DE1957358A1 - Film-forming paint binders hardenable by radiation and articles of daily use coated with them - Google Patents

Description

Radiation-curable film-forming paint binders and herewith Coated articles of daily use The invention relates to a radiation curable film-forming paint binders and articles of daily use coated therewith.

The subject of the invention is a radiation-curable film-forming film Lining binder consisting of a) a polyester which is olefinically unsaturated in the a, B-position and / or one which is olefinically unsaturated in the β-position and is composed of vinyl monomers Binder resin and b) a siloxane which is olefinically unsaturated in α, ß-position, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbyl groups, especially lower ones Alkoxy groups, with an ester bearing hydroxyl groups in an «, B-position olefinically unsaturated carboxylic acid was obtained. The binder can also contain vinyl monomers contain. The preferred hydroxyl containing esters are acrylates and methacrylates. The paint binder is applied as a natural film to a base and on top of it cured by ionizing radiation, especially with an electron beam. The invention also relates to such paints or coatings formed therefrom equipped utensils.

The invention relates to the field of coatings and is concerned with Paints and coated articles of daily use where the coated surface has a high resistance to weathering and wear and tear. In particular, the invention relates to articles of daily use with external surfaces made of wood, metal or polymeric solids with a polymerisation product formed in situ a radiation-curable paint binder that is applied to the surface by ionizing Radiation is crosslinked, coated ind, and the one from a film-forming solution in a, ß-position olefinically unsaturated polyester and / or one in a, ß-position olefinically unsaturated binder resin composed of vinyl monomers and one in a, ß-position there is olefinically unsaturated polysiloxane, which is the reaction product from a molar proportion of a siloxane with at least two hydroxyl and / or hydrocarbon oxy groups and preferably at least two molar proportions of one having hydroxyl groups Represents an ester of a carboxylic acid unsaturated in a, ß-position. In a preferred In the embodiment, the film-forming solution also contains vinyl monomers.

The subject of the invention are therefore paint binders, which in combination a siloxane which is olefinically unsaturated in, ß-position together with one in a, B-position olefinically unsaturated polyester and / or olefinically together with one in a, ß-position unsaturated binder resin made up of vinyl monomers, so-called vinyl resin, for example acrylic type monomers. This is the easiest way to incorporate siloxanes in coating films to ensure weather resistance outdoors to obtain. This procedure is far simpler and more flexible in that you can use any desired amount of the siloxane, since the two basic materials, optionally with the addition of vinyl monomers, by ionizing radiation, in particular Electron beams to be networked can. A chemical association The siloxane with the acrylic resin or the polyester before curing is far more complicated and severely limited in terms of flexibility in terms of concentrations. According to the invention, excellent wear-resistant and weather-resistant results radiation cured coatings.

The term "paint" or "paint" as used herein includes both Materials that contain pigments and / or finely ground fillers, the binder without pigment and / or filler or only with a very low content thereof, whereby the material may, if desired, be colored. Thus, the binder that eventually converted into a permanent, weather-resistant film will consist of all or practically all of the material welrohes for Formation of the film is used, or it can be used as a carrier ft- pigments and / or serve particulate filler material.

The siloxanes used in making the binder have reactive ones Hydroxyl or hydrocarbon oxy groups attached to at least two of their silicon atoms are bound. The term siloxanes denotes compounds that form a bond - Si - O - Si - or -C - O -Si - contain, the remaining valences by a Hydrocarbon residue, a carbon dioxide group, hydrogen, a hydroxyl group or an oxygen atom connecting the silicon atoms and the like Valence with a further silicon atom results, are saturated.

The acyclic siloxane molecules which can be used to prepare the paint binder resins according to the invention advantageously contain from about 3 to about 18 silicon atoms per molecule with the corresponding acidic acid bonds. The preferred siloxanes are represented by the following general formula: where n is at least 1 and x is 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 hydrocarbon 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 1, which are separated by a bond X - Si - 0 - Si - X, either from a group (b) ' or (c) consists of hen.

The cyclic siloxanes which can be used to prepare the paint binder resins according to the invention contain at least 3, preferably 6 to 12, and usually no more than 18 silicon atoms with the corresponding oxygen bonds. The cyclic polysiloxanes used can be in the form of compounds corresponding to the following forms: I.) InsSinOnn where n is an odd positive number of at least 3, n 'the value of 2n and n "the value of 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) a hydrogen atom mean, in which at least two of the groups X, which are separated by a bond X - Si - O - Si - X, have either the meaning (b) or (c), for which the following formula is given as an example: II.) XntSinOnn where n is an odd positive number of at least 5, n 'the value n + 3 and n' the value 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 group with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy group with 1 to 8 carbon atoms, preferably an alkoxy group with 1 to 4 carbon atoms, or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the groups 1, which are separated by a bond 1 - Si - 0 - Si - X, either have the meaning (b) or (c); for which the following structural formula is given as an example: III.) Xn, SinOn "where n is the number 6 or a multiple of 6, n 'the numbers 8, 8 + 6 or 8 + a multiple of 6, n" the numbers 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, in which at least two of the groups 1, which are separated by a bond x - Si - O - Si - x, have either the meaning (b) or (c), of which the following is an example Structural formula is given: or dimers, trimers and the like formed therefrom by condensation with loss of water or alcohol, IV.) XntSinOnn where n is an even positive number of at least 4, n 'is the value of n + 4 and n "is the value 4, 4 + 3 or 4 + a multiple of 3, 1 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, in which at least two of the groups 1, which are separated by a bond X - Si - 0 - Si - x, either have the meaning (b) or (c) have, for which the following structure is given as an example: wherein m is the number 0 or a positive whole number; V.) Xn, SinOn "where n is your even positive number of at least 8, n 'the value n + 2 and n" the value 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 group with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbonoxy group with 1 to 8 carbon atoms, preferably an alkoxy group with 1 to 4 carbon atoms, or (c) a hydroxyl group or (d) a hydrogen atom , where at least two of the groups 1, which are separated by a bond X - Si - O - Si - X, either have the meaning (b) or (c); for which the following structural formula is given as an example: where m is a positive integer.

A large number of processes are known for the production of siloxanes, This includes the regulated hydrolysis of silanes, the polymerization of a siloxane of lower molecular weight, the reaction of silicon tetrachloride with a Alcohol and the like. The manufacture of siloxanes and their incorporation into organic resins is in U.S. Patents 3,154,597, 3,074,904, 3,044,980, 3,044,979, 3,015 637, 2 996479, 2 973 287, 2 937230 and 2 909 549 described Der hydroxylgruppenhaltige Ester preferably consists of a monohydroxyalkyl ester which is olefinic in the α-position unsaturated monocarboxylic acid0 The preferred hydroxyesters are the aorylates and Methacrylates because they have olefinic unsaturation between the terminal carbon atoms and easily at relatively low doses of ionizing radiation are polymerizable The following is a list of such acrylates as an example or methacrylates given: 2-hydroxyethyl acrylate or methacrylate 2-hydroxypropyl acrylate or methacrylate, 2-hydroxybutyl acrylate or methacrylate 2-hydroxyoctyl acrylate or methacrylate, 2-hydroxydodecanyl aorylate or 4 methacrylate 2-hydroxy-3 "chloropropyl acrylate or methacrylate 2-hydroxy-3-acrylate propyl acrylate or methacrylate 2-hydroxy-3-methacryloxypropyl acrylate or methacrylate 2-hydroxy-3-allyloxypropyl acrylate or methacrylate, 2-hydroxy-3-cinnamylpropyl 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-acetoxypropyl 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- (224,6-trichlorophenoxy) propyl acrylate or methacrylate, 2-hydroxy-3- (2,4,5-trichlorophenoxy) propyl acrylate or methacrylate 2-hydroxy-3- (o-chlorophenoxyacetoxy) propyl acrylate or methacrylate 2-Hydroxy-3-phenoxyacetoxypropyl acrylate or methaerylate 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 acrylate 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 the acrylates and methacrylates, the cinnamates, Crotonates and the like. The term 11ionizing as used herein Radiation "denotes radiation with sufficient energy to cause polymerization of the paint films described here, i.e. equivalent to an energy to about 5000 e-volts or greater. The preferred method of curing the films consists of the above coats of paint on substrates to which they are applied in that these films have a beam of polymerization-triggering electrons exposed to an average energy in the range of about 100,000 to about 500,000 e-volts will. When using such a beam it is preferred to have a minimum of 25,000 e-volts Each 2.5 cm distance to land between the radiation emitting source and to be used on the workpiece if the space is taken up by air. One Appropriate adjustment can be made in terms of the relative resistance of the intermediate Gas are made, which preferably consists of an oxygen-free inert gas, like nitrogen or helium An electron beam is preferred used, which at its emission source has a durohson center energy in the range of has about 150,000 to about 500,000 e-tolt.

As used herein, the term "vinyl monomers" refers to monomeric compounds having a terminal group or however does not include allyl compounds. 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 9 to 15 carbon atoms, can also can be used to produce these acrylates and methacrylates. Vinyl hydrocarbon monomers such as styrene and alkylated styrenes such as vinyl toluene, α-methyl styrene and the like can be used separately or together with the acrylates or methacrylates. Furthermore, together with aorylates and / or methacrylates and / or vinyl carbon monomers, smaller amounts of other vinyl monomers, such as nitriles, for example acrylonitrile, acrylamide, N-methylolacrylonitrile, vinyl halides, for example vinyl chloride, and vinyl carboxylates, for example vinyl acetate, can be used.

The term "copolymers of vinyl monomers" refers here to polymers in which the greater proportion (above 50% by weight) of the built-in monomers consists of two or more vinyl monomers.

The films formed from the paints according to the invention will advantageously at relatively low temperatures, for example between room temperature (20 to 25t) and the temperature at which there is significant evaporation of the most volatile Components begins to harden, usually between 20t and 700C0 The radiant energy is preferred in dosages from about 0.1 to about 100 Mrads per second to one moving workpiece applied, the coating having a total dosage in Range from about 0.5 to about 100, usually between about 1 and about 25 and am the cheapest between 5 and 15 Mrad. The films are made by the electron beam The abbreviation is transformed into tough, wear-resistant and weather-resistant coatings "Mrad" means 1,000,000 rads. The term "rad" denotes that radiation dosage, which has an absorption of 100 ergs of energy per gram of absorber, for example a coating film, results. The electron emitting device may be a linear electron accelerator be the one to form a direct current potential in the above Area is suitable. In such a device, the electrons become ordinary emitted by a hot filament and through a uniform tension gradient accelerated, the electron beam, which has a diameter of about 3.2 mm at this May have place, is then distorted, 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 derglo of about 0.0075 cm thick The inventively used, Polyesters which are olefinically unsaturated in the α, β-position have a molecular weight in the range from about 500 to about 20,000, preferably in the range from about 2,000 to about 10 000. The polyester advantageously contains about 0.5 to about 5, preferably about 1 to about 3.5 units with olefinic α, ß unsaturation per 1000 units the molecular weight.

Among the unmodified polyester resins, essentially those composed of carbon, hydrogen and oxygen become the preferred resins from a polyhydric alcohol, a dicarboxylic acid which is olefinically unsaturated in a, ß-position and a second polybasic carboxylic acid is formed. The expression nolefinic a, ß-not saturation11 here comprises the radiation-sensitive olefinic unsaturation, due to the incorporation of maleic acid or other acids with corresponding Unsaturation results in the polyester for the purpose of polymerization by irradiation.

The preferred dicarboxylic acid for forming the desired olefinic a, ß-unsaturation consists of maleic acid, preferably in the form of its anhydride is applied. Other acids and / or anhydrides used for this purpose include, but are not limited to, fumaric acid, itaconic acid, Chloromaleic acid, dichloromaleic acid and the like.

The second polybasic carboxylic acid, i.e. dicarboxylic acid or tricarboxylic acid, is chosen from acids which do not see any additional olefinic «, ß-unsaturations deliver, and the relative amounts of the two acids are adjusted so that gives the desired concentration of unsaturation in the form of the anhydrides. to suitable Anhydrides for this purpose include phthalic acid, tetrahydrophthalic acid, 1, 2,4-benzenetricarboxylic acid (trimellitic acid) and similar acids.

The polyhydric alcohol preferably consists of a diol, triols and other polyhydric alcohols can be used, however it is advisable to use these Use alcohols in smaller amounts compared to the diols. To suitable diols include, without being limited to, ethylene glycol, propylene glycol, 1,3-butylene glycol, 2-butene-1,4-diol, 1w4-butane glycol, neopentyl glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol b Decamethylene glycol, dimethylolbenzenes, dihydroxyethylbenzenes and similar compounds, The polyhydric alcohols include, but are not limited to, glycerine, Pentaerythritol and the like, those to be used according to the invention in a, ß-position olefinic Unsaturated binder resins made up of vinyl monomers have a molecular weight above about 1,000 and below about 50,000, usually below about 25,000. In a preferred embodiment, these resins have molecular weight in the range from about 3,000 to about 10,000. Advantageously, those made from vinyl monomers contain built up resins about 0.5 to about 5, preferably about 1 to about 3.5 units olefinic α, β-unsaturation per 1000 units of the molecular weight; you can can be manufactured using a variety of processes0 In one embodiment the binder resin composed of vinyl monomers consists of the copolymerization product a smaller proportion of glycidyl methacrylate and of a bigger one Portion of at least two vinyl monomers, which are preferably selected from the group of Styrene, esters of acrylic acid and esters of methacrylic acid exist, which then is reacted with acrylic acid or methacrylic acid. Other vinyl hydrocarbons, for example, α-methylstyrene, vinyltoluene and the like. Can be used in place of styrene can be used. The starting copolymer can also contain smaller amounts of acrylic acid and / or methacrylic acid.

In a second embodiment, that is built up from vinyl monomers Binder resin by reacting an unsaturated glycidyl ether with white or more different vinyl monomers and reaction of the polymer obtained with a Allyl alcohol is formed.

In a third embodiment, that is built up from vinyl monomers Binder resin by reacting an allyl alcohol with two or more different ones Vinyl monomers and reaction of the polymer obtained with an allyl glycidyl ether educated.

The allyl alcohols used in the second and third embodiment are usually allyl alcohols with 3 to 10 carbon atoms, for example allyl alcohol, 2-methyl-2-propen-1-ol, cinnamyl alcohol (3-phenyl-2-propen-1-ol), 2-phenyl-2-propen-1-ol and the like .. The alcohols listed above can have alkyl substituents, thereby increasing the number of carbon atoms per molecule up to about 14 can.

Those which can be used to prepare the copolymers listed above Allyl glycidyl ethers are usually glycidyl ethers with 6 to 13 carbon atoms, but can also Contains 17 carbon atoms if the ether was formed from a C14 alcohol and epichlorohydrin. This includes connections, such as allyl glycidyl ether, 1-butene glycidyl ether and glycidyl ether derived from the above listed allyl alcohols were formed. These ethers can be known by the Implementation of such alcohols with epichlorohydrin or according to the Williamson synthesis getting produced.

In a fourth embodiment, it consists of vinyl monomers Binder resin made from a copolymer of two or more vinyl monomers, including at least one hydroxyl-containing monomer component, which with an acyl halide was implemented.

In a fifth embodiment, this is built up from vinyl monomers Binder resin by reacting a styrene-allyl alcohol copolymer with methacrylyl chloride or acrylyl chloride.

In a sixth embodiment that is built up from vinyl monomers Binder resin by reacting a partially hydrolyzed polyvinyl acetate or styrene-vinyl acetate copolymer or ethylene vinyl acetate copolymers with methacrylyl chloride or acrylyl chloride.

It can be seen that in the above embodiments Binder resin composed of vinyl monomers has a backbone or basic carbon-carbon chain possesses, which is composed essentially of vinyl monomers, the side chains have terminal unsaturation. This olefinic nitrogen saturation between the terminal carbon atoms of the side chain is from the basic carbon-carbon chain through at least one ester bond or Aether bond separated.

The film-forming material should have an application viscosity which is sufficiently low for rapid application to the substrate in practical of uniform depth and that is high enough that a minimum of 25 The strong film is held on a vertical surface without seepage Films are usually produced at an average depth of about 2.5 to 100 square meters applied with suitable adjustment of viscosity and application method o Of course, by choosing the siloxane and the hydroxyester in the Production of the ß-position olefinically unsaturated siloxane constituent of Binder solution the viscosity of the siloxane component can be varied. From the molecular weight the polyester and / or the vinyl binder resin can be varied to adjust the viscosity adjust the binder solution. Also the type and amount of vinyl monomers in the Binder solution can easily be adjusted to a suitable consistency of application by customary paint application methods, for example spraying, mounting, roller application and the like., to yield. It is also within the scope of the invention, the polyester or the vinyl copolymer and the reaction product of siloxane and unsaturated ester as the only polymerizable constituents of the binder in solution with a volatile Solvent, for example toluene, xylene and the like. To apply which after can be removed prior to application and prior to curing, if the binder is essentially from the polyester which is olefinically unsaturated in a, ß-position and that in a, ß-position olefinic consists of unsaturated polysiloxane, the binder contains about 20 to about 80, advantageously about 30 to about 70 parts by weight of the polyester and about 80 to about 20, advantageously about 80 to about 30 parts by weight of the siloxane.

If the binder contains significant amounts of vinyl monomers, contain it advantageously about 10 to about 200, preferably about 20 to about 100 parts by weight the vinyl monomers and a resinous ingredient composed of about 30 to 70 parts by weight of the polyester and about 70 to 30 parts by weight of the siloxane, smaller amounts of other polymerizable monomers, for example allyl compounds, can may be used and form the resto The invention particularly relates those coatings in which the film-forming solution, excluding vinyl monomers, essentially of the unsaturated polyester and the product of siloxane and unsaturated ester as described herein; H. Coating compounds, wherein these ingredients constitute at least 85% by weight of the film-forming binder If the binder consists essentially of the olefinically unsaturated in a, ß "position, Binder resin composed of vinyl monomers and that which is olefinically unsaturated in a, ß-position Polysiloxane consists, the binder contains about 20 to about 80, advantageously about 30 to about 70 parts by weight of the vinyl binder resin; and about 80 to about 20, advantageously about 70 to about 30 parts by weight of the siloxane ball of the binder is significant Containing amounts of vinyl monomers, the binder advantageously has about 10 to about 200, preferably about 20 to about 100 parts by weight Vinyl monomers and the resinous ingredient, which consists of about 20 to 80, preferably about 30 to about 70 parts by weight of the vinyl resin and about 80 to 20, preferably about 70 to about 30 parts by weight of the siloxane consists, smaller amounts of other polymerizable Monomers such as allyl compounds can be used if desired and make up the rest.

The invention particularly relates to such coatings in which the film-forming Solution, excluding vinyl monomers, essentially consisting of vinyl monomers built-up binder resin and the product of siloxane and uno saturated ester, such as they have been described here, i. e. Coating compositions in which these ingredients make up at least 85% by weight of the film-forming binder.

The following examples serve to further illustrate the invention.

Example 1 A paint made from an unsaturated Solyester and the Product of siloxane and unsaturated ester was made from the following ingredients in prepared in the manner indicated (a) Preparation of the siloxane constituent reactants Part by weight of acyclic siloxane with functional methoxy groups 178 hydroxyethyl methacralate 118 tetraisoropa titanate 0.32 hydroquinone 0.06 (1) Customary 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 kethoxy groups per molecule 3 - 4 Das Siloxane, the methacrylate monomer and the hydroquinone as polymerization inhibitors were fitted to 100t in one with a Barrett-type still trap Flask heated. The titanate was added as a catalyst and the temperature increased 150S increased for 3 hours, during which time the methanol was removed by distillation was removed. The cooled reaction product had a viscosity of 0.6 stoke at 25t.

(b) Preparation of polyester resin This resin contains about 1.5 units of olefinic a, ß-unsaturation per 1000 units of the molecular weight.

Starting materials parts by weight maleic anhydride 147 phthalic anhydride 429 neopentyl glycol 503 Procedure All respondents were placed in a cattle-necked flask fitted with a stirrer, thermometer, nitrogen inlet tube and a Vigreux column of 25 cm with a Barrett trap to remove the condensation water was equipped. The reactants were slowly raised to 165, where the Distillation of the water of condensation began. Nitrogen was released from the reactants blown during implementation. The reaction temperature rose when the water was continuously removed until a maximum temperature of 225T was reached The column was then removed and 3 wt.% Xylene for azeotropic water removal added and heating continued until the acid number reached 30. The product was cooled to 100 ° C. and 0.03% by weight hydroquinone was added as an inhibitor and the polymer to a non-volatile content of 80% with styrene diluted (c) binder solution parts by weight of siloxane ester product according to (a) 10 polyester resin according to (b) 12.5 methyl methacrylate 5 The binder solution was applied to metal sheets with a Rod, which was wrapped with a No. 30 wire, spread out and under the following Hardened conditions: electron beam potential 270 KV current intensity 25 ma dosage 15 Mrad atmosphere N2 The films produced thereby showed the following properties: 1 2 film thickness (/ u) 40.6 27.9 pencil hardness H H solvent resistance (a) 6 15 (a) Rubbed by hand using a soft rag dipped in 2-butanone Excellent coatings were obtained.

Example 2 The procedure of Example 1 was repeated, however the polyester component in the following manner from the following components prepared: reactants parts by weight maleic anhydride 14.7 tetrahydrophthalic anhydride 72.3 Neopentyl Glycol 75.0 Dibutyl Tin Oxide, Catalyst 7.06 Procedure The reactants were placed in a reaction vessel and then heated to about 170 and at held at this temperature for 1 hour. The temperature of the charge was then increased to 227 ~ and held there until the acid number of the resin obtained was below about 20. The excess of glycol and water was in vacuo removed and after the acid number was below about 10, 14.5 g of hydroquinone were added. The feed was allowed to cool to about 82 ° C and then 37.0 parts by weight of styrene were added to.

Excellent rates were obtained.

Example 3 The procedure of Example 2 was repeated, however an equivalent amount of 1,2-cyclohexenedicarboxylic anhydride in place of the tetrahydrophthalic anhydride 8 (4-cyclohexene-1,2-dicarboxylic acid anhydride) was added.

EXAMPLE 4 The procedure of Example 2 was repeated, however an equivalent amount of trimellitic anhydride in place of the tetrahydrophthalic anhydride used.

Example 5 The procedure of Example 2 was repeated, however one fifth of the neopentyl glycol replaced by an equivalent amount of pentaerythritol0 Example 6 The procedure of Example 2 was repeated, but an equivalent one Amount of ethylene glycol used instead of neopentyl glycol.

EXAMPLE 7 The procedure of Example 2 was repeated, however an equivalent amount of 2-butene-1,4-diol glycol is used instead of the neopentyl glycol.

Example 8 The procedure of Example 2 was repeated, however an equivalent amount of 1,6-hexamethylene glycol is used instead of the neopentyl glycol.

Example 9 The procedure of Example 2 was repeated, however an equivalent amount of fumaric acid is used instead of the maleic anhydride.

Example 10 The procedure of Example 2 was repeated, however an equivalent amount of chloromaleic anhydride in place of maleic anhydride used.

The products of Examples 3 to 10 also showed excellent coatings.

Example 11 The procedure of Example 1 was repeated, however the polyester component in the following manner from the following components manufactured: Reactant parts by weight maleic anhydride 353.0 Tetrahydrophthalic Anhydride 973.8 Neopentyl Glycol 1458.1 Method One Melt conversion of tetrahydrophthalic anhydride and neopentyl glycol carried out over a period of 23 hours. Water passed over at 165 ° C and a maximum temperature of 180 ° C was reached. The resin obtained had a Acid number below 15 and was cooled to room temperature, whereupon the maleic anhydride together with 1.39 parts by weight of hydroquinone and 330 cc of xylene was added Charge was heated to an acid number of 10 with the water at about 140! passed and a maximum temperature of 180 ° C was reached.

Example 12 The procedure of Example 1 was repeated, however as a polysiloxane, a methoxylated partial hydrolyzate of monophenyl and phenylmethylsilanes used, which consisted essentially of dimethyltriphenyltrimethoxytrisiloxane and had the following properties: Average molecular weight 470 compound weight 155 Specific weight at 25 ° C 1.105.

Viscosity at 25t, Centistokes 13 Also the products of the examples 11 and 12 gave excellent coatings Example 13 Sin coating material the reaction product of siloxane and unsaturated ester became the following Ingredients prepared in the manner indicated: reactants parts by weight Cyclic siloxane with (1) functional hydroxyl groups 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 - 1.539 softening point, mercury method according to Durran, t 93 at 60 solids in xylene specific gravity at 25S 1.075 viscosity at 25t, Centipoise 33 Gardner-Holdt A 1 method A three-necked flask that comes with Stirrer, thermometer, nitrogen inlet and Barrett-Palle was fitted loaded with the siloxane, the methacrylate, the xylene and the hydroquinone. These Solution was brought to reflux, 138t while Heated for 30 minutes. nitrogen was bubbled through the reaction mixture throughout the procedure. The by-product Water was slowly removed and the temperature gradually rose to 146t. To In 5 hours, 8.5 ml of water were collected, which resulted in an almost complete conversion indicates that the xylene was distilled off under reduced pressure and the product then diluted with methyl methacrylate to a non-volatile content of 70%, 100 parts by weight of this solution and 30 parts by weight of that prepared according to Example 1 Polyesters were mixed and made the first paint binder. 100 parts of this Solution and 70 parts by weight of the polyester prepared according to Example 1 were mixed and made the second paint binder.

These coatings were pigmented and placed on metal substrates, Wood and polymeric materials (ABS, i.e. acrylonitrile-butadiene-styrene copolymer) applied and then with an electron beam, as in the examples above, hardened at a dosage of about 20 Mrad.

Excellent coatings were obtained on the documents.

Example 14 The procedures of Examples 1, 12 and 13 were repeated however, an equivalent amount of 2-hyaroxyethyl acrylate instead of hydroxyethyl methacrylate Used in the manufacture of the product from siloxane and unsaturated ester.

Example 15 The procedures of Examples 1, 12 and 13 were repeated, but equivalent amount of 2-hydroxypropyl methacrylate instead of of hydroxyethyl methacrylate in the manufacture of the product from unsaturated Ester and siloxane used0 Example 16 The procedures of Examples 1, 12 and 13 were repeated, but using an equivalent amount of 2-hydroxybutyl acrylate instead of hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Ester used.

Example 17 The procedures of Examples 1, - 12 and 13 were repeated, however, an equivalent amount of 2-hydroxyoctyl acrylate instead of the hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester Example 18 The procedures of Examples 1, 12 and 13 were repeated, but one equivalent close to 2-hydroxydodecanyl methacrylate instead of hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester0 Example 19 The procedures of Examples 1, 12 and 13 were repeated but one equivalent amount of 3-chloro-2-hydroxypropyl acrylate instead of the hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester.

Example 20 The procedures of Examples 1, 12 and 13 were repeated, however, an equivalent amount of 3-acryloxy-2 hydroxypropyl methacrylate instead of Hydroxyäthylmeth acrylate in the manufacture of the product from siloxane and unsaturated ester O Example 21 The procedures of Examples 1, 12 and 13 were repeated, but using an equivalent amount of 3-crotonoxy-2-hydroxypropyl acrylate instead of hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated esters are used.

Example 22 The procedures of Examples 1, 12 and 13 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropylcinnamate in place of the Hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Ester used example 23 The procedures of Examples 1, 12 and 13 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropyl crotonate instead of the Hydroxyethyl methacrylate in the manufacture of the product from suloxane and unsaturated Ester used, the products obtained according to Examples 14 to 23 also had excellent coatings.

Example 24 The procedures of Examples 14 to 23 were repeated, however, an amount of the monohydroxy ester in a, ß- Position olefinic unsaturated monocarboxylic acid used, which was sufficient to with at least one functional hydroxyl or hydrocarbonoxy group of the siloxane react, however, it was not sufficient to deal with all such groups of the siloxane molecules to react in the reaction mixture.

Example 25 The procedures of Examples 14-23 were repeated, however, such an amount of the nonohydroxy ester that is olefinically unsaturated in the α, β-position Monocarboxylic acid used, which is in excess over the saturation of all functional hydroxyl and hydrocarbon oxy groups of the siloxane molecules in the reaction mixture required.

Amount present Excellent coatings were also obtained here0 Example 26 The procedure of Example 1 was repeated, but as a polysiloxane for the production of the α, β-olefinically unsaturated siloxane dipropoxytetramethylcyclotrisiloxane used, Example 27 The procedure of Example 1 was repeated, but as Polysiloxane for the production of the α, β-olefinically unsaturated siloxane Dibutoxytetramethyldisiloxane used Example 28 The procedure of Example 1 was repeated, but as a polysiloxane for the preparation of the a, ß-position olefinic Unsaturated siloxane used pentamethyltrimethoxytrisiloxane, Also the products of Examples 26 to 28 gave excellent coatings. Example 29 A pigmented one Paint composition was made by adding 75 parts by weight of the product from siloxane and unsaturated ester according to Example 12 with 150 parts by weight of a commercially available Titanium dioxide pigment and 20 parts by weight of methyl methacrylate were premixed. That Mixture was made by shaking with an equal amount of glass beads in a usual Sarb shaker ground for 30 minutes, the premix was additionally with a further 75 parts by weight of the product composed of siloxane and unsaturated ester 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 35 Parts of methyl methacrylate and 65 parts by weight of the polyester according to Example 1 were added.

The paint was made on substrates made of metal, folz and polymer Substances (ABS, i.e. acrylonitrile-butadiene-styrene copolymer) to an average Depth of about 38 applied and then applied with an electron beam as in the cured above examples.

It was found to be extremely resistant to abrasion and weathering Coatings.

Example 30 A paint was made from one modified with diisocyanate Polyester and a product made from siloxane and unsaturated ester made in the following manner: (a) Making Polyester A Reactant Parts by weight succinic acid 340.1 tetrahydrophthalic anhydride 1387.6 1,2-propanediol 1004.4 The monomers were added together with 200 com xylene, heating in the solvent Subjected for a period of 10 hours, the temperature gradually increasing was increased to 260 ° c. The resin obtained had an acid number of about 5.7. The xylene was separated from the resin.

(b) Preparation of polyester B reactant parts by weight of resin A 200 tolylene diisocyanate 17.4 styrene 86 The diisocyanate was slow and partial was added to the solution of styrene and resin A and charging continued during stirred for 5.5 hours to form Resin 3.

(c) Production of the polyester a To the reaction mixture containing the resin B. 13 parts by weight of 2-hydroxyethyl methacrylate were added slowly and in parts and the loading continuously during a period of 25 hours stirred and the resin C obtained in the process.

(d) Preparation of the coating composition, components, parts by weight, solution of the resin C 55 Product of siloxane and unsaturated ester according to Example 1 (a) 35 This coating composition was applied to the documents with a rod wrapped with wire and with dried with an electron beam. The above approach was here with 10, 25 and 50 parts by weight of methyl methacrylate diluted Documents applied and thereon by an electron beam, as in the preceding Examples, hardened.

Excellent coated documents were obtained.

Example 31 A modified siloxane paint was made from the following Ingredients manufactured: Ingredients GewO parts product made from siloxane and unsaturated Ester according to Example 1 (a) 25 solution of the product of siloxane and modified polyester 75 (1) The solution of the product of siloxane and modified polyester in vinyl monomers was made in the following way: Were in a reaction vessel 70 parts by weight of neopentyl glycol, 10 parts by weight of xylene and 35 parts by weight of the in example 13 introduced cyclic polysiloxane with functional hydroxyl groups0 The charge was heated to about 174 for 2.5 hours, whereupon 13.7 parts by weight Maleic anhydride, 54.2 parts by weight of tetrahydrophthalic anhydride and 0.22 part by weight Dibutyltin oxide were added. The temperature of the feed slowly rose about 221- increased and this temperature maintained until the resin obtained has an acid number of about 10 had. Some of the xylene and the water formed in the reaction were removed during the yoke and the excess was then removed in vacuo.

To the charge was added 0.027 parts by weight of hydroquinone and the loading to 82.5! cooled and diluted with 40 parts by weight of styrene.

The paint was applied to substrates and then with one. Electron beam cured as in the previous examples. There were Received excellently coated documents.

Example 32 The procedure of Example 1 was repeated, however curing with a beam potential of 175,000 volts at a distance from the workpiece of 7.5 cm from the emitting source and with 400,000 volts at a distance of about 25.cm carried out, each time working in a nitrogen atmosphere, Containing small amounts of carbon dioxide Excellent coatings were obtained.

Example 33 The products of siloxane and unsaturated ester of Examples 1, 12 and 13 were used together with the polyester resins of Examples 1 and 2 and diluted with xylene to spray consistency. These solutions were based on Backings made of wood, metal and synthetic solid polymers are applied and how cured in the previous examples after the xylene had been driven off, Excellent uppers were obtained.

Example 34 Paint compositions were prepared by adding 160 parts by weight of the product of siloxane and unsaturated ester according to Example 1 and 150 parts by weight of the polyester resin according to Example 1 were mixed, this mixture in two bleach Parts was divided and one of these parts with 100 parts by weight of methyl methacrylate and the other was diluted with 200 parts by weight of methyl methacrylate.

The film-forming solutions obtained were printed on metal documents applied and then with an electron beam, as in the previous examples, networked.

Example 35 Paint compositions were prepared by adding 40 parts by weight of the product of siloxane and unsaturated ester according to Example 13 and O parts by weight of the polyester resin according to Example 8 were mixed, this mixture in the same Parts was divided and one of those parts with 10 parts by weight Methyl methacrylate and the other part diluted with 20 parts by weight of methyl methacrylate became.

The film-forming solutions obtained were on metal substrates applied and then with an electron beam, as in the previous examples, networked.

Excellent coatings were also obtained in Examples 34 and 35.

Example 36 A paint comprising a product of siloxane and unsaturated ester and an unsaturated vinyl resin became the following Ingredients prepared in the manner indicated: (a) Preparation of the siloxane component Reactant parts by weight of acyclic siloxane with (1) methoxyl functional groups 178 Hydroxyethyl methacrylate 118 Tetraisopropyl titanate 0.32 Hydroquinone 0.06 (1) see Example 1 siloxane, methacrylate monomer and hydroquinone as polymerization inhibitor were to 100 in one equipped with a Barrett-type still Flask heated. Titanate as a catalyst was added and the temperature was increased to 150 cm increased over a period of 3 hours, during which time the methanol was removed by distillation has been removed. The cooled reaction product had a viscosity of 0.6 stoke at 25to (b) production of the binder resin made up of vinyl monomers Starting materials parts by weight xylene 600 methyl methacrylate 196 ethyl acrylate 333 Glycidyl methacrylate 71 azobisisobutyronitrile hydroohinone 0.12 methaoryleic acid 42 Triethylamine 0.96 Process The solvent for the reaction, xylene, was in a Flask fitted with stir bar, addition triohter, thermometer, nitrogen inlet tube The amount of xylene was the same as the total weight of the vinyl monomers to be added. The xylene was heated to reflux and nitrogen bubbled through the solution during the warm-up and during the reaction. the combined monomers and the initiator (azobisisobutyronitrile) were added to the on The refluxing solution was added uniformly over the course of 2 hours. The weight of the initiator was 10 parts by weight per 1000 parts by weight of the vinyl monomers.

The reaction solution was refluxed until conversion of monomers in the polymer was greater than 97% (8 to 16 hours).

In the second stage, hydroquinone was added as an inhibitor and then methacrylic acid to react with the remaining epoxy groups of the polymer added triethylamine was used as a catalyst. These Esterification reaction was carried out at reflux temperature until 80% Esterification was achieved (determined by the remaining acid number). The xylene was then removed by vacuum distillation and the polymer diluted in methyl methacrylate, so that the weight ratio of polymer to solvent was 2.

(c) Preparation of the paint. Ingredients Parts by weight of the product from siloxane and ester according to (a) 10 acrylic resin according to (b) 15 methyl methacrylate 2.5 Die The paint was applied to a steel base with a stick attached to a wire No. 30 was wrapped and applied to a hard film using the following Hardened irradiation conditions: Electron beam potential 270 KV current intensity of the electron beam 25 ma dosage 15 Mrad atmosphere nitrogen distance, workpiece to emitting point 25 cm Example 37 The procedure according to Example 36 was repeated, however, the polymer composed of vinyl monomers is composed of the following ingredients manufactured in the following way: Parts by weight of ethyl acrylate 38.8 Methyl methacrylate 23.2 Allyl glycidyl ether 37.0 Benzoyl peroxide 1.0 Xylene solvent In a reaction vessel equipped with a condenser, thermometer, stirrer and dropping funnel became an equal amount of xylene by weight as that in the first reaction stage reactants to be added, added.

The xylene was about 100 to 120! heated, the four respondents were mixed thoroughly and slowly added to the heated one with a dropping funnel Xylene added over 4 hours. The reaction was carried out at this temperature during Maintain for 1 to 2 hours after the addition is complete, followed by room temperature has been cooled.

The binder polymer was made from the following in a second reaction stage Materials formed: parts by weight of copolymer from stage I 69.4 allyl alcohol 30.4 Potassium Hydroxide 0.2 A solution of allyl alcohol and potassium hydroxide became the Copolymers added at room temperature. The Gemisoh was then brought to a temperature heated from 100 to 120 ° C. This temperature was maintained for about 7 hours and then cooled. The reaction mixture of binder and polymer was about 60t heated and xylene and excess reactants by vacuum distillation removed.

At a temperature of about 60t, styrene and hydroquinone became too added to the polymer and a film-forming solution with the following composition obtained: parts by weight of polymer from stage II 66.66 styrene 33.27 hydroquinone 0.07 Example 38 The procedure of Example 36 was repeated, but that for vinyl monomers composed polymers made from the following ingredients in the following way: Parts by weight of ethyl acrylate 39 methyl methacrylate 24 allyl alcohol 36 benzoyl peroxide 1 Xylene Solvent Into a equipped with a condenser, thermometer, stirrer and dropping funnel The reaction vessel became an equal weight xylene harrow as that in the first one Level to be added reactants introduced. The xylene was about 100 heated to 120t. The four reactants were mixed thoroughly and slowly added with the dropping funnel into the heated xylene over 4 hours. The implementation was kept at this temperature for 1 to 2 hours after the addition was complete, then it was cooled to room temperature.

The binder polymer was in a second reaction stage from the following Materials produced: parts by weight of copolymer from stage I 69 allyl glycidyl ether 30.8 Potassium hydroxide 0.2 A solution of the allyl glycidyl ether and potassium hydroxide was added to the copolymer at room temperature. The mixture was then on a temperature of 100 to 120t. This temperature was heated for about 7 Hold for hours and then cooled. The reaction mixture of binder and polymer was heated to about 60t and xylene and excess reactants through Vacuum distillation removed at a temperature of about 60t were styrene and Hydroquinone is added to the polymer and a film-forming solution with the following Composition obtained: parts by weight of polymer from stage I1 67 styrene 32.93 hydroquinone 0.07 Example 39 The procedure of Example 36 was repeated, except that from Polymers composed of vinyl monomers from the following ingredients Way made: Stage 1 reactant parts by weight of methyl methacrylate 400 ethyl acrylate 400 hydroxyethyl methacrylate 195 toluene 1000 benzoyl peroxide 30 Das Benzoyl peroxide was in a solution of methyl methacrylate, ethyl acrylate and hydroxyethyl methacrylate and one half of the toluene dissolved, this solution was added proportionately to the remainder Toluene was added at reflux temperature over a period of 7 hours, whereby finally a pot temperature of around 138 to 140! was achieved. The heating reflux was maintained for a further 3 hours and the solution then cooled Stage II reactants parts by weight of solution from stage I 500 acrylyl chloride 33.8 Toluene 30 The solution from stage I was heated to 60 ° C. and a solution of acrylyl chloride and toluene added dropwise over 4 hours, the temperature to about 90 ° C rose. After heating for an additional 2.5 hours, standard infrared analysis indicated about 14 remaining hydroxyl groups in the solution. The solution was made with a Gaer-Holdt viscosity obtained from B - a. This solution was subjected to a vacuum below 10 mm Hg at 70 and won the acrylic polymer.

Example 40 The procedure of Example 36 was repeated, however the polymer composed of vinyl monomers from the following components in the following Way produced: 100 parts by weight of a styrene-allyl alcohol copolymer with a Content of 21.4 wt .-% allyl alcohol and with an average molecular weight of about 1620 and 0.1 part by weight of hydroquinone were dissolved in toluene and reduced to 90 ~ heated and 41.8 parts by weight of methacrylyl chloride in toluene dropwise during 1 Hour added. Heating was continued and the temperature was increased to the reflux temperature of the toluene allowed to rise until, after a further 5 hours, the gas was released practically had stopped completely. Infrared analysis showed about 10% remaining hydroxyl groups. The solvent was removed using the water jet pump, the one obtainable therefrom electron polymerizable paint gave excellent coatings.

Example 41 The procedure of Example 36 was repeated, however the polymer composed of vinyl monomers from the following ingredients in the prepared as follows: 250 parts by weight of a 25% non-volatile solution Substances made from a polyvinyl acetate polymerized in solution, which is in a mixture Made up of about 85% toluene and 15% methanol were placed in a 1 liter flask brought, equipped for distillation, stirring and dropwise addition of solvent was. The polyvinyl acetate was hydrolyzed to contain about .5 hydroxyl groups. The methanol was removed as an azeotrope with toluene and additional toluene was added, to maintain volume. When the methanol removal was complete, the solution became kept at reflux and 16 parts by weight of methacrylyl chloride in 20 parts by weight of dry Dioxane added dropwise over 1/2 hour.

Heating was continued for an additional 5 hours.

Toluene was added during the distillation and then the Excess of acid chloride and the excess of toluene on the water pump removed0 The resin obtained was recovered.

The products of Examples 36 to 41 also became excellent Received coatings.

Example 42 The procedures of Examples 36 to 41 were repeated, however, the vinyl monomer content of the paint binder solution consisted of one Mixture of styrene and methyl methacrylate and was about 10% by weight of the solution 43 The procedures of Examples 36 through 41 were repeated except that the content passed on vinyl monomers of the paint binder solution from a mixture of methyl methacrylate, Butyl acrylate and 2-ethylhexyl acrylate and was about 60% by weight of the solution.

Example 44 The procedures of Examples 36 to 41 were repeated, however, the vinyl monomer content of the paint binder solution consisted of one Mixture of ethyl acrylate, butyl methacrylate and octyl acrylate and was about 25 wt. " of the solution Example 45 The procedures of Examples 36 to 41 were repeated, however, the vinyl monomer content of the paint binder solution consisted of one Mixture of styrene and vinyl toluene and was about 50% by weight of the solution.

Example 46 The procedures of Examples 36 to 41 were repeated, however, the content of the α, β-olefinically unsaturated siloxane to 30% by weight of the paint binder solution and the content of the α, ß-position olefinic unsaturated binder resins built up from vinyl monomers to 70% by weight of the binder solution, excluding vinyl monomers, discontinued; Example 47 The procedures of the examples 36 to 41 were repeated, but the content of the in «, ß-position became olefinic unsaturated siloxane adjusted to 70 wt .-% of the paint and the Content of that which is olefinically unsaturated in a, ß-position and built up from vinyl monomers Binder resin adjusted to 30% by weight of the binder solution, excluding the vinyl monomers.

Also according to Examples 42 to 47, excellent coatings were obtained obtain.

Example 48 The procedures of Examples 36-47 above were followed repeated, but the α, β-olefinically unsaturated siloxane from the following Ingredients prepared in the following manner: reactants parts by weight Oyclic siloxane with functional hydroxyl groups (1) 200 hydroxyethyl methacrylate 71 hydroquinone 0.1 xylene, solvent 116 (1) see example 13.

Procedure A three-necked flask fitted with a stirrer, thermometer, nitrogen inlet and Barrett's case was equipped with the siloxane, the methacrylate, the xylene and charged to the hydroquinone. This solution was brought to the reflux temperature of 138! heated for 30 minutes0 nitrogen was in the reaction mixture during the blown in throughout the process. The by-produced water became slow decreased and the temperature gradually rose to 146t9. After 5 hours it was 8.5 ml of water collected, indicating almost complete conversion. The xylene was removed by distillation at reduced pressure and then the product on a Content of 70% non-volatile substances diluted with methyl methacrylate.

Example 49 The procedure of Example 36 was repeated, however as a polysiloxane for the production of the ß-position olefinisoh unsaturated siloxane a methoxylated partial hydrolyzate of monophenyl and phenylmethylsilanes is used, which consisted essentially of dimethyltriphenyltrimeth oxytrisiloxane and the following typical properties: average molecular weight 470 compounds weight 155 Specific weight at 25! 1.105 viscosity at 25t, centistokes 13 example The procedure of Example 36 was repeated, but as a polysiloxane for the preparation the α, β-olefinically unsaturated siloxane dipropoxytetramethylcyclotrisiloxane used, Example 51 The procedure of Example 36 was repeated, but as Polysiloxane for the production of the α, β-olefinically unsaturated siloxane Dibutoxytetramethyldi siloxane is used.

Example 52 The procedure of Example 36 was repeated, however as a polysiloxane for the preparation of the α, β-olefinically unsaturated siloxane Pentamethyltrimethoxytrisiloxane is used.

Excellent coatings were also obtained in Examples 48 to 52.

Example 53 The procedures of Examples 36, 48 and 49 were repeated, however, an equivalent amount of 2-hydroxyethyl acrylate instead of the hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester.

Example 54 The procedures of Examples 36, 48 and 49 were repeated, however, an equivalent amount of 2-hydroxypropyl methacrylate instead of the hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester, Example 55 The procedures of Examples 36, 48 and 49 were repeated, however an equivalent amount of 2-hydroxybutyl acrylate in place of the hydroxyethyl methacrylate used in the manufacture of the product from siloxane and unsaturated ester, Example 56 The procedures of Examples 36, 48 and 49 were repeated, however an equivalent amount of 2-hydroxyoctyl acrylate in place of the hydroxyethyl methacrylate Used in the manufacture of the product from siloxane and unsaturated ester, example 57 The procedures of Examples 36, 48 and 49 were repeated but an equivalent Amount of 2-Hydroxydodecanylmethacrylat instead of Hydroxyäthylmethaorylats used in the manufacture of the product from siloxane and unsaturated ester.

Example 58 The procedures of Examples 36, 48 and 49 were repeated, however, an equivalent amount of 3-chloro-2-hydroxypropyl acrylate instead of the hydroxyethyl methacrylate Used in the manufacture of the product from siloxane and tongue saturated ester.

Example 59 The procedures of Examples 36, 48 and 49 were repeated, An equivalent amount of 3-aoryloxy-2-hydroxypropyl methacrylate instead of hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Ester used.

Example 60 The procedures of Examples 36, 48 and 49 were repeated, however, an equivalent amount of 3-crotonoxy-2-hydroxypropyl acrylate in place of the Hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Ester used, Example 61 The procedures of Examples 36, 48 and 49 were repeated, but an equivalent amount of 3-acryloxy-2-hydroxypropyloinnamate instead of of hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Ester used.

Example 62 The procedures of Examples 36, 48 and 49 were repeated, however, an equivalent amount of 3-acryloxy-2-hydroxypropyl crotonate in place of the Hydroxyethyl methacrylate in the manufacture of the product from siloxane and unsaturated Esters used. The products of Examples 53-62 also gave excellent results Coatings Example 63 The procedures of Examples 53 to 62 were repeated, however such an amount of the monohydroxy ester that is olefinically unsaturated in the β-position Monocarboxylic acid used that was sufficient to be functional with at least one To react hydroxyl or hydrocarbonoxy group of the siloxane, but not sufficient to deal with all functional groups of the siloxane molecules in the reaction milk to react, Example 64 The procedures of Examples 53 to 62 were repeated, however, such an amount of the monohydroxy ester that is olefinically unsaturated in the α, β-position Monocarboxylic acid used, which is in excess over the reaction with all functional hydroxyl and hydrocarbon oxy groups of the siloxane molecules in the reaction mixture sufficient Amount was present.

The products of Examples 63 and 64 also gave excellent results Coatings.

Example 65 A pigmented paint composition was prepared by 75 parts by weight of the product of siloxane and unsaturated ester according to Example 48 with 150 parts by weight of a commercially available titanium dioxide pigment and 20 parts by weight Methyl methacrylate premixed. The mixture was shaken with a the same amount of glass beads in a standard paint shaker for 30 minutes ground. The premix was made with a further 75 parts by weight of the product from siloxane and unsaturated ester and 65 parts by weight of the mixture obtained were with 35 parts by weight of an equimolar mixture of styrene and methyl methacrylate diluted. This mixture became 35 parts of methyl methacrylate and 65 parts by weight of the acrylic resin according to Example 36 was added.

The paint was applied to metal, wood and polymer substrates Substances (ABS, i.e. acrylonitrile-butadiene-styrene copolymer) for an average Depth of about 38 T and then applied with an electron beam, as in the above examples, cured.

Excellent coatings were obtained.

Example 66 The procedure of Example 36 was repeated, however curing with a beam potential of 175,000 volts at a Distance of the workpiece of 7.5 cm from the emitting point and with 400,000 volts carried out at a distance of about 75 om, in each case in a nitrogen atmosphere, which contained small amounts of carbon dioxide, was worked.

Example 67 The procedures of Examples 36, 48 and 49 were repeated, however, the copolymer which is olefinically unsaturated in the α, β-position and that in the α, β-position olefinically unsaturated siloxane used in the absence of vinyl monomers, with the viscosity was brought to spray consistency with toluene, which was taken before curing was aborted.

Examples 66 and 67 also gave excellent coatings.

Example 68 Paint compositions were prepared by adding 160 parts by weight of the product of siloxane and unsaturated ester according to Example 36 and 160 parts by weight of the vinyl copolymer according to Example 36 were mixed, this mixture in two equal Parts was divided and one of these parts with 100 parts by weight of methyl methacrylate and the other part was diluted with 200 parts by weight of methyl methacrylate.

The film-forming solutions obtained were on metal substrates applied and then with an electron beam, as in the previous examples, crosslinked, Example 69 Paint compositions were prepared by adding 4C parts by weight of the Product made from siloxane and unsaturated ester Example 48 and 40 parts by weight of the vinyl copolymer according to Example 37 were mixed, this Mixture was divided into two equal parts and one of these parts with 10 parts by weight Methyl methacrylate and the other part diluted with 20 parts by weight of methyl methacrylate became.

The film-forming solutions obtained were on metal substrates applied and then with an electron beam, as in the previous examples, networked.

The products of Examples 68 and 69 also gave excellent results Coatings.

Example 70 The procedure was as in Example 68, but instead of 160 parts by weight of the vinyl copolymer according to Example 36, a mixture of 80 parts by weight of this vinyl copolymer and 80 parts by weight of the unsaturated polyester used according to Example ib0 Excellent coatings were again obtained.

Due to the invention, therefore, result from ionizing radiation curable paint binders and articles of daily use with firmly adhering coatings, obtained from these paint binders by ionizing radiation, wherein the paint binder from 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 hydrocarbonoxy groups, with a hydroxy ester which is olefinically unsaturated in a, ß-position Carboxylic acid and (b) an a, B-position olefinically unsaturated polyester and / or an α, β-olefinically unsaturated copolymer of vinyl monomers consists. Conveniently, the siloxane contains from about 3 to about 18, preferably about 3 to about 12 silicon atoms per molecule. The hydroxy ester is preferably composed of an acrylate or methacrylate, preferably a monohydroxy ester of acrylic acid or methacrylic acid. For making the unsaturated siloxane are preferred Siloxanes with hydroxyl groups and / or alkoxanes with 1 to 4 carbon atoms used as starting material.

The film-forming solution contains from about 20 to about 80, preferably 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 polyester and / or the ß-olefinically unsaturated polyester Copolymers from vinyl monomers0 The olefiniscbea, ß-unsaturation of the in aß-position olefinically unsaturated polyester or the one which is olefinically unsaturated in the a, B-position Copolymers of vinyl monomers is about 0.5 to 5, preferably 0.5 to 3.5 Units per 1000 units of molecular weight. In preferred embodiments the film-forming solution can additionally contain about 10 to about 200 parts by weight free vinyl monomers, optionally also particulate pigments to be available.

In preferred embodiments, radiation is thus produced curable paint binder made from a film-forming solution containing from about 20 to about 80, preferably 30 to about 70 parts by weight of the α, ß-position olefinically unsaturated siloxane, which consists of a siloxane with at least two functional groups, namely hydroxyl groups and lower alkoxy groups, with a Monohydroxyester of acrylic acid or methacrylic acid was obtained, and about 80 up to about 20, preferably about 70 to about 30 parts by weight of an in «, ß-position olefinically unsaturated polyester and / or one which is olefinically unsaturated in a, ß-position Copolymers of vinyl monomers, the concentration of units with olefinic a, unsaturation in the unsaturated polyester or the unsaturated copolymer from vinyl monomers about 0.5 to 5, preferably 0.5 to 3.5 units per 1000 units of the molecular weight.

Another favorable form of training is film-forming Solution plus about 10 to about 200 parts by weight of vinyl monomers, about 20 to about 80 Parts by weight of the α, 2-position olefinically unsaturated polyester and / or des in a, ß-position olefinically unsaturated copolymers of vinyl monomers and about 20 to about 80 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 lower alkoxy groups, with a monohydroxy ester one in a, ß position olefinically unsaturated carboxylic acid was formed.

A particularly preferred radiation curable paint binder consists essentially of about 20 to about 100 parts by weight vinyl monomers, about 30 to about 70 parts by weight of an α, β-olefinically unsaturated polyester containing from about 0.5 to about 5 units of olefinic α, B unsaturation to 1000 units of the Molecular weight and / or one in a, ß-position olefinically unsaturated copolymers of vinyl monomers with about 0.5 to about 5 Units of olefinic α, ß-unsaturation per 1000 units of the molecular weight and about 30 to about 70 parts by weight of one which is olefinically unsaturated in the α, β-position 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 obtained, is preferred in this embodiment an olefinic α, ß-unsaturation of the unsaturated polyester or the unsaturated Copolymers of vinyl monomers from about 1 to about 3.5 units per 1000 units the molecular weight, the α, ß-olefinically unsaturated siloxane preferably consists of a reaction product of a molar proportion of a siloxane with at least two functional groups, namely hydroxyl groups and hydrocarbonoxy groups, in particular lower alkoxy groups, preferably hydroxyl groups and / or methoxy groups, with at least two molar proportions of a nonohydroxyester of acrylic acid or Methacrylic acid, there is therefore a particularly favorable form of Coating of paint formed on the object of use, which is on the surface cross-linked by ionizing radiation, in particular by means of an electron beam from the in situ formed polymerization product of a film-forming solution from about 20 to about 100 parts by weight of vinyl monomers, about 30 to about 73 parts by weight an in α, ß-position olefinically unsaturated polyester with about 1 to about 3.5 units of olefinic a, ß-unsaturation to 1000 units the molecular weight and / or a copolymer which is olefinically unsaturated in the α, β-position from vinyl monomers with about 1 to about 3.5 units of olefinic α, ß-unsaturation to 1000 units of the molecular weight and about 30 to about 70 parts by weight of one in a, ß-position olefinically unsaturated reaction product from a molar fraction a siloxane with at least two functional groups, namely hydroxyl groups and / or methoxyl groups, with at least 2 molar proportions of a monohydroxy ester acrylic acid or methacrylic acid.

The preferred monohydroxy esters for making the unsaturated ones However, siloxanes consist of the monohydroxy esters of acrylic acid and / or methacrylic acid with dihydric aliphatic alcohols having 2 to 8 carbon atoms

Claims (1)

Patent claims 1. Radiation-curable paint binder, thereby marked. that it consists of a film-forming solution of (a) one in a, 3-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, B position olefinically unsaturated carboxylic acid was obtained, and from (b) one in asß-position olefinically unsaturated polyester and / or one which is olefinically unsaturated in a, ß-position Copolymers composed of vinyl monomers. 2. Radiation-curable paint binder according to claim 1, characterized in that characterized in that the siloxane has about 3 to about 18, especially 3 to 12 silicon atoms contains per molecule. 3. Radiation-curable paint binder according to claim 1 or 2, characterized. that the hydroxy ester is made from a monohydroxy ester of acrylic acid or methacrylic acid. 4. Radiation-curable paint binder according to claim 1 or 2, characterized in that the hydroxyester consists of a cinnamate or a Crotonate is made up. 5. Radiation-curable paint binders according to claims 1 to 4, characterized. that the functional groups of the siloxane consist of hydroxyl groups or alkoxy groups having 1 to 4 carbon atoms be. 6. Duroh radiation-curable paint binder according to claims 1 to 5, characterized in that the α, β-olefinically unsaturated polyester or the copolymer of vinyl monomers which is olefinically unsaturated in the α, ß-position about 0.5 to 5, in particular 0.5 to 3.5 units with olefinic α, ß-unsaturation to 1000 units of molecular weight. 7. Duroh radiation-curable paint binder according to claims 1 to 6, characterized in that the film-forming solution is from about 20 to about 80, preferably 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 that in the α, β position olefinically unsaturated polyester or that which is olefinically unsaturated in the α, ß-position Contains copolymers of vinyl monomers. 8. Radiation-curable paint binders according to claims to 7, characterized in that the film-forming solution additionally about 10 to about Contains 200 parts by weight of vinyl monomers. 9. Radiation-curable paint binders according to claims 1 to 8, characterized. that the film-forming solution is also a particulate Contains pigment. 10. Utility item, consisting of a base and one attached to it adhesive coating of a paint on the outer surface, characterized. that the coating consists of the polymerization product formed in situ a film-forming solution of (a) a olefinic in a, ß-position unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups, in particular alkoxy groups, with a hydroxy ester in a, ß-position olefinic unsaturated carboxylic acid was obtained, and from (b) one in a, ß-position olefinic unsaturated polyester and / or one which is olefinically unsaturated in a, ß-position Copolymers composed of vinyl monomers that are ionizing on the surface Radiation has been networked. 11e commodity according to claim 10, characterized in that it that the siloxane contains 3 to 18, in particular 3 to 12 silicon atoms per molecule. 12. commodity according to claim 10 or 11, characterized in that that the hydroxy ester is made from a monohydroxy ester of acrylic acid or methacrylic acid consists, 13. commodity according to claim 10 or 11, characterized in that that the hydroxyester consists of a cinnamate or grotonate, 14. commodity according to claim 10 to 13, characterized in that the functional groups from Consists of hydroxyl groups or alkoxy groups with 1 to 4 carbon atoms, 15. commodity according to claims 10 to 14, characterized in that the a, ß-position is olefinic unsaturated polyester or the α, β-olefinically unsaturated copolymer from vinyl monomers about 0.5 to about 5, preferably 0.5 to about 3.5 units of olefinic α, ß-unsaturation per 1000 units of the molecular weight Contains0 16Q article of daily use according to claims 10 to 15, characterized in that the film-forming solution from about 20 to about 80, preferably from about 30 to about 70 parts by weight of the a, β-olefinically unsaturated siloxane and about 80 to about 20, preferably about 70 to about 30 parts by weight of the α, β-olefinically unsaturated polyester and / or the copolymer of vinyl monomers which is olefinically unsaturated in the a, B-position contains, 17. commodity according to claim 10 to 16, characterized in 1 that the film-forming solution additionally contains about 10 to about 200 parts by weight of vinyl monomers contains. 18. commodity according to claim 10 to 17, characterized in that that the film-forming solution also contains a particulate pigment.