DE2063135C3 - Coating composition curable by ionizing radiation on the basis of acrylic-siloxane resin and unsaturated monomers and their use - Google Patents

Description

By electron curable, modified with siloxane $$ polyester coatings are described in U.S. Patent 37 512 and 34 37 513, respectively. In one embodiment, these resins are prepared by reacting a siloxane with functional hydroxyl or Hydroxycarbonoxygruppen with a diol and subsequent (, _0-closing reaction of the siloxane-containing product with two different anhydrides, a which in a λ / i-Siellung olefinically unsaturated material, for example maleic anhydride, whereby the desired amount of the olefinic:! λ, (, _s / i-unsaturation is introduced into the resin getting produced.

Electron curable siloxane acrylate reaction products are in the German patent 19 57 356.9 suggested. These materials are made through implementation a molar proportion of a siloxane with functional hydroxy-oiler hydrocarbon-based oxy radicals with preferably at least two molar proportions of a hydroxyl-containing ester in (\, / i-S (or olefinically unsaturated carboxylic acid.

One object of the invention consists in siloxane-containing compounds Acrylic paints curable by irradiation with electron beams and an improved one I laftuiig on the base!.: Result on what it hardened will. Another object of the invention is to provide siloxane-containing acrylic paints produced by electron siren are curable and show an improved resistance to wetting and are easily cured can be.

It was found to have improved posture, weather resistance, adhesiveness and flexibility of the paint film is obtained in an electron beam curable coating, which in combination Vinyl monomers and the new in \, / i-S'cllung olefinic unsaturated acrylic siloxane I larz. this in more detail below is specified contains.

The subject of the invention is a coating composition which can be hardened by ionizing radiation and is based on Acrylic siloxane resin and unsaturated monomers that is characterized in that it consists of 20 to 80 parts by weight vinyl and / or acrylic monomers ^ and 80 to 20 parts by weight of an acrylic siloxane resin, which by I) reaction of a siloxane with at least 2 functional groups with a monohydroxy ester from dihydric alcohols with 2 to 8 Carbon atoms and acrylic acid or methacrylic acid as hydroxyacrylate, 2) implementation of the obtained Siloxane acrylate with a mixture of vinyl and / or acrylic monomers, at least one of the Moiiomcr constituents consists of glycidyl acrylate and / or glycidyl methacrylate, and 3) implementation of the obtained siloxane-containing resin with acrylic acid or methacrylic acid or with a monohydroxy ester a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid has been made.

The functional groups preferably consist of hydroxyl groups and the siloxane has 2 to 5 of these groups per molecule, or from methoxy groups and the siloxane has 2 to 5 of these groups each Molecule on.

The invention thus provides coated articles of daily use in which the coated surface has a has high resistance to atmospheric agents.

In particular, the invention is concerned with the covering of substrates made of wood, metal, glass, polymeric solids and cloths made from synthetic or natural fibers and the hardening of the new ones Paints on it.

In general, the acrylic-siloxane resin is 1) by reacting a siloxane with a hydroxyacrylate, 2) Reaction of this product with vinyl monomers, one of which is made from a glycidyl acrylate or glycidyl methacrylate consists, and 3) reaction of this product with acrylic acid or methacrylic acid or with a Hydroxyacrylate or methacrylate obtained. The resin

w ij-tl <hi mi mil vinyl ucd / or acrylic monomers !! mixed, applied and hardened. This results in good flexibility, good flexibility and curing with a lower dosage.

The acrylic-siloxane resins, which are used here s eincsel / t are produced by a three-step reaction, whereby 1) a siloxane with two or more Functional hydroxyl or alkoxy groups per molecule with a Monehydroxyerylat with 5 to 12 carbon atoms, d. H. a monohydroxy ester of a diol with 2 to 8 carbon atoms and acrylic acid or Methacrylic acid, is reacted, 2) this siloxane acrylic product obtained in the first reaction column with a mixture of vinyl and / or acrylic monomers, the monomer component of which is at least one of the is Acrylate Glycidylacrykil and Glyeidylmethaerylat '. implemented and 3) the resulting siloxane aerylate vinyl monomoly copolymers with a monohydroxyacrylal of 5 to 12 carbon atoms, i.e. one Monohydroxyester of a diol with 2 to 8 carbon: o atoms and tier acrylic acid or methacrylic acid or reacted with acrylic acid or methacrylic acid.

The term "paint" or "paint" refers to the material including pigment and / or finely ground filler, the binder without> <; Pigment and / or filler or only with a very low content thereof, colored if desired can be. Thus, the binder, which ultimately turns into a permanent and weather-resistant film is transferred, from the total amount or practically the total amount of the for the formation of the film Material used exist or it can be used as a carrier for pigment and / or particulate Filler material are referred to.

The siloxanes used in the manufacture of the binder have a reactive hydroxyl group or an alkoxy group having 1 to 4, preferably 1 to 2 carbon atoms attached to at least two silicon atoms are bound. The term siloxane denotes compounds that form a bond

-Si — O — Si—

- C — Ο — Si—

The remaining valencies are saturated by a hydrocarbon radical, a llydrocarbonoxy radical, a hydrogen atom, a hydroxyl group or an oxygen atom that connects a silicon alom with such a valency to another silicon atom. The siloxane can be either cyclic or acyclic. Suitable cyclic and acyclic siloxanes for use in the context of the ( _{) 0} invention are described in detail in the patents listed above. The preferred siloxanes contain 2 to 5 functional hydroxyl and / or alkoxyl groups. The choice of the reactants takes place vorieilhafterweise so that the siloxane (^ about 50 to about Gevv .-% constitutes IO of the binder resin prepared in the three stage reaction process.

Out in d ^ \ - first Keaklionsslufe eingesel / Kn I lydrovyacrylale are lister having 5 to 12 carbon atoms of zweiweiligen alcohols having 2 to 8 carbon atoms and of acrylic acid methacrylic acid oiler. These include 2- 1 iydroxyäthylacrylal and -nielhacrylal, 2 lydroxypropyl acrylat and methacrylate, 2-i-lydroxybulylaerylat and -melhaerylat, 2-J tyriroxyoctylacrylat and methacrylate and similar compounds. A sufficient amount of the hydroxy acrylate is used in the first reaction column for reaction with at least two functional groups of the siloxane molecules used. In the preferred embodiment, the amount of the hydroxyacrylal is sufficient to react with all of the functional groups on the siloxane.

The vinyl used in the second reaction stage and / or acrylic monomers contain one component of one of the acrylates glycidyl acrylate and / or Glycidyl methacrylate. The glycidyl compound is present in a smaller proportion, advantageously in one Amount of about 10 to 45% by weight of this monomer mixture. The greater proportion by weight of these monomers consists of a mixture of acrylates from esters of monohydric alcohols with I to 8 Carbon atoms and acrylic acid or methacrylic acid. These include methyl methacrylate, ethyl acrylate, Propyl acrylate, butyl acrylate, butyl methyl acrylate, 2-ethylhexyl acrylate and similar connections. This vinyl monomer mixture can also contain a smaller proportion of vinyl hydrocarbons, such as styrene and alkylated styrenes such as vinyl toluene, ix-methylistyrene and like., included. A smaller proportion of other vinyl monomers such as acrylonitrile, acrylamide, Methacrylonitrile, vinyl halides !!, for example vinyl chloride, and vinyl arboxylates, for example vinyl acetate, be used.

The acrylic acid and / or methacrylic acid used in the third reaction stage is sufficient Amount to react with a substantial amount, preferably all of the glycidyl molecules of the resin.

The hydroxyacrylates used in the third reaction stage can be the same as in the first Be reaction stage. A sufficient amount of the hydroxyacrylate is applied to with a substantial Amount, preferably the total amount of glycidyl molecules in the resin to react.

The acrylic siloxane resin thus formed is used with the vinyl and / or acrylic monomers containing 5 to 12 carbon atoms to form the paint binder solution mixed, which in the usual way, for example by spraying, roller application and the like., is applied to a base and thereon by ionizing radiation, preferably in the form of a Electron beam with an average energy in the range of about 100,000 to about 500,000 Electron volt, is polymerized.

The monomers in which the acrylic-siloxane resins are used Formation of the paint binder solution are dissolved, preferably consist of a mixture of Acrylals from esters of monohydric alcohols with 1 to 8 carbon atoms and acrylic acid or Methacrylic acid, as already mentioned above. Vinyl hydrocarbons can also be used alone are used, but are preferably used in a small proportion together with a larger proportion Share of acrylates used. Other acrylates, for example hydroxy acrylates and methacrylates and

(Ii-, tii- and letrafunctional acrylates can be included in smaller proportions. Meanwhile, in combination with acrylals and / or vinyl carbon water, smaller amounts of other vinyl and / or acrylic monomers can be used, for example acrylonitrile, acryhimide, methacrylonitrile Vinyl halide, for example vinyl chloride, and vinyl arboxylak'ii, for example vinyl acetate, can be used.

In the preparation of the coating according to the invention, the olefinically unsaturated resin constituent in Λ, / i-Sielkmg, based on the carboxyl group, can contain up to about 80 wt .-%. Preferably, the resin constitutes from about 35 to about 65 percent by weight of the resin monomer solution, with the vinyl monomers being from about 65 to about 35 percent by weight thereof. Of course, other polymers which are olefinically unsaturated in the "," - position can also be used in place of a smaller proportion of the acrylic-siloxane resin according to the invention.

The designation "Mrad" means 1,000,000 rads. The term "rad" means the dose of radiation that the absorption of 100erg energy per gram of absorber, for example a coating film, results. the Electron emitter device can consist of a Lincar electron accelerator exist to form a direct current potential in the above Area is suitable. In such a device, the electrons are usually made of one Heating wire emitted and accelerated by a uniform tension gradient. The electron beam, which can have a diameter of about 3.2 mm at this point, is then in one direction directed so that there is a funnel-shaped beam and then through a metal window, for example from Aluminum, with a small amount of copper, alloyed aluminum, a magnesium-chlorium alloy and the like, about 0.075cm thick guided.

The binder is preferably applied to the substrate as a continuous TiIm of practically uniform depth applied and cured, preferably at a depth in the range from about 2.5 to about 100 μ depending of the substrate and the intended end use of the coated product. The film-forming Binder solution should have a sufficiently low viscosity to allow rapid application to the backing in to allow practically uniform depth, and preferably a sufficiently high viscosity so that a film of about 25 μ is held on a vertical surface without the formation of drops. The viscosity of the binder can be by varying the molecular weights of the resin or resins and / or by Varying the relative concentrations of the resin component and / or by varying the relative concentrations of the different monomers Set within the vinyl and / or acrylic mono component. The binder is preferably applied to the Support practically free of non-polymerizable organic solvents and / or thinners applied, but it is also possible within the scope of the invention to use such solvents and diluents apply and remove them before hardening. The acrylic-siloxane Har / e advantageously have Molecular weights above about 2500 and below about 50,000. Preferably in the range of about 5000 to about 25,000.

It ei pi el I

An acrylic siloxane skin was made in the following manner manufactured:

(1) Implementation of most of the slule:

I Inseizierung of the siloxane with the I lydroxyacrylat

Rcakiionsieiliielimer iiiul I lillsmiiicl

ίο siloxane (l)

I hydroxyethyl acrylal

Tctraisopropyltitanium

Hydroquinone

(Jew l'i.'i

206
40
0.4
0.1

(I) Acyclic polysiloxane with a molecular weight in the ¹ ^ range from 700 to 10000 with an average of 3 to 4 functional Metlioxygmppen per molecule.

proceedings

3u The reactants were heated to 100 "C and brought from 100 to 150 ⁰ C for a period of 2 hours and 11 parts Mcthanoldcsiillat removed by Barrett's Destillationsaufnähme.

3s (2) reaction of the second stage:
Implementation of the siloxane acrylate mil
Monomers

Rciiktionsicilnclimcr and
ll auxiliaries

Siloxane acrylate according to (l)

Ethyl acrylate

Methyl methacrylate

Glyeidyl methacrylate

Azobisisobutyronitrile

Xylene

G e w. Parts

100

30th

32

46

490

The reactants and catalysts were added uniformly to ₀ xylene at reflux for a period of 2 hours. The resulting solution was refluxed for 6 hours.

(3) Third stage reaction:
·)? Implementation of the acrylic acid with the product
the second stage

26 parts by weight were added to the refluxing solution of xylene and the product of the second stage

so methacrylic acid, 0.1 part by weight of hydroquinone and 0.5 Gcw.-Tcile Tctraäthylammoniumchlorid added. Heating was continued until the acidity level decreased to about 0.053 milliequivalents per gram had dropped. The resin was separated from the xylene and poured into 100

S3 parts by weight of methyl methacrylate dissolved.

A film of the solution was placed on a metal pad to an average depth of about 25 μ and applied by exposure to a dosage of 8 Mrads of energy from an electron beam at 270

ho kilovolts and 25 milliamps in a nitrogen atmosphere networked.

Example 2

The procedure of Example 1 was repeated (-5 but an electron beam with an average energy of 325 kilovolts was used and films with average thicknesses of about 5. 12. 5. 38, 63 and 100 u irradiated.

Example i

The procedure of Example 1 was repeated, but as a base Hol / used and the The monomer component of the paint binder solution consisted of a mixture of 2 molar parts Methyl methacrylate and 1 molar part styrene.

B e i s ρ i e I 4

The procedure according to Example I was repeated, but the base was made of a synthetic one polymeric solid, namely an acrylonitrile-butadiene-styrene copolymer, and the monomer component of the paint binder solution from 2 molar parts of methyl methacrylate, 2 molar parts of ethyl acrylate, 1 molar proportion of vinyl toluene and '/ 2 molar proportion is 2-ethylhexyl acrylate consisted.

Example 5

The procedure according to Example 1 was repeated, but the base consisted of wood and the The monomer component of the paint binder solution consisted of a molar proportion of butyl acrylate, one molar portion of ethyl acrylate and 2 molar portions of styrene, and the paint binder solution was particulate! Pigmented titanium dioxide. : s

Example b

The procedure according to Example I was repeated, but the backing consisted of cotton fabric, the Acrylic-siloxane-Har / .bcsiandteil amounted to 20 wt .-% of the v> The film-forming solution and the monomer component consisted of an equimolar mixture of methyl methacrylate, Ethyl acrylate and 2-ethylhexyl acrylal.

B e i s ρ i e I 7

The process according to Example 1 was repeated, but the film-forming solution consisted of 80 Parts by weight of acrylic siloxane I larzes and 20 parts by weight of methyl methacrylal and it became an iiquimolaiv Amount of Glycidylacrylal instead of ties Glycidyl-. | <> Meihacrylates at the second Reaklionstufe tier I creation ties I larzes used.

The products of Examples I through 7 showed excellent cured coatings.

Examples

The procedure according to Example I was repeated, but this was acyclic siloxane with lunkiionellen Methoxyl groups by a commercially available cyclic * Siloxau with functional hydroxyl groups with the following > ilen l'.igeusehaflen replaces:

I lydroxylgehaii, Dean Siark

% counter-compensable ^r >. ^r >

% free (>. "> ss

Overdrive

Molecular weight IW) O

Connection thread ¹ I (IO

Refraction intlex l. ^r > H LVi ¹ )

Lrweiehungspunkl («1

according to D urra η,
Mercury Process, C
at W) ¹ Vu solid in xylene ¹ M

specific weight

at 2Vf 1.075 ₍ , _s

Viscosity at 2Vf.
Cenlipoise il

HoItIl Λ I

Ls uuiile a functionally equivalent amount of tliescs Siloxane was used instead of the siloxane according to Example I and the rest of the procedure was carried out according to Example I.

Example 9

The process according to Example 1 was repeated, but using hydroxyethyl acrylate instead of hydroxyethyl acrylate used in the first reaction stage, while the paint binder solution 65 wt .-% des Resin and 35 wt .-% methyl methacrylate contained.

Example 10

The process of Example 1 was repeated, but using hydroxyoctyl acrylate instead of hydroxyethyl acrylate used in the first reaction stage, while the paint binder solution consists of 35 parts by weight Resin and 65 parts by weight of a vinyl monomer mixture composed of 2 molar proportions of methyl methacrylate, 1 molar proportion of ethyl acrylate and I molar proportion of butyl methacrylate existed.

Example 11

The process according to Example 1 was repeated, but the monomer component of the paint binder solution consisted of 3 molar proportions of methyl methacrylate, ¹ molar portion of vinyl chloride, 1 molar portion of vinyl acetate and 1 molar portion of styrene.

Example 12

The procedure of Example I was repeated, but the bestund Monomerbestandieil the paint binder solution of i molar proportions Methylmclhaerylat '/.· molar proportion of acrylonitrile, V. " molar proportion of styrene and '/: molar proportion of divinylbenzene.

example 1
according to example

The procedure of Example I was repeated, but animal vinyl monomer component consisted animal paint binder solution of i molar proportions of styrene and I molar proportion of divinylbenzene.

Example 14

The procedure according to Example I was repeated, however, an equiinolar amount of methacrylic acid was used instead of acrylic acid in the reaction Drillen level at tier I lerslelhing ties Acryl-Siloxan-I larzes used.

■ Search the product !. ' tier shows examples H to ΙΊ excellent coatings.

Example I ^r )

l'lin acrylic siloxane resin was used in the following ways hergeslflll;

(I) I Isolation at the first level.:

I use of siloxime with the I lydioxvacrylai

lU'iiktioiisU'iliR'liiiK'i 'ti ml
llillsiniik'l

Siloxane (I)

I hydroxyalkyl acrylate

leiniisopropylitanal

I ivdroquinone

(ii'W, - l'eile

2 (Ki
Ί0
0.Ί
0.1

(I) Ai'yelisi'lies l'nlysiloMin mil
Ik'iL-kh of 7 (10 his MO (I mn ilmvliseliiiiiilii'li i
liiiiklidiK'lleii Melliii \\ |! ni | i | ii'ii n Mulekiil.

proceedings

The respondents were heated to U) O C and then from 100 to 150 C over the course of 2 hours heated and 11 parts by weight of methanol distillate over a Barrett distillation head removed.

(2) Implementation of the second stage:
Implementation of the siloxane acrylate with
the monomers

Solution a

Respondent and

Aids Parts by weight Siloxane acrylate according to O) 100 Ethyl acrylate 43 Methyl methacrylate 42 Glycidyl methacrylate 23 Azobisisobutyronitrile D. Xylene 490 Solution b Respondents and Aids Parts by weight Hydroquinone 0.1 Methacrylic acid 13th Tetraethylammonium chloride 0.5 proceedings

Solution A became evenly true to xylene at reflux! Added 2 hours. The resulting solution was refluxed for b hours. The product had a (lehall of non-volatile of 29%. The solution 15 was added to the located refluxing solution and the Lrhilzen fortgesel / t until the acid content to about O ₁ Of) J Milliäquivalcnte per gram was dropped (77% conversion) . The silo \ anhallige product hold a (ϊ c hall of 0.5 Linheiten to olefinic! '\, Ji Nichtsälii supply to 1000! .Inheilen molecular weight.

(i) Implementation of the third stage:
Umsel / ungdesSiloNan-Acrylai I We / es
with the hydroxyl acrylate

keakl uiitst c iluoluni'i '

l'rodukl according to (2)
I lydro \ yälhylaervlai

<ii-w.

150
I /

The reaction parts were heated to IiOV and i parts by weight of distillate in an Itanvi template enll'enil. The xylene was then by I KM illation im Vacuum (10 mm I Ij '., 110 V) ent lern ι and the I We / in MO (Icw.-parts of methylineethacrylal dissolved.

l'.in IiIm this 1, ösiing was on a MelallunicHa ge to a Durclisclinillsiiel'i · from elwn .'Ί | i aiil'gctra gen and a Lucrgic with a dosage of H Mrad from a l-electron tube with 270 kilovolts and. "> Milliamps in SlieksloH'almospharc aiisgesel / l. Ls I got a tough solution to the problem ten. The l'ilin hold a llleisiiftliilil ·. · I 'and hiell I < can be combined with one mixed in methyl ethyl ketone th cloth.

Example Ib

The process of Example 15 was repeated, but using the monobutyl ether of ethylene instead of the Hydroxyäthylacrylats used in the third Reaklionssiul'e. The one in Sticksiolfaimosphere at a Dosage of 8 Mrad with an energy from an electron beam of 270 kilovolts and 25 milliamps obtained film was its soft and had a bad one l. solvent resistance. for example a Blcisiil'thärtc of 2B, and only 3 rubs with a cloth soaked in methyl ethyl ketone, which results in the importance of the use of hydroxyacrylate in the third reaction stage results from this comparison.

Example 17

The procedure of Example 15 was repeated, but using an electron beam with an average energy of 325 kilovolts and films with average thicknesses of 5 μ, 12.5 μ, 38 μ, 63 μ and 100 μ irradiated.

Example 18

The process according to Example 15 was repeated, but using wood as the base and as the monomer component the paint binder solution is a mixture of 2 molar proportions of methyl methacrylate and 1 molar Share of styrene used.

Example 19

The procedure of Example 15 was repeated but a synthetic polymer base! ! - "cststotT, i.e. an acrylonitrile-butadiene-styrene copolymer uses μκΙ the mono-component part of the The paint binder solution consisted of 2 molar parts of methyl methacrylate, 2 molar parts of ethyl acrylate, I. molar proportion of Vin \! toluene and '/.· molar proportion 2-ethylhexylhexyl acrylate.

Example 20

The procedure of Example 15 was repeated! However, glass was used as the base, while the monomer component of the visual binder solution consisted of 1 molar proportion of Huiylacral, 1 molar proportion of ethyl aerylate and 2 molar proportions of styrene in the form of an additional solvent solution with partly tilandi oyul pigmeiitieri,

Example 2 \

The procedure of Example 15 was repeated! A shark wool was used as a base, while the acrylic silo was 20% by weight of the transforming solution and an amount of glycidylicrylal was used instead of the glycidylmcth aerylals for the oil island , wide level cingesel / became and the Moiioiiicrhcsiaiidlcil consisted of an iU | iiiino laren (ionic from Melhylineihacrylal, Älhyliicryliit around 2 Älhylhewliicrylal.

Example 22

according to Example 15 is repeated the l'iiinbildoid solution from H

The veilai
however existed

nildeiide solution

Parts by weight of the Aeiyl-Silo \ aii I lar / es and 20
Leile Melhylinelhiicrylat.

The rods of Examples 17 to 22 show ebciilii
outstanding ("b

Hey spit I 23

The procedure according to Example 15 was repeated, however, the acyclic siloxane with functional meihoxy groups is replaced by a commercially available cyclic> Siloxane with functional hydroxy groups set / t.

The specific properties of this siloxane are in Example 8 given.

A functionally equivalent amount of this siloxane was used in place of the siloxane according to Example 15 and continued to work according to Example 15.

Example 24

The procedure according to Example 15 was repeated, except that hydroxyethyl methacrylate was used in place of the Hydroxyethyl acrylate used in the first reaction stage, hydroxybutyl acrylate instead of hydroxyethyl acrylate used in the third reaction stage, while the paint binder solution 65 wt .-% des Resin and 35 wt% methyl methacrylate contained.

Example 25

The procedure of Example 15 was repeated, but using hydroxyoctyl acrylate instead of hydroxyethyl acrylate used in the first reaction stage, while the paint binder solution consists of 35 parts by weight Resin and 65 parts by weight of a monomer mixture au; 2 molar proportions of methyl methacrylate, 1 molar Share of ethyl acrylate and 1 molar share of butyl methyl acrylate consisted.

Example 26

The procedure according to Example 15 was repeated, but the monomer component of the paint binder solution consisted of 3 molar proportions of methyl methacrylate, ¹ atomic molar portion of vinyl chloride, 1/2 molar portion of vinyl acetate and 1 molar portion of styrene.

Example 27

The process according to Example 15 was repeated, but the monomer component of the paint ^{binder solution consisted of 3 molar proportions of methyl methacrylate, 1} molar portion of acrylonitrile, 1/2 molar antitrile styrene and 1/2 molar portion of divinylbenzene.

Example 28

The procedure of Example 15 was repeated except that the vinyl monomer component passed Paint binder solution from 3 molar parts styro and 1 molar part divinylbenzene.

The products of Examples 23 to 28 also had excellent coatings.

Claims (5)

Patent claims: 1. Coating material curable by ionizing radiation on the basis of acrylic-siloxane resin and s unsaturated monomers, ('a d u r c h g e k e π π /. e i c h η e t that they come from a! 'transforming solution from 20 to 80 parts by weight of vinyl and / or acrylic monomers and 80 to 20 parts by weight of one Acrylic-siloxane resin, which by 1) reaction ■ <> of a siloxane with at least 2 iunklionellen Groups with a Moiiohydroxyester from dihydric alcohols with 2 to 8 carbon atoms and acrylic acid or methacrylic acid as the hydroxyacrylate, 2) conversion of the obtained Siloxane acrylate with a mixture of vinyl and / or acrylic monomers!), At least one the monomer components consist of glycidyl acrylate and / or glycidyl methacrylate, and 3) reaction of the resulting siloxane-containing resin with acrylic acid or methacrylic acid or with a monohydroxy ester a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid made wi, exists. 2. Paint composition according to claim I, characterized in that it additionally contains pigments and / or contains fillers. 3. Paint composition according to claim I and 2, characterized in that the! 'Transforming solution from 35 to 65 parts by weight of monomers and 65 to 35 parts by weight of the aeryl-siloxane resin. 4. Paint composition according to claim I to 3, characterized in that the monomers of esters Acrylic acid or methacrylic acid with monohydric alcohols with 1 to 8 carbon atoms exist. 5. Paint composition according to claim I to J, characterized in that the monomers consist of one Mixture of vinyl hydrocarbons with 8 to 10 carbon atoms and esters of acrylic acid or Methacrylic acid with monohydric alcohols with 1 to 8 carbon atoms exist. b. Use of the compositions according to claims 1 to 5 for coating a substrate, the film-forming solution being applied to the surface of the substrate in an average layer thickness of 2.5 to 100 μ and using an electron beam with an average energy of 100,000 to 500 000 electron volts is hardened. 5 °