DE2063256A1 - Acrylic siloxane resins, coating compositions here from and coating processes - Google Patents

Description

The basis of the invention is a new acrylic-siloxaniinstrichsMnderhara, which can be crosslinked with vinyl monomers when exposed to an electron beam and which is obtained by a two-stage reaction, where (1) a giloxane with two or more functional hydroxyl or alkoxyl groups per molecule with one functional Hydroxyl copolymers from acrylic monomers is reacted and (2) the siloxane-containing reaction product obtained in the first reaction stage with a conoester of a C _? - Until Cg-diol and acrylic acid or methacrylic acid is implemented.

Electron-curable siloxane-acrylate reaction products are suggested in the patent. ....,. (Patent application P 19 57356.9).

Electron curable, modified with an oiloxane Polyester paints are honored in the U! J patents 3,437,512 and 3,437,513.

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One object of the invention consists in siloxene-containing Coating compounds., Which are produced by irradiation with electron beams are curable and which show improved adhesion to the substrate on which they are cured.

Another object of the invention consists in siloxane-containing Paint compositions which are curable by irradiation with electron beams and which are applied to the various Extent of flexibility. Can be tailored «-. _ ,.

So it is supposed to have improved, and improved adhesion "Flexibility can be achieved under irradiation.

It has been found that improved adhesion, Weather resistance and flexibility of the paint film in one hardened with an electron beam Coating can be obtained which in combination vinyl monomers and new ones which are olefinically unsaturated in the α, ß-position Acrylic Siloxane Resins, hereinafter im. individually described are, contains. The invention is thus concerned with coated. Commodities ^ where the coated surface. a high resistance to Weather influences, improved flexibility, an improved adhesion to the base and an improved one Shows hardenability with a method of manufacture such a coated surface, which at to be used with this method and with a process for the production of in.der paint used new paint binder resins. In particular, the invention is concerned with the overtaking of documents made of wood, -GIa.?:, .. metal ,, polymeric solids and

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Cloths made of synthetic or natural fibers and the Curing the new paints on it.

In general, the new acrylic-oiloxane paint binder resins are obtained by reacting a siloxane with a hydroxyl copolymer of vinyl monomers and then reacting this product with a hydroxy acrylate. Specifically, the new acrylic-oiloxane paint binder resins according to the invention are produced in a two-stage reaction, where (1) a siloxane having two or more functional hydroxyl or alkoxyl groups per molecule is reacted with a functional hydroxyl copolymer of acrylic monomers and (2) the siloxane-containing reaction product of the first reaction stage is reacted with an O ₁ - to C ₁ 2 - ^on ohyäroxylacrylat, for example a flonoester of a Cp- to Cp-diol and acrylic acid or methacrylic acid.

. ', (- the term "paint or coating composition" is used under the term "pigment and / or particulate filler", for the hindrance without pigment and / or filler or only a very small amount of it, which may be jfTf. \ ·;..? _Γ}, +, .His can understand Thus, the Mnder, Oer pc .'- lieili-ch rw a "durable film which is opposite .i ⁺ ^ t rungseinflüHnen resistant, is transferred from ' J.HT -i ^ similar or practically the total amount of the material used for the formation of the film consist of can be regarded as a carrier for pigment and / or particulate filler material.

The siloxanes used in the manufacture of the binder have reactive hydroxyl or alkoxyl groups,

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advantageously a C ₁ to C 1 and preferably a C ₁ or C ₂ alkoxy group which is bonded to at least two of the silicon atoms. The term "siloxane" here denotes compounds that form a bond

Si - 0 - Si - or - C - 0 - Si

■ I l. - '. ι

Contain, the remaining valencies by a hydrocarbon residue, an Ilydrocarbonoxyrest, water. substance atoms, a hydroxyl group or an oxygen atom, which the silicon atom endowed with such a valency with a further silicon atom connects, are satisfied. The siloxanes can be either cyclic or acyclic. Suitable cyclic and acyclic siloxanes for use within the scope of the invention are in the patents listed above and described in other literature. The preferred siloxanes contain 2 to 5 functional parts Hydroxyl and / or alkoxyl groups. The choice of Rep action participants is advantageously made so that the siloxane about 10 to about 50 wt .- ^ of the two-stage Process produced binder resin.

The acrylic resin reactant, i.e., the functional hydroxyl copolymer of acrylic monomers, is made by copolymerization made from various acrylic monomers and contains from about 0.2 to about 2, preferably about 0.5 up to 1.5 reactive hydroxyl groups per 1000 units of the molecular weight. These are advantageous

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Adhesively formed in the copolymer by using a monohydroxyacrylate or methacrylate, for example the monohydroxyl ester of a C 1-4 diol and acrylic acid or methacrylic acid, as a reaction participant. These include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, 2-hydroxybutyl acrylate or methacrylate, 2-hydroxyoctyl acrylate or methacrylate and similar materials. The remainder of the comonomers consists preferably of esters of a monohydric C ₁ - to Cg alcohol and acrylic acid or methacrylic acid, for example methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate. 2-Ethylhexyl acrylate and the like. The comonomers used to produce this resin can also contain smaller proportions of other vinyl monomers together with a larger proportion of the above-listed esters of monohydric C 1 -C 6 alcohols and acrylic acid or methacrylic acid. Such monomers used in smaller amounts include acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate and / or vinyl hydrocarbons, for example otyrene, vinyl toluene, ex-methyl styrenes and the like and / or acrylonitrile, acrylamide, methacrylonitrile and / or vinyl halides, for example vinyl chloride, and / or vinyl carboxylates, for example vinyl acetate. These resins have average molecular weights in the range from about 1000 to about 25,000 and preferably in the range from about 5000 to about 15,000 obtained prepolymers is reacted with acrylic acid or methacrylic acid.

bad original 109829/1830 & l <

According to the preferred embodiment, the proportions of hydroxylated-te-m. Acryl säureliarζ and the -. Oiloxan with functional hydroxyl o'dex: alkoxyl groups adjusted so that as close as possible ^ a Fro- - ■ - -. product in which a functional group des. : ■ / ■■ = siloxane with a hydroxyl group of the Harzraoleküles to ^ -. is set, with the remaining functional groups' remain siloxane to react with the Hydroxyaerylat in the second reaction stage .. Ea the forthcoming ψ ferred siloxanes 2 to 5 ■ functional Jruppe per molecule of. have, the siloxane molecule of the preferred end product resin contains bound ■ 1 mole of acrylic acid and 1 to 4 ^ acrylate molecules. However, complete control is not expected and therefore the siloxane molecules in the paint binder solution have an average of about 0.5 to about 1.5 molecules of acrylic acid reactant. Thus, the molar ratio of the acrylic murine to the siloxane is more advantageous at this stage of the reaction. wise in the range of -0.5 to 1.5: 1. A sufficient amount of hydroxyerylate is used in the second stage for the reaction, at least with a substantial proportion, preferably with the total amount of the remaining functional groups of the siloxane. On the other hand, the hydroxylated acrylic resin may have an inverse number of reactive hydroxyl groups per molecule, preferably 1 to 10, and therefore a number of siloxane molecules may be bonded to one molecule of the aerylic resin component. ■

The acrylic acid reaction participant of the second reaction stage can be the only measure for the delivery of the oil- * "" ¹ '"finischen α, β-unsaturation or the delivered ·

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Light saturation can be present together with the α, ß-light saturation of the acrylic resin previously reacted with the iiloxane. Suitable acrylates include 2-hydroxy acrylate or methacrylate, 2-Uydroxypropylacrylat acrylate or methacrylate, 2-hydroxybutyl acrylate or methacrylate, 2- iydroxyoctylacrylat ^T or -nethacrylat and similar materials. "

The flexibility of the cured paint film made of the obtained acrylic acid-siloxane resin can be significant by varying the molecular weight of the acrylic copolymer and / or the number of acrylic copolymer molecules varies per oiioxane molecule in the acrylic acid-oleoxane resin will.

The acrylic-siloxane resin obtained in this way is used with vinyl monomers having 5 to 12 carbon atoms for Formation of the paint binder solution mixed, which in the usual / eise, for example spraying, roller application and the like, is applied to a base and then with ionizing radiation, preferably with an electron beam with an average Energy in the range from about 100,000 to about 500,000, preferably about 150,000 to about 350,000 electron volts.

IAe in, solution used together with the Acryl-Oiloxan-IIarz Vinyl monomers preferably consist of acrylic monomers, for example methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, the Hydroxyacrylates or mixtures of such listed above for use in resin production

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Acrylic monomers and vinyl hydrocarbon monomers such as styrene and alkylated styrenes such as Vinyltoluene, α-methylstyrenes, divinylbenzene and the like. Vinyl hydrocarbons can also be used alone as a vinyl monomer component of the paint binder. In combination with the monoacrylates and / or hydrocarbons monomers, smaller proportions of di-, tri- or tetrafunctional acrylates can also be used. Also in combination with the acrylates or methaerylates and / or vinyl hydrocarbons can contain minor amounts of other vinyl monomers, e.g. Acrylonitrile, acrylamide, methacrylonitrile, vinyl halides, e.g. vinyl chloride, and vinyl carboxylates, e.g. Vinyl acetate can be used.

In the preparation of the paint compositions according to the invention The olefinic α, β-unsaturated resin component, i.e. the acrylic-siloxane resin, can be up to about 80% by weight of the paint binder solution on a pigment and particulate filler free basis and down to make up about 20 wt .- ^. The resin preferably contains about 35 to 65 wt .- ^ of the resin-monomer solution, the Vinyl monomers make up about 65 to about 35 percent by weight thereof. Of course, other polymers which are olefinically unsaturated in the α, β-position can also be used instead of one smaller proportion of acrylic-siloxane paint binder resin are used according to the invention.

The abbreviation "Mrad" used here means 1 000 000 wheel. The term "rad" denotes a dose of radiation, which is the absorption of 100 erg. energy per gram Absorber, such as a coating film, results. The elec-

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electron emitting device can consist of a linear electron accelerator, which is capable of developing a direct current potential in the range specified above, exist. In such a device, the electrons are usually emitted from a filament and accelerated by a uniform voltage gradient »The electron beam, which is about 3.2 mm in diameter this point is then directed in one direction, so that a funnel-shaped beam results, and then through a metal window, for example made of aluminum, with a small amount of copper, Iegiprtem Aluminum, a magnesium-thorium alloy, about 0.007 cm thick.

The binder is preferably applied to the substrate as a continuous film of practically uniform depth ^. cured thereon, preferably to a depth in the range of about 2.5 to about 100 η (0.1 to 4.0 mils), depending on the substrate and the intended use of the coated product. The film-forming binder solution should have a sufficiently low viscosity to allow rapid application to the substrate at a practically uniform depth, and preferably have a sufficiently high viscosity so that a 25 Ά (1 rail) film is held on a vertical surface without seepage will. The viscosity of the binder is adjusted by varying the relative concentrations of the resin component and / or varying the relative concentrations of the different ionomers within the vinyl monomer component. The binder is preferably practically free of non-polymerizable organic solvents on the substrate

109829/1830

and / or diluents applied, although suitable Volatile solvents can also be used if they are stripped off prior to curing.

The following examples serve to further. Explanation the invention.

example 1

An acrylic-siloxane resin was made in the following way:

1) An acrylic acid resin, Resin I, was made from 80 moles Ethyl acrylate »10 mol- # hydroxyäthylaerylat and 10 Mol- $ glycidyl methacrylate produced. The copolymerization was carried out by adding the monomers dropwise together with 1.5% by weight, - ^ azobisisobutyronitrile to form one equivalent weight of xylene refluxed. After the completion of the reaction, acrylic acid was added in an equimolar amount to the glycidyl methacrylate and reacted with the resin.

2) Implementation of Stage I; Resin I is reacted with siloxane: *

Resin I reactant

cyclic siloxane with functional hydroxyl groups (I)

Xylene
Hydroquinone

Parts by weight

75 (0.07 mol hydroxyl groups)

100. (0.07 mol. Hydroxyl groups)

120

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(1) Commercially available cyclic polysiloxane with functional hydroxyl groups Dow Coming Z-6O18) Having the following properties: Hydroxyl content, Dean Stark:

fo condensable 5.5

$> free 0.5

average molecular weight 1600

Link weight 400

Refractive index 1.531-1.539

Softening point, according to Durran, 3ueeksilber method, ⁰ C ( ⁰ S ¹ ) 93 (200) at 60% solids in xylene

specific weight at 25 ⁰ C 1.075

Viscosity at 25 ⁰ C, 33 centipoise

Gardner-Holdt A-1

procedure

The lieaktionsteilnehmer were heated to reflux (142 ⁰ C) during 1 Jtunde. The acid formed as a by-product was removed by azeotropic distillation. The product, resin JI, is a slightly cloudy _f Yir-ko ^ e liquid.

3} T'i3set -: iiH ^ the Jtufe TI: Resin II becomes with the hydroxy acrylate u ^. ^

Reaction participants · Uew.-parts

Wvtt I] 209

Hydroxy ethyl acrylate 11.5

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"The reactants were heated to reflux for 2 hours. The water of condensation passed through azeotropic distillation removed. 65 parts by weight of the obtained acrylic-siloxane resin were together with 35 Parts by weight of methyl methacrylate mixed and a film this solution drawn onto a steel plate. A continuous one Non-adhesive film was formed when this coating was exposed to an electron beam of 275 kilovolts and 25 milliamps.

Example 2

An acrylic-siloxane resin was made following the procedure of Example 1 with the difference that ■ that functionally equivalent amounts of a different acrylic resin and a siloxane with functional methoxyl groups instead of the acrylic resin and siloxane used in Example 1, * were used. A catalytic amount Tetraisopropyl titanate (0.4 parts by weight) was used as a catalyst.

The acrylic acid resin used in this example was obtained by co-polymerizing a mixture of monomers, its composition 40 MoI- ^ methyl methacrylate, 50 mol # ethyl acrylate and 10 mol # hydroxyethyl acrylate fraud. The copolymerization was carried out by adding the monomers dropwise along with 1.5 wt .- ^ Azobisisobutyronitrile to an equivalent weight of refluxed xylene causes.

The siloxane used in this example consisted of an acyclic polyeiloxane with a durohschnittli-

ORiQlNAL

10 9 8 2 9/1 8 3 0

chen molecular weight in the range of 700 to 800 with an average of 3 to 4 functional methoxyl groups per molecule.

The obtained acrylic-siloxane resin (65 parts by weight) and 35 parts by weight of methyl methacrylate were mixed and get the paint binder solution. A film of this solution was drawn onto a steel sheet and made tack-free by exposure to an electron beam of 8 ■ Mrad with an energy of 275 kilovolts and 25 Milliamps cured in a nitrogen atmosphere.

Example 5

The procedure of Example 2 was repeated, however used as Ilydroxylacrylat in the second reaction stage 2-hydroxyethyl methacrylate.

Example 4

The process according to Example 2 was repeated, but as the hydroxyacrylate in the second reaction stage 2-hydroxybutal acrylate is used.

Example 5

The procedure of Example 2 was repeated, however used as hydroxy acrylate in the second reaction stage 2-hydroxybutyl methacrylate.

109 8 2 9/1830 ^BAD original.

2Ü63256

Example 6

The process according to Example 2 was repeated, but "2-hydroxyoctyl acrylate was used as the hydroxy acrylate in the second reaction stage and an average rate of the applied and cured film of about 5 / x was used *" -

-; ■; ■ -. Example 7 -

The process according to Example 2 was repeated, but using 2-hydroxyoctyl methacrylate as the hydroxy acrylate in the second reaction stage and using an average depth of the applied and cured film of about 100 μm .

Example 8

The procedure of Example 2 was repeated, but the paint binder solution contained 80 parts by weight of the Acrylic ^ iloxane resin and 20 parts by weight of methyl methacrylate, the substrate was made of glass and hardening was achieved by exposure to a 295 electron beam Kilovolts and 25 milliamps causes.

Example 9 ■

The procedure of Example 2 was repeated, but ,, the paint binder solution contained 20 parts by weight of the Acryl-üiloxan-Harses, and. 80 parts by weight of an equimolar Mixture of methyline ethacrylate, jtyrene,.-Ithylacrylate, Butyl acrylate and 2-ethylhexyl acrylate, the backing consisted of made of wood and the hardening was through suspension

ψ ORIGINAL

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to a Llektronejiststrahl with 325 kilovolts and 25 milliamps causes »

Example 10

The procedure of Example 2 was repeated, however the paint binder solution contained 35 sewing parts of the Acrylic-siloxane resin and 65 parts by weight of a mixture from 2 molar portions of methyl methacrylate, 1 molar portion of ethyl acrylate, 1/2 molar portion of vinyl toluene, i / 2 molar proportion of divinylbenzene, i / 2 molar proportion Vinyl acetate and 1/2 molar proportion of butyl methacrylate, the base consisted of a polymeric substance, namely an acrylonitrile-butadiene-styrene copolymer.

Example 11

What procedure according to Example 2 was repeated, but a mixture of 4 molar parts of ethyl methacrylate, 1 molar part of vinyl acetate, '·.' ?. : r.olar- ^r .: / n part of P- ■ iydroxy'ithylacrylat and 1/2 molar

-: part, 'i ^v ylr _k loriu v ^ rv / ends and as a base a ^T L ⁿ rriV / oll' -, ch is used.

Example 12

;, & s 7s. after Peinpiel 2 it was repeated, however was the paint index solution with particulate titanium dioxide pigmented.

In Examples 1 to 12, excellent coated and cured products were obtained.

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Corresponding acrylic-siloxane resins can also be obtained by (1) reaction of a molar proportion of a siloxane with
at least two functional groups per molecule as
Hydroxyl groups and / or alkoxyl groups with C ₁ - * to C ^ ₂ monohydroxyl esters of dihydric Cg to Cg alcohols
as hydroxy acrylate and acrylic acid or methacrylic acid in sufficient quantity to react with at least one molecule of acrylate with a functional group of one molecule of siloxane and (2) reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5
molar amounts of a copolymer of vinyl monomers, the copolymer being composed of

(A) at least one monomer as a component of a dihydric Cp- to Cg-alcohol and acrylic acid
or methacrylic acid,

(B) a larger proportion by weight of the constituent monomers from esters of a monovalent C .- "" to Cg-

Alcohol and acrylic acid or methacrylic acid and '-

(c) about 0.2 to about 2 hydroxyl groups per 1000 units the molecular weight,

are made or consist of it.

Subject matter of the invention and thus objects of use, consisting of a base and one adhering to it
Coating of a paint on an external surface
the same, the coating being the in situ formed polymerization product of a film-forming solution of 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight
an α, β-olefinically unsaturated acrylic-siloxane resin applied to the surface as a paint film and then exposed to the film

BATH

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has been crosslinked to ionizing radiation, represents, the acrylic giloxane resin through

(t) Reaction of a molar amount of a siloxane resin with at least two functional hydroxyl and / or alkoxyl groups per molecule with 0.5 "to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer being composed of
Ca) as at least one monomer component from a monohydroxy ester with 2 to 5 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and .der acrylic acid or methacrylic acid,

(b) a greater proportion by weight of the constituent monomers from esters of a monohydric alcohol with 1 to 8 carbon atoms and acrylic acid

: or methacrylic acid and

(c) about 0.2 to about 2 hydroxyl groups per 1000 units the molecular weight, and

(2) Reaction of the resin obtained with a monohydroxy ester having 5 to 12 carbon atoms of a divalent alcohol having 2 to 8 carbon atoms and acrylic acid or methacrylic acid in sufficient quantity to react with at least a substantial part of the unreacted hydroxyl or alkoxyl groups of the rjiloxane

was obtained.

The base preferably consists of wood, a synthetic polymeric solid, glass, a cloth or tissue,

1 0982 9 / 1Ö30

The invention of a particle-shaped pigment and a film-forming solution consist essentially of up to 80 ^{parts by} weight: vinyl monomers and 80 to 20 parts by weight of an acrylic-siloxane resin, the acrylic-siloxane resin by

(1) Reaction of a molar amount of a siloxane resin with at least two funk ti one Il en. Hydroxyl and / or alkoxyl groups per molecule with 0.5 to about 1.5 molar proportions of a copolymer of "vinyl monomers, where

, the copolymer of _:

(a) as at least one mono-heir was pending a monohydroxy ester of 2 to 5 carbon atoms of a dihydric alcohol of 2 to 8 Carbon atoms and ^ of acrylic acid or methacrylic acid,

(b) a greater proportion by weight of the constituent monomers from esters of a monohydric alcohol with -1- to 8 carbon atoms and acrylic acid or methacrylic acid and

(c) about 0.2 to about 2 hydroxyl groups for 1000 units units of the molecular weight, and

(2) Reaction of the resin obtained with an Ilonohydroxyester with 5 to 12 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in sufficient amount for Reaction with at least a substantial part of the unreacted hydroxyl or alkoxyl groups of the Siloxanes

was formed.

BAD ORiGiNAL

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The method according to the invention for coating a base, whereby on the surface of the base to an average depth in the range from about 2.5 to about 100 μ a forming solution of practically 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight an α, β-olefinically unsaturated acrylic-giloxane resin is applied and the vinyl monomers and the resin on the surface is crosslinked by exposing the coating to an electron beam with an average energy in the range of about 100,000 to about 500,000 volts , is that an acrylic-siloxane resin is used, which by

(1) Reaction of a molar amount of a siloxane resin with at least two functional hydroxyl and / or alicoxyl groups per molecule with 0.5 to about 1.5 molar parts of a copolymer of vinyl monomers, where d is' v polymers from
'a. a ¹ s r.in- ^{: at} least one. Monomer component from one

^ rohydroxyester with 2 to 5 carbon atoms ^ i nee /.v/eiv/ertigen alcohol with 2 to 8 carbons: · o ^ r-! ⁴ : ο me π and acrylic acid or! - "ethacrylic acid, 'r. <■ - \ nen irr'""? * - ren 'JewicLts component of the constituent ■: .. ΐΓ: θπ:': Γβπ -ViB" . star of a monohydric alcohol j : .. '. *. ' V j π ^u . / ohlenstoffatonen and the. ^A -cryls "ure y.er"! Eti.a ^ rylsMure consists and

(c / FTV / fe ', - ,? V.is etv / a 2 hydroxyl groups on H). OO units of "olekulargewichtes contains, and (2) lmsetzun £ ^r of the obtained resin with a monohydroxy

ester with 5 to 12 foal atoms of a divalent- gene, alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in sufficient quantities for implementation with at least a substantial part

BAD ORlGiNAL

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the unreacted hydroxyl or alkoxyl groups of the siloxane
was formed.

The acrylic-siloxane resin of the present invention is obtained (1) by reacting a molar proportion of a siloxane with at least two functional hydroxyl groups and / or Alkoxyl groups in from about 0.5 to about 1.5 molar proportions of a copolymer of yinyl monomers, the copolymer fe off

(A) as at least one component of the monomer a monohydroxy ester of 5 to 12 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid and

(b) a greater proportion by weight of the monomer component from esters of a monohydric alcohol with 1 to 8 carbon atoms and acrylic acid or Methacrylic acid consists and

(c) about 0.2 to about 2 hydroxyl groups per 1000 units the molecular weight, and

(2) reaction of the resin obtained with a monohydroxy

ester with 5 to 12 carbon atoms of a two-

W valued alcohol with 2 to 8 carbon atoms and

the acrylic acid or methacrylic acid in a sufficient Amount to implement at least one significant proportion of the unreacted hydroxyl or alkoxyl groups of the siloxane *

The inventive method for producing a Acrylic siloxane resin is that (1) a molar Proportion of a siloxane with at least: two functional Hydroxyl groups and / or alkoxyl groups with about 0.5 to

0.9-8 29-7 1: 830

1.5 molar parts of a copolymer of vinyl monomers, wherein the copolymer consists of

.Ca) - as at least one component from dee monomers a honey hydroxyester having 5 to 12 carbon atoms a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid and

(b) a greater proportion by weight of the monomer component from esters of a monohydric alcohol with 1 to 8 carbon atoms and acrylic acid or methacrylic acid exists and *

(c) about 0.2 to about 2 'hydroxyl groups per 1000 units the molecular weight, and

(2) the resulting resin with a monohydroxy ester with 5 to 12 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in an amount sufficient to react in at least a substantial proportion the unreacted hydroxyl or alkoxyl groups of the diloxane

is implemented.

The siloxane here preferably consists of an oiloxane λ with functional hydroxyl groups or with functional methoxyl groups. The siloxane preferably has 2 to 5 functional groups per molecule and the functional groups consist of hydroxyl groups and / or methoxyl groups.

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Claims (1)

- 22 - 2063258 Pat e ηtan claims Utility object, consisting of a base and an adhering coating of paint on an outer surface thereof, characterized in that the coating is the in situ formed polymerization product of a film-forming solution of 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight an a, ß-position olefinically unsaturated acrylic-siloxane resin, which is applied to the surface as. Paint film has been applied and has been crosslinked thereon by exposure of the film to ionizing radiation, showing the acrylic-siloxane resin through (1) Reaction of a molar amount of a siloxane resin with at least two functional i-hydroxyl and / or alkoxyl groups per molecule with 0.5 to about 1.5 molar proportions of a copolymer Vinyl monomers, the copolymers being made of a) as at least one Monomerbe constituent of a monohydroxy ester with 2 to 5 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid, b) a larger proportion by weight of the constituent monomers from esters of a monovalent Alcohol with 1 to 8 carbon atoms and acrylic acid or methacrylic acid and c) about 0.2 to about 2 hydroxyl groups for 1000 Contains units of molecular weight, and (2) Reaction of the resin obtained with a honey hydroxyester with 5 to 12 carbon atoms one 109829/1830 - ■ 23-206325Θ dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in sufficient quantity to react with at least a substantial part of the unreacted hydroxyl or alkoxyl groups of the 3iloxane
was received, 2. commodity according to claim 1, characterized in that the siloxane consists of a 3iloxane with functional hydroxyl groups, 3. utensil according to claim 1, characterized in that the _t is oiloxan of a siloxane having functional methoxyl groups, 4. commodity according to claim 1 to 3, characterized in that the siloxane has 2 to 5 functional groups per molecule and the functional groups consist of hydroxyl groups and / or ethoxyl groups, 5 «commodity according to claim 1 to 4, characterized in that the base consists of wood. 6, utility article according to claims 1 to 4 » characterized in that the base consists of a synthetic polymeric solid. 7, utensil according to claim 1 to 4, characterized in that the substrate is made of glass. BAD ORfGINAL 109829/1830 8. commodity according to claim 1 to 4, characterized in that the base consists of a cloth or fabric, -: 9 · Article of use according to claims 1 to 4, characterized in that the base consists of a metal, 10. Particulate Figment and paint a film-forming solution, consisting essentially of P chen from 2C to 80 parts by weight Vinylconomefeii and BC to 2C Sew "parts of an acrylic-siloxane resin, characterized in that the acrylic-3iloxane & r through (1) Implementation of a molar amount of a silicone resin with at least two functional hydroxyl and / or alkoxyl groups ie molecule with 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer consisting of a) as at least ^; a standardized component made of a hydroxydroxy ester with 2 to 4 carbon atoms, of a dihydric alcohol with ^ 2 to 6 carbon atoms and acrylic acid or ilethacrylic acid, b) a greater weight share of the Sestard ■ partly eonomers from esters of a monohydric "alcohol with 1 to 6 carbon atoms unc the acrylic acid or kethacrylic acid and c) about 0.2 to about 2 hydroxyl groups on ¹ CC? .Units of the Kolefciilar weightedB contains, and (2) reacting the resulting resin with a l-'or.ohydroxyester with 5 bi · t2 Kohlenstoffatomen.eines BATH ORIGINAL 109829/1830 - 25 - 2053256 dihydric alcohols with 2 "to 8 carbon atoms and acrylic acid or methacrylic acid in sufficient quantity to react with at least a substantial part of the unreacted hydroxyl or alkoxyl groups of the siloxanes
was formed. 11. Paint maase according to claim 10, characterized in that the copolymer has 1 to 10 reactive hydroxyl groups per molecule * 12. Ar_3trichsmasse according to claim 10, characterized in that the copolymer has about 0.5 to about 1.5 hydroxyl groups per 1000 units of molecular weight. 13. Anarrichaaiasse according to claim 10 to 12, characterized . that the 3ilioxane has 2 to 5 functional groups per molecule and the functional groups consist of hydroxyl groups and / or methoxyl groups. 14 · Painting composition according to claims 10 to 13, characterized in that the vinyl monomers consist of esters of acrylic acid or methacrylic acid with alcohols with T to 3 carbon atoms. 15. Aii3trichama3se according to claim 10 to 13, characterized ge Ice nnze rest t that the Yinylmono kidney essentially of "a mixture Yon Tiny! Hydrocarbons. 3 big 10 carbon atoms and esters of P * Q ORIGINAL 1QS8-29 / 1830 206 3258 Acrylic acid or methacrylic acid with alcohols with up to 3 carbon atoms, 16, Anatrichsmasse claim tu to ¹ -5, characterized in that the solution filmbiliende daae essentially of 35 Ma 65 parts by weight of the acrylic-siloxane Harzea and 65 ^T ois 35 parts by weight of Ieilen T is monomeric. 17 »Method for covering a base, whereby on ■ the surface of the base to a 1juroh: 3chr_ittdiefe in the range from about 2.5 to about ¹ CO, u a film-forming solution of practically 20 to 30 -Jew, -Teile Tinylmonoeren and 30 to Jew 20, parts by an olefinically unsaturated in .x, 3-otellung oiloxan acrylic resin is applied νικΐ iie Tinyl- monomeric uni dag resin on the Jberfl'iche by exposure of the coating to a ilelctronenstranl m ± z an average energy in the range of about IGO 000 to about 5CO COO ToIt is networked, la through . characterized that the acrylic oiloxane resin by (1) reaction of a molar amount of a 3ilc-xane resin with at least two funlcti one Ilen hydroxyl and / or alkoxyl groups per molecule with 0.5 to about 1.5 molar proportions of a copolymer ^ from vinyl monomers, the copolymers from a) as at least one monomer component a monohydroxy ester of 2 to 5 carbon atoms a dihydric alcohol with 2 to 3 carbon atoms and acrylic acid or methacrylic acid, b) a larger weight fraction of the constituent monomers from esters of a monovalent BATH Ϊ09829 / Ι83Ο,. "ordered xinä c)" to 8 carbon atoms, and ^Λ .Acrylsäure oäer with ^{Kethacrylsäure:} ^ twa-Q, 2 "to about 2 hydroxyl groups on 100fr - .. ^ f ^ NIT of T'lDlekTilargewichtes contains UNAE (.2) reacting of the resin obtained with a mono- ^ hyurexyester with 5 Ms 12 carbon atoms of a dihydric alcohol with 2 to 8 carbon atoms and the acrylic acid or Rethacr3 ^T lactic acid in sufficient amount for reaction with at least a substantial part of the unreacted hydroxyl or alkoxyl groups of dilozans was formed » -Liloxar obtained resin (I ^ yours. Reacting a mclarer. Siiozane proportion of a having at least two functional I-Iydroxylgruppen and / or Allioxylgripper, with about ₁ L ice 5 about 1.5 molar idateilen eir.ee CcpoiyiLeren from vinyl monomers, v 'ofcei the copolymer ai; e (A) as at least one component of the r.onomeren from eir.em, Xoiohydroxyester with 5 to 12 carbon atoms of a divalent. .- "Ikoholes with" g 2 ci-s c carbon atoms and acrylic acid or iiethacrylssure and ^(b% - a larger 3-evichtsanteil of Konor.erbestandteilet; ενε .Estern a monovalent alcohols ε having 1 to 6 carbon atoms, and d ~ r .acrylsäure CCER T-Iexhacrylsäure is and (c 'about Z _f c to about 2 hydroxyl groups on IZOO Contains iunits of molecular weight, and (2) Umse xz -.mg of the resin obtained with a? 1onohyäroxyester with 5 to ¹ 2 carbon atoms BATH ORIGINAL 109829/183 0 -ze- 20G325§ divalent alcohols with 2 to 8 carbon atoms and the acrylic acid or methacrylic acid in an amount sufficient to react with at least one significant proportion of the unreacted hydroxyl or alkoxyl groups of the siloxane, 19,. ¥ erfairren for the production of an acrylic siloxane harses after. Claim 18, characterized in that a 'molar proportion of a siloxane with at least 3% functional hydroxyl groups and / or alkoxyl groups aitv / a 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer from (A) as at least one component of the monomer from one! f-ionohydroxy esters having 5 to 12 carbon atoms a dihydric alcohol with 2 to 8 carbon atoms and acrylic acid or kethacrylic acid and (Tj) a larger proportion by weight of the monomer component from esters of a monovalent alcohol ax 1 to 8 carbon atoms and the acrylic acid or methacrylic acid and Cc) about 0.2 to about 2 hydroxyl groups per 1000 ZirJxeiten of the molecular weight, and (2) the resin obtained with a honey hydroxyester with 5 rock 12 carbon atoms of a divalent alkoxylic hole with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in an amount sufficient to react with at least a substantial proportion of the unreacted hydroxyl or alkoxyl groups of the siloxane
is implemented. BAD ORiGjfsJAL 109829/1830 20. The method according to claim 19, characterized in that an oiloxane with functional hydroxyl groups is used as the siloxane. 21. The method according to claim 19 » characterized in that an oiloxane with functional methoxyl groups is used as the siloxane. 22. The method according to claim 19 to 21, "characterized in that that a siloxane with 2 to 5 functional groups per molecule is used and the functional groups Groups made up of hydroxyl groups and / or kethoxyl groups exist. BATH ORIGINAL 109829/1830