassen were prepared by 160 parts by weight of the unsaturated siloxane ester product according to Example 42 and 160 parts by weight of the Epoxy resin according to Example 42 were mixed, this mixture in two equal parts was divided and such a proportion with 100 parts by weight of methyl methacrylate and the other portion was diluted with 200 parts by weight of methyl methacrylate. The received film-forming solutions were applied to metal substrates and then with a Electron beam crosslinked according to the preceding examples.

Example 72 paint compositions were prepared by adding 40 parts by weight of the unsaturated siloxane enter product according to Example 42 and 40 parts by weight of the epoxy resin were mixed according to Example 42, this mixture was divided into two equal parts and such a portion with 10 parts by weight of methyl methacrylate and the other Portion was diluted with 20 parts by weight of methyl methacrylate. The obtained film-forming Solutions were applied to metal substrates and then applied with an electron beam crosslinked according to the preceding examples.

The products of Examples 71 and 72 also had excellent coatings on.

Example 73 The procedure was as in Example 71, but instead of the 160 parts of the epoxy resin according to Example 42, a mixture of parts of this Epoxy resin and 80 parts by weight of the diurethane used in Example ib. There were again received excellent coatings.

The invention therefore results in radiation curable Paint binders and coatings formed with them and hardened by ionizing radiation on substrates made from a film-forming solution of (a) an olefinic in α, ß-position unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups, in particular lower alkoxy groups, with a hydroxy ester which is olefinically unsaturated in a, ß-position Carboxylic acid was obtained and from (b) one olefinically unsaturated in a, B-position Epoxy resin and / or a, ß-position olefinically unsaturated diethane, which by reacting a diisocyanate with a hydroxy ester in a, ß-position olefinically unsaturated carboxylic acid was obtained. The hydroxyesters are preferably made from monohydroxy ester of acrylic acid or methacrylic acid. The siloxane preferably contains about 3 to about 18, especially 3 to 12 silicon atoms per molecule.

The preferred hydroxy esters for making the unsaturated siloxanes however, consist of the monohydroxy esters of acrylic acid and methacrylic acid with dihydric aliphatic alcohols having 2 to 8 carbon atoms.

The a, ß-position favorably contains that which is olefinically unsaturated Epoxy resin about 0.5 to about 5, preferably about 1 to 3.5 units of olefinic a, ß-unsaturation per 1000 units of the molecular weight. Preferably will the a, B-position olefinically unsaturated diurethane by converting a molar Part of a diisocyanate with 2 molar parts of a monohydroxy ester of acrylic acid or methacrylic acid produced and used.

The film-forming solution conveniently contains about 20 to 80, preferably about 30 to about 70 parts by weight of the a, B-position olefinically unsaturated siloxane and about 80 to about 20, in particular about 70 to about 30 parts by weight of the α, β-position olefinically unsaturated epoxy resin or that which is olefinically unsaturated in a, B-8-position Direthans. In a favorable embodiment, there are also about 10 to about 200 parts by weight of vinyl monomers contained in the filmbilanaen solution. Possibly can still further 20 to 80 parts by weight of a further in the α, ß-position olefinically unsaturated organic resin may be included.

Examples include polyesters, which are preferably about 1 up to about 3.5 units of olefinic α, ß-unsaturation per 1000 units of des Have molecular weight. Further examples are copolymers of vinyl monomers, preferably about 1 to about 3.5 units of å, B olefinic unsaturation to 1000 units of molecular weight.

A favorable embodiment is a radiation-curable paint binder, that from a film-forming solution of about 20 to about 80, preferably about 30 up to about 70 parts by weight of an α, ß-olefinically unsaturated siloxane, which by Implementation of a siloxane with at least two functional groups, namely hydroxyl groups and / or alkoxy groups, with a monohydroxy ester of acrylic acid or methacrylic acid and from about 80 to about 20, preferably about 70 to about 30 parts by weight an epoxy resin which is olefinically unsaturated in a, ß-position and which is about 0.5 to about 5, preferably 1 to 3.5 units of olefinic α, β-unsaturation per 1000 units of the molecular weight, and / or one which is olefinically unsaturated in the α, β-position Diurethnas, which by reacting a molar proportion of an organic diisocyanate and two molar proportions of a monohydroxy ester of acrylic acid or methacrylic acid has been obtained.

Another inexpensive radiation-curable paint binder is from a film-forming solution of about 20 to about 80, preferably about 30 to about 70 parts by weight of an α, β-olefinically unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely Hydroxyl groups and / or methoxyl groups, with a monohydroxy ester in a, ß-position olefinically unsaturated carboxylic acid, and from about 80 to about 20, preferably about 70 to about 30 parts by weight of one which is olefinically unsaturated in the α, β-position Epoxy resin made by reacting an epoxy resin with Acrylic acid or methacrylic acid was obtained.

Advantageously, these coating compounds can also contain about 10 contain up to about 200 parts by weight of vinyl monomers.

There is a very inexpensive radiation-curable paint binder consisting essentially of about 20 to about 100 parts by weight of vinyl monomers, about 30 to about 70 parts by weight of an α, β-olefinically unsaturated epoxy resin, which about 1 to about 3.5 units of olefinic α, B-Ni saturation per 1000 units of the molecular weight, and from about 30 to about 70 parts by weight of an in a, ß-position of olefinically unsaturated reaction product from a molar fraction a siloxane with at least two functional groups, namely hydroxyl groups and / or methoxyl groups, and at least 2 molar proportions of a monohydroxy ester acrylic acid or methacrylic acid.

In a further embodiment of the invention, there is through Radiation curable paint binders made from a film-forming solution of about 20 to about 80, preferably about 30 to about 70 parts by weight of an α, ß-position olefinic unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or methoxyl groups with a monohydroxy ester the acrylic acid or methacrylic acid was formed, and from about 80 to about 20, preferably about 70 to about 30 parts by weight of one which is olefinically unsaturated in the α, β-position Diurethane, which is obtained by reacting a molar proportion of an organic diisocyanate and 2 molar proportions of a monohydroxy ester of acrylic acid or methacrylic acid was obtained. Such coating compositions can also add about 10 to about 200 parts by weight of vinyl monomers, especially styrene and / or acrylic or methacrylic monomers, contain.

A cheap radiation-curable paint binder consists of a film-forming solution consisting essentially of about 20 to about 80 parts by weight of vinyl monomers, about 30 to about 70 parts by weight of one in the α, β position olefinically unsaturated siloxane, which is produced by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or methoxyl groups, with a monohydroxy ester of acrylic acid or methacrylic acid and about 30 to about 70 parts by weight of a diurethane which is olefinically unsaturated in the α, ß-position, which by reacting a molar proportion of an organic diisocyanate with Obtained 2 molar proportions of a monohydroxy ester of acrylic acid or methacrylic acid became.

Furthermore, the masses can additionally contain about 20 to about 80 parts by weight contain further in a, B-position olefinically unsaturated organic resins. Examples this includes polyesters, copolymers of vinyl monomers or epoxy resins, respectively preferably about 1 to about 3.5 units of olefinic α, ß-unsaturation per 1000 Have units of molecular weight.

A cheap radiation-curable paint binder consists of a film-forming solution consisting essentially of about 20 to about 80, preferably about 50 to about 70 parts by weight of a ß-olefinically unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namliQ hydroxyl groups and / or methoxyl groups, with a monohydroxy ester Acrylic acid or methacrylic acid, about 20 to about 80, preferably 30 to 70 parts by weight of a diurethane which is olefinically unsaturated in a, ß-position and which by reacting an organic diisoxyanate with a monohydroxy ester of acrylic acid or methaoryl acid was formed, and about 20 to about 80 parts by weight of such further in a, ß-position olefinically unsaturated organic resin is built up.

Another inexpensive coating composition consists of a film-forming one solution from about 10 to about 300 parts by weight of vinyl monomers, about 20 to about 80, preferably about 30 to about 70 parts by weight of an a, B-position olefinically unsaturated siloxane, which by reacting a siloxane with at least two-functional groups, namely hydroxyl groups and / or methoxyl groups, with a monohydroxy ester of Acrylic acid or methacrylic acid was formed, about 20 to about 80, preferably about 30 to about 70 parts by weight of a diurethane which is olefinically unsaturated in the α, ß-position, which by reacting an organic diisocyanate with a monohydroxy ester the acrylic acid or methacrylic acid was formed, and about 20 to about 80 parts by weight an in a, ß-position olefinically unsaturated organic resin with about 0.5 to about 5, in particular about 1 to about 3.5 units of olefinic α, β-unsaturation to 1000 units of molecular weight it.

Aromatic diisocyanates are preferably used.

The invention results in excellent abrasion resistance and weatherproof coatings provided with articles of daily use with documents of any kind, for example made of metal, wood or polymeric materials that on the substrates by curing and crosslinking of the applied according to the invention Coating compositions with ionizing radiation, in particular electron beams, obtained became. The invention also includes those with such paints and cured Articles of daily use provided with coatings. The hardening takes place favorably with Electron beams that have a potential of about 100,000 to about 500,000 e-volts and at dosages of from about 0.1 to about 100 Mrad, preferably between about 1 and about 25 Mrad per second. The coatings conveniently have thicknesses of 2.5 up to about 100

Claims (25)

Patent Claims Radiation-curable paint binder, thereby characterized in that it consists of a film-forming solution of (a) one in a, ß-position olefinically unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups, especially lower alkoxy groups, with a hydroxy ester in a, ß-position olefinically unsaturated carboxylic acid 1 and from (b) one in a, ß-position olefinically unsaturated epoxy resin and / or one which is olefinically unsaturated in a, ß-position Diurethane, which is obtained by reacting a diisocyanate with a hydroxy ester in a, ß-position olefinically unsaturated carboxylic acid was obtained. 2. Radiation-curable paint binder according to claim 1, characterized in that characterized in that the siloxane is about 3 to about 18, in particular about 3 to about Contains 12 silicon atoms per molecule. 3. Radiation-curable paint binder according to claim 1 or 2, characterized in that the hydroxyester consists of an acrylate or methacrylate consists. 4. Radiation curable paint binder according to claim 1 or 2, characterized in that the hydroxyester consists of a crotonate or cinnamate consists. 5. Radiation-curable paint binders according to claims 1 to 4, characterized in that the ß-position olefinically unsaturated siloxane by reacting a siloxane with functional hydroxyl groups or methoxyl groups with a monohydroxy ester of acrylic acid or methacrylic acid was obtained. 6. Radiation-curable paint binders according to claims 1 bis 5, characterized in that the a, ß-position olefinically unsaturated epoxy resin about 0.5 to about 5, preferably 1 to 3.5 units with olefinic α, B unsaturation to 1000 units of molecular weight. 7. Radiation curable paint binder according to claim 6, characterized in that characterized in that the in a, ß-position olefinically unsaturated epoxy resin by Implementation of an epoxy resin with acrylic acid or methacrylic acid was obtained. 8. Radiation-curable paint binders according to claims 1 bis 5, characterized in that the diurethane which is olefinically unsaturated in a, ß-position by reacting a molar proportion of diisocyanate with 2 molar proportions of a Monohydroxyesters of acrylic acid or methacrylic acid was obtained. 9, Radiation-curable paint binders according to Claims 1 to 3 8, characterized in that it is about 20 to about 80, in particular about 30 to 70 parts by weight of the a, ß-olefinically unsaturated siloxane and about 80 to about 20, in particular about 70 to about 30 parts by weight of the olefinic in the a, B-position unsaturated epoxy resin or the α, β-olefinically unsaturated diurethane contains. 10. The radiation curable paint binder of claim 9, characterized in that characterized, he daps in addition about 10 to about 20 parts by weight of vinyl monomers contains. 11. Radiation-curable paint binder according to claim 9 or 10, characterized in that he also has about 20 to about 80 parts by weight of a contains further in a, ß-position olefinically unsaturated organic resin. 12. Radiation curable paint binder according to claim 11, characterized in that characterized in that the organic resin which is olefinically unsaturated in a, ß-position of a polyester, preferably having from about 1 to about 3.5 units of olefinic a, B-unsaturation per 1000 units of the molecular weight. 13. Radiation curable paint binder according to claim 11, characterized in that characterized in that the organic resin which is olefinically unsaturated in a, ß-position from a copolymer of vinyl monomers, preferably with about 1 to about 3.5 units of olefinic a, ß-unsaturation per 1000 units of the molecular weight. 14. Utility item, consisting of a base and one attached to it adhesive coating of a paint on an outer surface, characterized in that, that the coating of the in situ formed polymerization product from a -ailm-forming Solution of (a) a siloxane olefinically unsaturated in a, ß-position, which by Implementation of a siloxane with at least two functional groups, namely hydroxyl groups and / or carbon gas oxy groups, in particular lower alkoxy groups, with obtained a hydroxy ester of a carboxylic acid which is olefinically unsaturated in a, ß-position and of (b) an epoxy resin which is olefinically unsaturated in a, B-position and / or a diurethane which is olefinically unsaturated in a, ß-position and which is produced by reaction of a diisocyanate with a hydroxy ester in a, ß-position olefinic unsaturated Carboxylic acid was obtained, the coating on the surface by ionizing Radiation have been crosslinked. 15. commodity according to claim 14, characterized in that that the siloxane contains 3 to 18, in particular 3 to 12 silicon atoms per molecule. 16. commodity according to claim 14 or 15, characterized in that that the hydroxy ester is made from a monohydroxy ester of acrylic acid or methacrylic acid consists. 17. commodity according to claim 14 or 15, characterized in that that the hydroxy ester consists of a cinnamate or crotonate monohydroxy ester. 18. commodity according to claim 14 to 17, characterized in that that the in a, ß-position olefinically unsaturated siloxane by reaction of a silaxon with functional hydroxyl groups or methoxyl groups with a monohydroxy ester the acrylic acid or methacrylic acid was obtained. 19 commodity according to claim 14 to 18, characterized in that that the in a, ß-position olefinically unsaturated epoxy resin about 0.5 to about 5, preferably about 1 to 3.5 units with olefinic α, B unsaturation to 1000 Contains units of molecular weight. 20. commodity according to claim 19, characterized in that that the in a, ß-position olefinically unsaturated epoxy resin by reaction of a Epoxy resin with acrylic acid or methacrylic acid was obtained. 21. commodity according to claim 14 to 20, characterized in that that the film-forming solution is about 20 to about 80, in particular about 30 to about 70 parts by weight of the α, β-olefinically unsaturated siloxane and about 80 to about 20, preferably about 70 to about 30 parts by weight of the α, β position olefinically unsaturated epoxy resin or that which is olefinically unsaturated in the α, ß-position Contains diurethane. 22. commodity according to claim 21, characterized in that that the film-forming solution additionally contains about 10 to about 200 parts of vinyl monomers contains, 23. commodity according to claim 21 or 22, characterized in that that the film-forming solution additionally has about 20 to about 80 parts by weight of another contains in a, ß-position olefinically unsaturated organic resin. 24. commodity according to claim 23, characterized in that that the ß-position olefinically unsaturated organic resin made of a polyester, preferably with about 1 to about 3.5 units of olefinic α, β-unsaturation to 1000 units of molecular weight. 25. commodity according to claim 23, characterized in that that the in a, ß-position olefinically unsaturated organic resin from a Copolyseren of vinyl monomers, preferably having from about 1 to about 3.5 units of olefinic a, ß-unsaturation per 1000 units of molecular weight.