DE1644796A1 - Radiation-curable silicone-modified paints and coatings - Google Patents

Description

Radiation curable silicone modified paint - =========================================== =============== and coating compositions ================== The invention relates to radiation-curable, Silicone-modified paints and coatings, especially for coating of wood and / or metal surfaces with decorative and weather-resistant Cover. Improved paints result for this purpose. The invention also relates to the use of these coating compounds for painting wooden and metal objects. As a result of the invention, there is an improved binder made from a silicone-modified one organic resin and a resin that can be copolymerized with it by ionizing radiation Vinyl monomers.

The object of the invention consists in radiation-curable silicone-modified ones Paint and coating compounds with exceptionally good weather resistance. The. Acc. To #en paints and coatings are chemical designed to allow rapid curing by ionizing radiation, for example an electron beam.

The term "paint", "coating compound" or "coating compound" used here includes both a binder that contains finely ground pigment and / or Plilletoff, a binder without pigment and / or filler or with a very low content dereelben, which can be colored or tinted anoh if desired, as well as others Surface oversize compositions which contain the binder and which are generally found to be can be labeled analogously to enamel, varnish or lacquer primers. Thus, the Binder, which eventually becomes permanent, compared to usual operating conditions resistant pill is transferred through the final hardening, completely or practically consist entirely of the binder used to produce the film, or it can be referred to as a carrier for pigment and / or mineral filler material will.

The term "ionizing radiation" used here denotes radiation with sufficient energy to remove an electron from a gas valley Formation of an ion pair su remove and as a result radiation with a Energy of about 5,000 electron volts or an equivalent size to this sur Carrying out the polymerization of the paint films described here applicable. The preferred method of curing the films from the present Color binders on the substrates to which they were applied consists in the fact that these films exposed to a beam of electrons causing the polymerization, the is between 150,000 and 450,000 electron volts at its distribution point or has an equivalent size. In this curing process, it is preferred to use a Minimum of 25,000 electron volts per 2.5 cm distance between the radiation emitting point and to apply the workpiece, the space in between being filled by air is. Regulations can also be made so that the gas in between is relatively stable, for which purpose an oxygen-free inert gas such as nitrogen is preferred or helium is used.

According to the invention, the polymerization can be carried out using the radiation commonly referred to as "high-energy particle radiation" as well as with "ionizing electromagnetic radiation".

The paint binders according to the invention consist of an improved silicone-modified organic resin having a molecular weight above about 1,000, advantageously between about 1,000 and about 50,000, and preferably between about 2,000 and about 20,000 with about 0.5 to about 3 , preferably about 1 to about 2, and preferably about 1.25 to about 1.75 olefinic light saturations per 1,000 units of molecular weight and from at least one, but possibly two different vinyl monomers, for example a vinyl hydrocarbon such as styrene and one Acrylic monomers such as methyl methacrylate. . The term "vinyl" as used herein denotes organic compounds with a terminal group The films formed from the preferred embodiments of the coating compositions according to the invention cure at relatively low temperatures, for example between room temperature (20 to 25 ° C) and the temperature at which significant evaporation of the most volatile component begins, but usually between 20 and 70 ° C. The radiation energy is applied in doses of about 0.1 to about 100 Mrad per second to a preferably moving workpiece, the coating taking up a total dose in the range of about 0.1 to about 100, preferably about 1 to 25 Mrad. These films are transferred by the electron beam b'.i adhesively bonded, abrasion-resistant and weather-resistant coatings that meet the following conditions: Applied underlay type of load requirements when trying wood or soaking in withstands immersion metal water at room temperature in water of 20 - 25 ° C temperature for 240 hours without significant loss of gloss or film cohesion, ie without pin cracks, cracks, cracks or peeling.

Repeated wood withstands 25 cycles and hits from each 4-hour baking immersion in boiling water and then 15 hours Dry at 62-63 ° C without significant loss of gloss or film cohesion.

Metal elongation withstands 25% elongation without breaking at one Coating from 0.025 mm to 0.05 mm and a core of 3.17 mm.

Wood or ultraviolet can withstand 2000 hours of metal exposure exposure in an Atlaa U3travi ole t t carbon arc standard weather meter without limescale and without loss of gloss or film cohesion.

The silicone-modified resins preferably used here are resins of the polyester type having the above-mentioned level of unsaturation, a Molecular weight above about 1000, which incorporated an acyclic or cyolic contain siloxane, which contains a reactive hydroxyl or Has oxyhydrocarbon group which is attached to at least two of the silicon atoms of the siloxane are bound. The oxyhydrocarbon group contains above all a lower alkyl radical with 1 to about 6 carbon atoms.

The term "siloxane" used here refers to compounds the one - Si - 0 - Si Sli - s: i (-0 - ~ ° ~) s! in 0 n1 or - contain C - O - Si - or - group, in which n is a positive integer iuid the remaining values through a hydrocarbon radical, an oxyhydrocarbon group, a hydrogen atom, a hydroxyl group or an oxygen atom, which connects a silicon atom with a further silicon atom , are saturated.

Contain the acyclic siloxanes used according to the invention advantageously at least three silicon atoms per molecule with the corresponding Oxygen bonds.

The preferred siloxanes can be represented by the following general formula: wherein n is at least 1 and X is either a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms or a monovalent oxyhydrocarbon radical having; I to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms or a hydroxyl group or a hydrogen atom, where at least two of the groups X separated by a group X - Si - 0 - Si - X from a hydroxyl group or an oxyhydrocarbon radical with 1 to 8 Carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms.

A variety of methods are known for the production of siloxanes. This includes regulated hydrolysis of silanes. Polymerization of a siloxane lower molecular weight in the presence of an alkoxysilane, conversion of silicon tetra chloride with an alcohol and similar procedures. The manufacture of siloxanes and theirs Incorporation into organic resins is described, for example, in American patents 3,154 597, 3 074 904, 3 044 980, 3044 979, 3 015 637, 2 996 479, 2 973 287 2 937 230 and 2 909 549.

The elic siloxanes suitable for use according to the invention contain at least 3, preferably 6 to 12 and usually not more than 18 silicon atoms per molecule with corresponding oxygen bonds. The eyclic polysiloxanes can in the form of compounds ont @ prechend the following general formulas used become: I.) Xn, Sin0n ", where n is an odd positive number of at least 3, n ' = 2n and n "= n and X (a) is a monovalent hydrocarbon radical with 1 up to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms or (b) a monohydric oxyhydrogen fabric frect with t up to 8 Carbon atoms, preferably an alkoxy radical having 1 to 4 carbon atoms or (c) represents a hydroxyl group or (d) represents a hydrogen atom, where at least two of the groups X separated by a grouping X = Si - 0 - Si - X either consist of grouping (b) or group (c).

An example of this is given by the following formula: II.) Xn, Sin0n ", where n is an odd positive number of at least 5, n '= n + 3 and nn means the numbers 6, 6 + 3 or 6 + a multiple of 3 and X (a) is a monovalent carbon m @ Substantial red 1 to 8 carbon atoms, preferably oinen alkyl radical r @@ 1 to @ carbon atoms or (b) an @ e @ verbal oxyhydrocarbon radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to carbon atoms or (c) a hydroxyl group or @ (a) represents a hydrogen aome @@ t, with at least @ av @@ de @ separated by the group @ r @ ng @ - Si - 0 - Si - X from either group (b) or group (c) An example is given by the following structural formula: III.) Xn, Sin0n ", where n is the number 6 or a multiple of 6, n 'the numbers 8, 8 + 6 or 8 + a multiple of 6 and n" the numbers 8 8 + 9 or ri + a multiple of 9 and X denote (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 oxyhydrocarbon radical having 1 to 8 carbon atoms, preferably an alkoxy radical having 1 to 4 carbon atoms or (c) A hydroxyl group or (d) represents a hydrogen atom, where at least two of the groups X separated by the grouping X - Si - O - Si - X consist of either group (b) or group (c). An example is given by the following structural formula: Dimers, trimers and the like formed therefrom by condensation can also be refused with loss of water or alcohol.

IV.) Xn, Sin0n ", where n is an even positive integer @ of at least 4, n '= n + 4 and rk' mean the numbers 4, 4 + 3 or 4 + a multiple of 3 and X (a) is a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms or (b) a monovalent one Oxy-carbon residue with 1 to E3 carbon atoms, preferably an alkoxy residue with 1 to r. Carbon atoms or (o) a hydroxyl group or (d) a hydrogen atom represents, where at least two of the groupings X - Si - O - Si - X obtained Groups X either from group (b) or group (e) exist.

An example is given by the following structural formula: where m is the number 0 or a positive whole number, V.) Xn, Sin0n ", where n is an even positive whole number of at least 8, n '= n # 2 and n" the numbers 11, 11 + 3 or 11! a multiple of 3 major and X. (a) an e @@ valued hydrocarbon residue with 1 to # carbon atom, preferably an ally @@ ent mi @ 1 am 4 carbon atoms or (b) ei @ en eim @@ tigen oxy carbon - @@@ @ sera @ offrest with 1 to 8 coals @@@@ @@@@@@@ vorr @ ga - @@@@@ e @ gen Alkoxy @@@@ with 1 or @ @@@@@@@@@ @@@ or represents, where at least two of the groups X separated by the grouping X - Si - 0 - Si - X do not consist of the grouping (b) or the group @@@.

An example is given by the following structural formula: where m is a positive integer.

A variety of methods are available for making such siloxanes known he most common process is the controlled hydrolysis of silanes. Other methods consist in the polymerization of an eyclic siloxane of lower value Molecular weight in the presence of a dialkoxysilane, referring to the e US patent 2 909 549 is referred, in the reaction of silicon tetrachloride with an alcohol, See US Pat. No. 2,777,202 will and similar Procedure. Cyclic siloxanes are included in this latter patent listed, which also contains substantial general remarks on alkoxysiloxanes. Siloxanes containing hydroxyl groups are described, inter alia, in US Pat. No. 2,973 287.

The starting resin or the monomer with which the siloxane is reacted, preferably contains only a minimum number of hydroxyl groups above that required for the reaction with the reactive hydroxyl or oxyhydrocarbon groups of the siloxane molecules, to be built into the resin, the required number.

At least two such reactive groups on the siloxane must be reacted with the starting resin or the monomer and in an Ausftllirungsform become the hydroxyl or oxyhydrocarbon groups remaining on the siloxane then reacted with a further monomer, as explained below will. The finished resin contains prior to its copolymerization under irradiation with the vinyl monomers advantageously from about 15 to about 50, preferably about 20 up to about 40 percent by weight silicones, i.e. structures that differ from siloxanes derive.

At. The preferred embodiment is a silicone-modified one Polyester type resin prepared by first adding the acyclic or cyclic siloxane with a polyhydric alcohol, preferably a branched chain polyhydric one Alcohol, such as E.g. neopentyl glycol is reacted, followed by the first obtained product with a acyclic, alpha, beta unsaturated Bicarboxylic acid or its anhydride, for example maleic anhydride, and / or a cyclic aliphatic dicarboxylic acid or its anhydride, for example Tetrahydrophthalic anhydride or 1,2-cyclohexanedicarboxylic acid is reacted.

In another embodiment, the polyester is formed first, by adding a polyhydric alcohol, especially a branched, polyhydric one Alcohol, an acyclic, alpha, beta-unsaturated dicarboxylic acid or its anhydride and / or a cyolic aliphatic dicarboxylic acid or its anhydride, optionally together with a straight-chain polyhydric alcohol, for example propanediol or butanediol, has been unset, whereupon this product with the cyclic or acyclic siloxane is implemented.

In another embodiment, an unsaturated polyester is used formed as in the above-described embodiments or it is a Saturated type polyester prepared by using a saturated acyclic dibasic Acid, such as succinic acid, in place of maleic acid or maleic anhydride is used, whereupon after the reaction of the siloxane with the monomer bzvi. dciii polymers the remaining hydroxyl or Oxykchlenwa @@ @erstoffgruppen des Siloxane with suitable unsaturated hydro kylgruppenhal term monomers or Low molecular weight esters, for example the reaction product of maleic anhydride and a polyhydric alcohol, can be reacted to produce the desired Unsaturation to give for the polymerization.

In a further embodiment, a hydroxyl group-containing one is used Vinyl resin is made using a vinyl monomer such as acrylic acid, methacrylic acid or esters thereof, at least one of which is composed of a hydroxyl group-containing compound Monomers, for example 2-hydroxyethyl methacrylate, consists, are implemented, whereupon some of the hydroxyl or oxyhydrocarbon groups of the siloxane with the hydroxyl groups of the resin are reacted and then the rest be reacted with a hydroxyl-containing unsaturated compound.

In addition to the silicone-modified resins discussed above in the paints and coating compositions according to the invention at least one vinyl monomer, however, two different vinyl monomers are preferably present. Is preferred at least one acrylic monomer and one vinyl hydrocarbon monomer are present. The acrylic monomers used here are monounsaturated monocarboxylic acids in the alpha, beta position or their esters and belonging to this without being limited to Acrylic acid, alkyl acrylic acids, for example methacrylic acid, monohydric esters or polyhydric alcohols of acrylic acid and alkyl acrylic acids, and in certain Cases of halogenated derivatives thereof, e.g. 33. Chloracrylic acids and their esters. Preferred the paints and coatings contain a Gomisoh made of acrylic monomers and vinyl monomers, whereby the acrylic monomers are preferred (Ren larger part the monomers @ mixed turn off.

In the reaction schemes below are two methods of preparation of the coating compositions according to the invention. The presentation was based on preferred reactant, namely neopentyl glycol, maleic anhydride, tetrahydrophthalic anhydride and a dihydroxysiloxane and a dimethoxysiloxane, respectively.

Reaction scheme @ Keation participant 0.113 OH3 of the recommended level H0-O-0OH2H + H0xanO11 + H0CH2CC1120H 0113 OH3 0.113 0.113} Intermediate product HO-OC-OH2-0Siloxa: -0112-C, -OH2-011 + 2 1120 0113 0113 I participant 11? 0o 0; the second stage + 110 112 V oa, U3 bind he + 71 A Reaction scheme 2 w HO OH 13th of the first stage OK + H / O + HO-O-0-C2-OH rl unsaturated 1W -O OH OH + 9 Pc parts 1 siloxane OCH3 the second study I < 10 \ + g The abbreviation Mrad used here means 1,000,000 rads. The term "rad" denotes the radiation dosage which results in an absorption of 100 ergs of energy per gram of the absorpti @ @ emitter, ie the coating film. The delivery device for electrons may be an electron linear accelerator which gives a DC potential in the above-mentioned range. In such a device, the electrons are usually emitted from a hot filament and accelerated by a uniform increase in voltage. The electron beam, which can have a diameter of about 3.1 mm at this point, is then deflected in one direction so that a fan-shaped beam results which then passes through a metal window, for example an alloy of magnesium and thorium about 75 microns thick to be led.

The paints and coating compositions according to the invention are film-forming Solutions of the silicone modified resin in the vinyl monomer. The binder becomes preferably on the base as a continuous film of practically the same Applied depth and cured thereon, preferably to a depth in the range between about 2.5 to 100 microns depending on the substrate and intended end use which is dependent on the coated product. The paint binder solution preferably contains about 30 to about 70, preferably 40 to 60, of silicone-modified binder resin and about 70 to about 30, preferably 60 to 40% of the nonpo @ ymorized Vinyl monomers. In a preferred embodiment, the vinyl monomers are the paint binder a mixture of about 30 to 70, preferably 40 to 60 and particularly preferably 45 to 55% acrylic monomers with the remainder being non-acrylic vinyl monomers. For example, increased resistance to weathering is achieved through increased Amounts of acrylic monomers, e.g. methyl methacrylate, obtained while a Lowering the required radiation dosage can be achieved if the The amount of vinyl hydrocarbon monomer such as styrene is increased - with the respective amounts of these monomers can be regulated so that they the correspond to the respective circumstances.

The paint binder can be applied to the substrate by conventional spraying be applied, including a viscosity in the range of about 5 to about 50, preferably Has about 10 to about 35 seconds (Ford cup), or it can be spread through Rollers are applied, coated by flow or by the generally known as Silk lattice processes are drawn processes with suitable adjustment of the viscosity be applied. The film-forming material should have a sufficiently low viscosity have to be applied quickly to the substrate in practically even depth to allow, and have a sufficiently high viscosity that a film of 25 micron thickness adheres to a vertical surface without seeping away. The viscosity of the binder can be changed by changing the molecular weight of the resin or the Resins and / or by changing the relative concentrations of the Resin component and / or by changing the relative concentrations of the various Set monomers within the monomer component. The binder is preferred on the base practically free of non-polymerizable organic solvents and / or diluents applied.

The term "olefinic unsaturation" as used herein relates relate to an alpha, beta-unsaturated acid or such an anhydride.

The binders can also contain pigments and dyes in the usual amounts and fillers, especially mineral fillers. The specified Percentages are given on a pigment and mineral filler-free basis.

Preferred examples of paint binders are made of a resin with a molecular weight above about 1,000, in particular 2 GOO to about 20,000 with a content of about 0.5 to about 3 olefinic unsaturations, in particular 1 to 2 olefinic unsaturations for every 1,000 units of the molecular weight, that from a copolymer of an acyclic, alpha, beta-unsaturated dicarboxylic acid or its anhydride, a cyclic olefinic dicarboxylic acid or its anhydride, a multi-word one composed only of carbon, hydrogen and oxygen A @@ bhol and a 3-bit acyciic siloxane; 12 silicon atoms with dissociable Hydroxyl groups or oxyhydrocarbon groups, di o at least 2 of the silicon atoms are bonded, as well as the vinyl monomers.

Another very favorable form of the paint binder is available in addition to the vinyl monomers from a silicone-modified organic resin with a Molecular face above 1,000, preferably 2,000 to 20,000 and about 1 to 2 olefinic unsaturations for every 1,000 units of molecular weight, which by converting a polyvalent one made of carbon, hydrogen and oxygen built-up alcohol with an acyclichen siloxane with 3 to 12 silicon atoms and with dissociable hydroxyl groups or osyhydrocarbon radicals at least 2 silicon atoms and by reacting the product obtained with maleic anhydride and tetrahydrophthalic anhydride. Preference is given here to being polyvalent Alcohol a branched chain alcohol, especially neopentyl glycol is used.

Paint binders made from a silicone-modified organic resin consist of vinyl monomers, this resin having a molecular weight above 1,000, in particular between 2,000 and 20,000 and about 1 to 2 olefinic Has unsaturations per 1,000 units of the molecular weight and atis a copolymer of a polyester resin, as @ from a mixed polymer of Maleic anhydride, tetrahydrophthalic anhydride and a polyvalent one Carbon, hydrogen and oxygen built up alcohol, with an acyclic siloxane with 3 to 12 silicon atoms and at least 2 silicon atoms standing hydroxyl or oxyhydrocarbon residues. Alcohol is preferred from a branched-chain alcohol, especially neopentyl glycol. Outstanding Paint and coating compositions are also obtained when in the above embodiments the acyclic siloxane with 3 to 12 silicon atoms by a cyclic siloxane with 3 to 18 silicon atoms, in particular 6 to 12 silicon atoms with a dissociable Hydroxyl group or oxyhydrocarbon group attached to at least two silicon atoms, is bound, is replaced.

Particularly cheap products are obtained when about 20 to about 50 percent by weight of the modified resin is acyclic or cyclic Derive silosans.

Excellent results are also obtained with paints, the about 50 to about 70 weight percent of the silicone modified ones listed above Polyester resins and about 50 to 30% by weight of this resin by ionizing radiation copolymerizable vinyl monomers, this resin having a molecular weight from about 2,000 to about 20,000 and about 1 to about 2 olefinic unsaturations to 1,000 units of molecular weight, with about 15 to 50 percent by weight the same of acyclic siloxanes with 3 to 18 silicon atoms or acyclic Derive siloxanes with 3 to 12 silicon atoms.

Paint binders from about 30 to about 50 are also very useful % By weight of silicone-modified polyester resins and about 70 to 50% by weight with this ionizing radiation of copolymerizable vinyl monomers, the resin having an average molecular weight between about 2,000 and about 20,000 and about 1 to 2 olefinic unsaturations to 1,000 units of molecular weight, with about 15 to 50 wt.% the same of cyclic siloxanes of 3 to 18 silicon atoms or acyclic ones Derive siloxanes with 3 to 12 silicon atoms.

The Parb binders listed in the following examples The silicone-modified resins used each had molecular weights above of 1,000, a level of unsaturation as noted above, and after application and hardening, they met the conditions listed above.

Example 1 A color binder resin with a silicon-modified polyester was produced in the following way: 1,330 kg of neopentyl glycol were placed in a raw material vessel and 1 080 kg of a customary methoxylated partial hydrolyzate of monophenyl @ - and Given phenylmethylsilenes, essentially from dimethyltripheny @ trimethoxytrisiloxane (Dow Corning - Sy @ kyd 50) and has the following properties: Average molecular weight 470 union weight 155 specific gravity at 2500 1.105 viscosity at 250C (centistokes) 13 The mass was heated to about 1740a, about 215 kg of methanol Were distilled off overhead. The feed was cooled to 12100, followed by 196 kg maleic anhydride, 964 kg tetrahydrophthalic anhydride, 2.2 kg dibutyltin oxide and 150 kg of xylene were added. The temperature of the feed slowly rose increased about 21500 and maintained this temperature until the resin obtained a Acid number of 10. Vacuum was applied to Ea to remove the xylene, followed by 61 kg hydroquinone was added and the feed cooled to 9300 and poured into a mixing tank was added along with 780 kg of styrene. A white grinding base became then made. adding 3 050 kg of TiO2, 1805 kg of the according to the previous paragraph resin produced, 146 kg of styrene, 507 kg of methyl methacrylate and 20 kg of bakers M.P.A., a high molecular weight waxy castor oil derivative for relief of grinding by adjusting the viscosity and to support maintenance the pigment dispersion were mixed in the grind, whereupon the above Mixture was passed through a conventional sand grinder.

This grinding base was continued with styrene and methyl methacrylate pre-thinned in such amounts that a paint made of about 40% RESIN, 30 % Styrene and 30% Methyl methacrylate yielded. A film of the received Paint was sprayed onto wooden panels and metal disks and treated with a Electron beam irradiated under the following conditions: Potential 295 kV current 1 milliampere distance, from the external point to the workpiece 25 cm linear speed 1.6 cm / sec.

Passes 2 total dosage 10 Mrad.

Example 2 A paint concentrate with a silicone modified Polyester was made from the following ingredients: Parts by weight White mill base according to example 1 5565 silicone-modified polyester resin, produced according to example 1 1785 styrene 1i0 methyl methacrylate 1 1552 red grinding base 198 The red grinding base was prepared @ # by first adding 130 parts by weight of a 50% solution of a common Acrylic paint binder resin (Gardner-Holdt viscosity bet 25 ° C W in Toluene, 40 parts by weight of burnt sienna pigment and 150 parts by weight of xylene mixed became. This mixture became one in 40 hours in a steel ball mill Fineness of 8 Heg ground, then added to 340 parts by weight of the same acrylic resin rden.

The paint meter concentrate listed above was made with styrene and methyl methacrylate diluted, so that a paint with a content of about 40% resin, 30% styrene and 30% methyl methacrylate on wood panels and metal sheets sprayed on and irradiated as in the previous example.

Example 3 The procedure of Example 2 was carried out using the the following substances for the production of the paint concentrate are repeated: Parts by weight: White grinding base according to Example 1 5680 silicone-modified polyester resin, manufactured according to Example 1 1676 styrene 1050 Mothylme @ hacrylat 1527 Green Mah @ base 267 The green milling base was prepared by adding 120 parts by weight of a 50% solution a common acrylic paint binder resin Gardner- @ oldi-Vi @@ onitä @ lei 25 ° C @@@ Ky @@@. @@@ @@@@@@@@@@@@@@ @@@@@@@@@@@@@ important parts Kylol were mixed. This mixture was placed in a steel ball mill for 48 hours ground to a fineness of 8 Heg, followed by 240 parts by weight of the above Acrylic polymers and 60 parts by weight of styrene added and the mixture a further 2 Has been ground for hours. 264 parts by weight of the same were added to this grist Acrylic polymers, 130 parts by weight of a melamine-formaldehyde resin containing butyl groups (60% solids, 20% xylene, 20% butanol) and 65 parts by weight of xylene were added.

The paint concentrate thus prepared was diluted with styrene and methyl methacrylate to form paints, the following composition had: resin% $ styrene% $ methyl methacrylate 60 20 20 SO 30 50 30 20 40 30 30 these Paint masses were sprayed onto wooden panels and metal sheets and passed through Irradiation cured as in the previous examples.

Example 4 The procedure of Example 1 was repeated with the exception that neopentyl glycol, maleic anhydride and tetrahydrophthalic anhydride together were reacted and then the product with the siloxane until it was clear was implemented at a maximum of 17600.

Example 5 The procedure according to Example 1 was repeated with the assumption that that an equivalent amount of dibutoxytetramethyldisiloxane instead of dimethyltriphenyltrimethoxytrisiloxane was used. el6 The procedure according to Example 1 was repeated with the exception that an equivalent amount of pentamethyltrimethoxytrisiloxane instead of dimethyltriphenyltrimethoxytrisiloxane was used.

Example 7 E @ n resin was prepared from the following monomers: Mol Grams of maleic anhydride 3.6 353.0 tetrahydrophthalic anhydride 6.4 973.8 neopentyl glycol 14.0 1458.1 i [in melt-cooking of tetrahydrophthalic anhydride and @eopentylglycol was carried out for 23 hours. Water passed over at 165 ° C and became a Get maxisal temperature of 1800a. The hard obtained had an acid number of below 15 and was cooled to room temperature, whereupon the maleic anhydride along with 1.39 grams of hydroquinone @md 300 com xylene was added. The loading became up to one. Heated acid number of 10, with water passed over at about 140 ° C and a maximum temperature of 180 ° C was reached.

A 25% silicone modified resin was made using 503.4 grams of the above resin and 167.8 grams of dimethyltriphenyltrimethoxytrisiloxane manufactured. The feed was heated for about 3 hours with methanol passed at about 1200C and a maximum temperature of 16300 was obtained. the Charge was then rapidly dropped to about 10,000, with 0.106 g of hydroquinone were added and then 212.3 g of styrene were added at 80.degree.

A paint binder was made with a content of 50 parts by weight of the above silicone-modified resin, 25 parts by weight of styrene and 25 parts by weight Methyl methacrylate produced. The binder was on wooden board and metal sheets sprayed on and irradiated as in the previous examples. lilaoh 8 passes the coating exhibited a Sward hardness of 18.

Another paint binder was made using 25 parts by weight of the above silicone-modified resin, 10 parts by weight of methyl methaorylate, 10 parts by weight of styrene and 5 parts by weight of ethylene glycol dimethacrylate produced Binder was sprayed onto wooden panels and metal discs and as in the above Examples irradiated.

After 4 or 6 DurohgMngen the coating showed a Sward hardness of 16-18 or 26-28.

A milling base was prepared from the following ingredients : 600 parts by weight TiO2 300 "of the silicone-modified resin from this example 100n styrene 100 "methyl methacrylate.

The mixture was ball milled for 17 hours. One Paint mousse lake was prepared from the following ingredients: 110 parts by weight the above mill base 34.3 # of the silicone modified resin made from it Example containing 25% styrene, 3.7N styrene 12.3 3 "clX methyl methacrylate 11.1 "ethylene glycol dimethyl methacrylate.

The paint was sprayed onto wood and Xetallbleohe and irradiated as in the previous examples.

This coating showed a Sward hardness of about 4 passes 22nd

Example 8 A resin was prepared from the following monomers: Mol Grams of maleic anhydride 3.44 337.3 tetrahydrophthalic anhydride 2.82 429.0 neopentyl glycol 12.4 1291.5 diallyl ether of pentaerythritol 3.72 604.6 hydroquinone 1.43 300 com Xylene A melt boiling with tetrahydrophthalic anhydride and neopentyl glycol was carried out until an acid number of about 10 was reached. Water went by about 170 ° C above and a maximum temperature of about 19500 was obtained. the Charge was cooled to room temperature and then maleic anhydride and the diallyl ether of pentaerythritol was added together with the hydroquinone. The loading was heated and reflux began at about 140 ° C. The heating was during 23 hours continued.

A maximum temperature of 180 ° C was obtained and the resin had an acid number of about 9.

A 50% silicone modified resin was made by heating 351.7 parts by weight of the above resin and 351.7 parts by weight of dimethyltriphenyltrimethoxy-trisiloxane manufactured. Methanol went over at about 12200.

Heating was continued for 2.5 hours and it became one Maximum temperature of 162 ° C obtained. The resin was to 10000 cooled, where then 0.105 parts by weight of hydroquinone were added. After another After cooling the resin to 80 ° C., 210.6 parts by weight of styrene were added.

A milling base was made by milling the following ingredients prepared in a ball mill for 20 hours: 300 parts by weight of the above Silicone modified resins 600 "TiO2 100 w styrene 100 n methyl methacrylate.

A paint or coating compound was made from the above grinding base, Styrene, methyl methacrylate and ethylene glycol dimethyl acrylate with the following composition manufactured: 32% TiO2, 68% carrier: 50 parts by weight resin 25 u styrene 25 methyl methacrylate 10 N ethylene glycol dimethylacorylate.

The paint was sprayed onto Holsplatten and metal disks and as in the previous examples using a potential of 260 kV irradiated.

Example 9 The procedure of Example 1 was followed with the exception. repeated, that the potential of the electron beam was 175,000 electron volts, the The exposure has been regulated so that a total dose equivalent to that after Example 1 revealed.

Example 10 The procedure of Example 1 was repeated with the exception that the potential of the electron beam was about 400,000 volts and the exposure was regulated in such a way that a total dosage is equivalent to that according to the example 1 resulted.

Example 11 A paint binder resin with a silicone modified one Polyester was made in the following way: In. one reaction vessel became 70 kg of neopentyl glycol, 10 kg of xylene and 35 kg of a commercially available hydroxyl functional ion ayollaohon polysiloxane (Dow Oorning Z-6018) added with the following properties: Hydroxyl content, dean Stark% condensable 5.5% free 0.5 average molecular weight 1600 union @ weight 400 Refractive index 1.531 to 1.539 Durran softening point Mercury method, ° C (° F) 93 (200) at 60% solids in xylene specific gravity at 2500 1.075 viscosity at 25 ° C, centipoise 33 Gardner-Holdt A-1 The feed was heated to about 174 ° C for 2 1/2 hours, whereupon 13.7 kg of maleic anhydride, 54.2 kg of tetrahydrophthalic anhydride and 220 g of dibutyltin oxide were added. The temperature of the feed was slowly increased to about 221 ° C and this was increased Maintain temperature until the Hars obtained has an acid number of about 10. Some of the xylene and water of reaction were removed during the boiling and the The excess is then stripped off in vacuo. To the charge was added 27.6 grams of hydroquinone added and the mass cooled to 82.5 ° C and diluted with 40 kg of styrene.

A white grinding base was made by adding 3050 kg of TiO2, 1805 kg of the resin prepared according to the previous paragraph, 146 kg of styrene, 507 kg Methyl methacrylate and 20 kg Bakers M.P.A., a waxy castor oil derivative of high molecular weight to facilitate grinding by means of viscosity adjustment and mixed to aid in maintaining pigment dispersion in the mill and passing the above mixture through an ordinary sand grinder.

This milling base was continued with styrene and methyl methacrylate diluted in such amounts that a coating composition of about 40% resin, 30% Styrene and 30% methyl methacrylate. A film of the resulting paint was sprayed on wooden panels and metal disks and with an electron beam irradiated under the following conditions: potential 295 KV, current 1 milliampere Distance, from the sending point to the workpiece 25 cm, linear speed 1.6 cm / sec.

Passes 2 total dosage 10 Mrad.

Example 12 A paint concentrate with a silicone modified Polyester was made from the following ingredients: Parts by weight White milling base according to Example 11 5565 silicone-modified polyester resin, prepared according to Example 11 1785 styrene 1100 methyl methacrylate 1552 red grinding base 198 the The red grinding base corresponded to that given in Example 2 above.

The paint concentrate listed above was made with styrene and methyl methacrylate diluted, with a paint or coating composition with About 40% resin, 39% styrene and 30 s methyl methaorylate resulted on wooden panels and metal disks sprayed on and irradiated as in the previous examples became.

Example 13 The procedure of Example 12 was repeated, wherein The following substances were used to produce the slaked corn concentrate: Parts by weight of white grinding base according to Example 11 5680 silicone-modified polyester resin, produced according to example 11 1676 styrene 1050 methyl methacrylate 1 1527 green grinding base age 267 The green mill base was the same as that used in Example 3 above.

The paint concentrate produced from this was made with styrene and methyl methacrylate diluted, so that paint @ masses of the following composition resulted in: Resin% styrene% methyl methacrylate 9s 60 20 20 50 20 30 50 30 20 40 30 30 These paints were applied to wooden panels and metal sheets sprayed and cured by radiation as in the previous examples.

Example 14 The procedure of Example 11 was followed with the exception repeats that neopentyl glycol, maleic anhydride and tetrahydrophthalic anhydride were reacted together and the product obtained in this way then with the siloxane was implemented.

Example 15 The procedure of Example 11 was followed with the exception repeats that a ethoxy-functional cyclic siloxane instead of the hydroxyl-functional cyclic siloxane was used. In the reaction, as a by-product Obtain methanol. This siloxane contains 6 silicon atoms and is the same as above listed formula type IV.

The procedure was also carried out using Dipropocytetremethylcyclotrisiloxane repeated.

Example 16 A resin was prepared from the following monomers: Mol Gram maleic anhydride 3.6 353 tetrahydrophthalic anhydride 6.4 973.8 neopentyl glycol 9,395 978.49 Diallyl ether of pentaerythritol 2.81 607.8 A melt boiling with Neopentyl glycol and tetrahydrophthalic anhydride were carried out for 21 hours.

Water @ing at about 157 ° C above and it became a maximum temperature reached by about 20500. The resin obtained had an acid number of about 17. Melic anhydride and dial ether of pentaerythritol were added along with about 1.46 g of hydroquinine and heating the charge for about 13 hours. Water went at about 140 ° C over and a maximum temperature of about 186 ° C was obtained.

A su 25% silicone modified resin was made at Use of 503.6 grams of the above resin and 167.8 grams of the hydroxyl functional cyclic siloxane used in Example 11, the hydrocarbon groups of which are predominantly consist of vinylphenyl groups. These substances were together for about 2.5 hours heated. Water passed at about 13900 and it became a maximum temperature of received around 16009. The feed was rapidly increased to about 100 ° C where 0.112 g of hydroquinone were added with stirring, and to about 80 ° C, where 223.8 g of styrene were added, cooled down.

The paint binder was made from 50 parts by weight of the above Silicone modified resin, 25 parts by weight @ styrene and 25 parts by weight methyl methacrylate manufactured.

This binder was sprayed onto wooden disks and metal plates and irradiated as in the previous examples.

The hardened color image showed a Sward hardness after 2 passes from about 28 to 30 (about 10 Mrad) and after 4 passes from about 56 to 38 (about 20 Mrad).

A pigmented coat of paint is produced by first applying The grinding base was made from the following components: 600 g TiO2 300 g of the silicone-modified Resin according to this example 100 g of Styr @ l 100 g of methyl methacrylate.

This material was ground in the ball mill for 20 hours and a paint made up of the following ingredients: 100 g of the above Grinding base 19.4 g silicone-modified resin according to this example 23.4 g methyl methacrylate 18.57 g of styrene 0.557 g of 2-hydroxy-4-acetyloxybenzophenone (UV adsorber) This paint composition was sprayed onto wooden panels and metal sheets and as in the preceding Examples irradiated. This paint shows a Sward hardness of about 26 2 passes.

Example 17 A 50% silicone modified resin was applied The following manner was prepared: The starting polyester resin was prepared from the following ingredients made: mole grams of maleic anhydride 3.24 317.7 tetrahydrophthalic anhydride 5.76 876.4 neopentyl glycol 10.67 1111.3 diallyl ether of pentaerythritol 3.03 655.4 Hydroquinone 1.48 The same order of heating was used as in the above Example. The heating was continued for a period of from 31 hours to one Acid number of 10 carried out, with water passed over at about 147 ° C and a maximum temperature of 190 ° C was reached.

Equal amounts by weight (375.8 g) of the above resin and the resin Siloxane according to Example 11 were heated together for 2.5 hours, Waseer passed at about 135 ° C and a maximum temperature of 173 ° C was obtained. the The feed was cooled to about 100 ° C where 0.124 parts by weight of hydroquinone were added became. After further cooling the charge to 80 ° C it became 247.9 parts by weight Styrene added.

A paint binder made from 50 parts by weight of the above, at 50% % silicone modified resin, 37.5 Parts by weight of styrene and 37.5 parts by weight of methyl methacrylate was sprayed onto test plates and how irradiated in the examples above. After 2 passes (10th Mrad) has a Sward hardness of around 44 - 48.

Example 18 The procedure of Example 11 was repeated with the Exception that the potential of the electron beam was 175,000 electron volts, the exposure being controlled to make a total dose equivalent to that of Example 11 resulted.

Example 19 The procedure of Example 11 was repeated with the Except that the potential of the electron beam was about 400,000 volts, where the exposure was controlled so that one of those of Example 11 was equivalent Total dosage resulted.

Claims (9)

Claims 1. Coating hardened by ionizing radiation and super-suction from a film-forming solution of a silicone-digested organic Harses into at least one. Vinyl mono-sera, characterized by the content of 30 up to 70 s of a Harses bit with a molecular weight of about 1000 and nit about 0.5 to 3 olefinic minor saturations per 1000 linear units of the molecular weight, which is at least 10% by weight of an acyclic siloxane bit 3 to 12 silicon atoms or a cyclic siloxane having 3 to 18 silicon atoms, and 70 to 30 % of at least one of these resins is copolymerizable by ionizing radiation Vinyl monomers. 2. Paint and Übersug @ mass according to claim 1, gekennseichnet by the content of a silicone-modified resin bit a molecular weight between 2000 and 20,000. 3. Paint and coating compound Mob claim 1 or 2, gekmzeich by the content of a silicone-modified polyester resin, with about 15 to 50% by weight, in particular 20 to 40% by weight, of an acyclic or acyclic siloxane with dissociable hydroxyl groups or oxyhydrocarbon groups attached to at least two silicon atoms are bonded, @tammen. 4. paint and coating composition according to claim 1 to 3, gekennseichnet due to the content of a silicone-modified polyester copolymer acyclic, α, ß-unsaturated dicarboxylic acid or its anhydride, a polyvalent one made up of carbon, hydrogen and oxygen and a cyclic alcohol Siloxane with 3 to 18 silicon atoms or an acyclic siloxane bit s to 12 silicon atoms. 5, paint and coating compound according to claim 1 to 4, characterized in that that the vinyl monomers are composed of a mixture of acrylic monomers and vinyl hydrocarbon monomers exist. 6. paint and coating composition according to claim 5, characterized in that that the mixture of a predominant proportion of acrylic monomers and a minor one There is a proportion of vinyl hydrocarbon monomers 7. Application of painting and Coating masses according to claims 1 to 6 for coating metal and wooden objects, characterized in that a film of the coating composition is applied to the base If the film is on the base with ionizing steel with copolymerization the silicone modified resin and vinyl monomers. 8. Use according to claim 7, characterized in that as ionizing Radiation an electron beam is used. 9. Application according to claim 7 or 8, characterized in that a ionizing radiation with a potential between about 150,000 and about 450,000 Electron volt is used 102. Application according to Claims 7 to 9, characterized in that that a film thickness between about 2.5 and 100 microns is used.