DE2063129A1 - Acrylic-siloxane resins, methods of coating objects and articles coated therewith - Google Patents

Description

Acrylic siloxane resins, process for coating Objects and objects coated therewith

The subject of the invention is a new acrylic-siloxane-paint-resin, which is crosslinkable with vinyl monomers on exposure to an electron beam and which is obtained by a two-stage reaction, whereby (1) a siloxane with 2 or more functional hydroxyl or alkoxy groups per molecule with a monohydroxy acrylate with Cj- to C. ₂ , for example a monohydroxyl ester of a Cp- to Cq-DIoIs, and the acrylic acid or methacrylic acid is reacted and (2) the reaction product containing the siloxane of the first reaction stage is reacted with a functional hydroxyl copolymer of the acrylic monomers.

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Electron-curable siloxane-acrylate reaction products are in the patent specification, ... ... (patent application P 19 573 56.9J proposed.

Electron-curable, siloxane-modified polyester paints are described in U.S. Patents 3,437,512 and 3,437,513.

One object of the invention consists in siloxane-containing paints, which are curable by irradiation with electron beams and which have improved adhesion show on the substrate what they are hardened on.

Another object of the invention consists in siloxane Electron beams are curable and which are tailored to the various degrees of flexibility can.

According to the invention, there is a way to silicone-modified acrylic paints, the siloxane Weather resistance results.

According to the invention, the acrylic-siloxane resins (1) by reacting a siloxane with a hydroxy acrylate and . (2) Reaction of the product with a copolymer obtained from vinyl monomers.

It was found that an improved adhesion, Weather resistance and flexibility of the paint film in the electron beam cured coating is obtained if this is combined with vinyl

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monomeric and new ones which are olefinically unsaturated in the α, β-position Acrylic-siloxane resins, which are detailed below are described contains.

The invention thus also relates to coated articles of daily use, in which the coated surface has a high resistance to atmospheric agents, a shows improved hardenability, improved flexibility and improved ■ adhesion to the substrate with one method for the production of such coated surfaces with the paints used in these processes and a method for producing the novel paint binder resin used in this paint composition. In particular the invention is concerned with the coating of substrates made of wood, glass, metal, polymeric solids and cloths made of synthetic or natural fibers and the curing of the new paints on them.

The new acrylic-siloxane paint binder resins according to the invention are produced by a two-stage reaction, whereby (1) a siloxane with two or more functional hydroxyl or alkoxy groups per molecule with a monohydroxyacrylate with 5 to 12 carbon atoms, for example a monohydroxy ester of a C ₂ - to Cg Diols and acrylic acid or methacrylic acid, and (2) the siloxane-containing reaction product of the first reaction stage is reacted with a functional hydroxyl copolymer of acrylic monomers.

In the context of the invention, the term "paint" refers to the material including pigment and / or particulate! Filler, the binder without pigment and / or

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Filler or only with a very low content of it, which can be colored if desired. Thus, the binder, which will eventually become permanent, can be opposed to Weather resistant film is transferred from the entirety or practically all of it exist what is used to form the film or it can be used as a carrier for pigment and / or particles shaped filling material are referred to.

The siloxanes used in the production of the binder have a reactive hydroxyl or alkoxy group, advantageously with C ^ to C and preferably an alkoxy group with C ₁ to Cp, which are bonded to at least two of the silicon atoms. As used herein, the term "siloxane" denotes compounds with a bond

- Si - 0 - Si - or -CO-Si it ι ι

where the remaining valencies are represented by a hydrocarbon radical, a hydrocarbonoxy radical, hydrogen atoms, a hydroxyl group or an oxygen atom are saturated, which connect the silicon atoms with such a valence with another silicon atom. The siloxane can be either cyclic or acyclic. Suitable cyclic and acyclic siloxanes for use in the context of the invention are described in the above US Pat. Nos. 3,437,512 and 3,437,513 and in other literature references. The preferred siloxanes contain 2 to 5 functional hydroxyl and / or alkoxyl groups. The choice of the reactants is advantageously made so that the siloxane is about 10 to about 50 _# - $ of the two-stage reaction process

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holding binder resin.

The acrylate used in the first reaction stage provides the olefinic α, β-unsaturation of the resin. Suitable acrylates include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, 2-hydroxybutyl acrylate or methacrylate, 2-hydroxyoctyl acrylate or methacrylate, and the like Acrylate compounds.

In a preferred embodiment, the relative Ratios of acrylate and siloxane adjusted so that a product results as closely as possible in which only a functional hydroxyl and / or alkoxyl group of the siloxane reactant with the acrylate / molecules is implemented. Such a group remains unreacted> so that it interacts with the hydroxylated acrylic resin in the second Reaction stage can react. As the preferred siloxanes Containing 2 to 5 functional groups per molecule, has the siloxane molecule in the preferred end product resins bound 1 to 4 acrylate molecules and 1 molecule of the hydroxylated acrylic resin. However, it is complete Control not expected and therefore the siloxane molecules in the paint binder solution are average about 0.5 to about 1.5 molecules of the acrylic resin bound as reactants. Therefore be the proportions of the reactants in the first reaction stage with respect to the total number of functional ones Groups of the siloxane adjusted so that the remaining unreacted functional groups of the siloxane average about 0.5 to about 1.5 per molecule. Those molecules that are completely through the

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Acrylate conversion are saturated, are copolymerizable with the acrylic-siloxane resin and with vinyl monomers and can thus remain in the paint solution. '* On the other hand, the hydroxyl-containing acrylic acid resin can contain a plurality of reactive hydroxyl groups per molecule, advantageously 1 to 10, and therefore a number are as reactants bound m of siloxane molecules to one molecule of the acrylic resin.

The acrylic resin as a reaction participant, ie the copolymer with functional hydroxyl groups from acrylic monomers, is produced by copolymerizing various acrylic monomers and contains about 0.2 to about 2, preferably about 0.5 to 1.5, reactive hydroxyl groups per 1000 units of molecular weight, These are advantageously formed in the copolymer by using a monohydroxy _{acrylate or methacrylate, for example the monohydroxy ester of a C 2} - to Cg diol, and acrylic acid or methacrylic acid, as a reactant. These include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, 2-hydroxybutyl acrylate or methacrylate, 2-hydroxyoctyl acrylate or methacrylate and similar acrylate esters. The comonomers are preferably balanced by esters of monohydric C 1-6 alcohols of 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 minor proportions of other vinyl monomers in connection with a greater proportion of those listed above

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'ίΓ j ¹ """■■■■■'" ■ ': ■: ■ T ^!

Esters of monohydric C ₁ - to Cg alcohols of acrylic acid or methacrylic acid contain. Such monomers to be used in smaller amounts include acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate and / or vinyl hydrocarbons, such as styrene, vinyl toluene, α-methylstyrenes and the like, and / or acrylonitrile, acrylamide, methacrylonitrile and / or vinyl halides, for example vinyl chloride and / or Vinyl carboxylates, for example vinyl acetate. Such resins have average molecular weights in the range from about 1000 to about 25,000, preferably in the range from about 5000 to about 15,000. The resins can also have α, β-unsaturation, so that, for example, glycidyl acrylate or glycidyl methacrylate can be contained as comonomer, whereupon the prepolymer obtained is reacted with acrylic acid or methacrylic acid.

The flexibility of the cured paint film formed from the thus obtained acrylic-siloxane resin can be significant by varying the molecular weight the acrylic copolymer and / or the number of acrylic copolymer molecules per siloxane molecule in the acrylic-siloxane resin can be varied.

The acrylic-siloxane resin obtained in this way is mixed with vinyl monomers with Cj- to C ^ ^ ⁿ ^ forms the paint binder solution, which is applied to a base in the usual way, for example spraying, roller mounting and the like ionizing- »radiation is hardened, preferably with an electron beam with an average energy in the range

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ranging from about 100,000 to about 500,000, preferably from about 150,000 to about 350,000 electron volts.

The vinyl monomers used in the solution together with the acrylic-siloxane resin are preferably composed of Acrylic monomers ^, for example methyl methacrylate, ethyl acrylate, Butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, those listed above in connection with resin preparation, and the like. Or Mixtures of such acrylic monomers and vinyl hydrocarbon monomers, e.g. otyrenes, and alkylated ones

en styrenes, such as vinyl toluene, α-methyl styrene / divinylbenzene and dergi .. The vinyl hydrocarbons can also be used alone as a vinyl monomer component of the paint binder be used. In connection with the monoacrylates and / or hydrocarbon monomers, lower Shares of di-, tri- or tetrafunctional acrylates be used. Can also be used in conjunction with acrylates and liethacrylaten and / or vinyl carbon also smaller amounts of other vinyl monomers, such as acrylonitrile, acrylamide, methacrylonitrile, vinyl halides, such as vinyl chloride, and vinyl carboxylates such as vinyl acetate can be used.

In the preparation of the paint compositions according to the invention can be that which is olefinically unsaturated in the α, β-position Resin component, i.e. the acrylic-siloxane resin up to about 80% by weight of the paint binder solution on pigment and particulate! Filler-free base and up to one Value of about 20 wt .- ^. Preferably do that Resin about 35 to about 65% by weight of the resin-monomer solution from, the vinyl monomers from about 65 to about 35

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the same amount,. '. Of course, others can also α, β-olefinically unsaturated polymers instead of one smaller proportion of acrylic oiloxan paint binder resin are used according to the invention.

The abbreviation "Hrad" means 1,000,000 rad. The expression "rad" means a radiation dosage that allows the absorption of 100 ergs of energy per gram of absorber, for example Coating film, results. The electron emitting device can consist of a linear electron accelerator that is used to develop a direct current potential is capable in the range given above. In such a device, the electrons usually become grounded emitted by a heating wire and accelerated by a uniform voltage gradient. The electron beam, which can have a diameter of about 3.2 mm at this point, is then in one direction to the training a funnel-shaped otstrahles distorted and then through a metal window, for example made of aluminum, with small amounts of copper-alloyed aluminum, magnesium-thorium alloy with a thickness of about 0.0075 cm.

The binder is preferably applied to the substrate as a continuous film of substantially uniform depth and cured thereon, preferably to a depth in the range of about 0.25 to about 100 yes depending on 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 substrate in a practically uniform depth and, preferably, a

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«TO -

2iS3t2S

sufficiently high viscosity so that a length of 0.0025 cm is held on a vertical surface without 'droplet formation'. The viscosity of the binder is carried Variierimg, the real tive concentrations of ^TI arzbestandteiles and / or by varying the relative concentrations of the various Ilonörneren within the Tinylmonoinerbe was partially set it. The "binder" is preferably applied to the substrate virtually free of non-polymerizable organic solvents and / or diluents, although suitable volatile solvents which are driven off prior to curing can also be used.

The following examples are provided for further explanation the invention.

Example. 1

A hydroxyl-containing copolymer of acrylic monomers, hereinafter referred to as Resin I: was prepared by copolymerizing a mixture of monomers, whose composition was 40 mol -; ^ methyl methacrylate. 50 moles of 1 ^ thylacrylate and 10 moles of hydroxyethyl acrylate. The copolymerization was accomplished by adding the monomers dropwise along with 1.5 wt .-% azobisisobutyronitrile to an equivalent weight of refluxed xylene.

The acrylic oiloxane resin was made in the following manner made of the following materials:

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I. Implementation of stage I

The siloxane-acrylate reaction product was obtained from the following materials:

Respondents . Parts by weight oleoxane with functional

liethoxyl groups ^ '250

Hydroxyethyl acrylate 80

(1) Acyclic polysiloxane having an average molecular weight in the range of 700 to 800 with an average of 3 to 4 functional Hethoxylgruppen per molecule.

procedure

The two reaction participants were ^{heated to 100 °} C. and the temperature increased to 150 ^{° C.} over a period of 2 hours in the presence of 0.5 part by weight of tetraisopropyl titanate (catalyst) and 0.2 part by weight of hydroquinone Parts by weight of methanol were distilled off.

II. Implementation of stage II

The siloxane aorylate reaction product according to I was with the resin I implemented.

Reactants parts by weight

Resin I ($ 50 in xylene) 202

Siloxane acrylate according to I 93

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• Procedure

The two ingredients were mixed and heated to 10O ⁰ C and raising the temperature to 130 ⁰ C for 1 hour. Xylene and other volatile reaction products were then removed by vacuum distillation (10 .mm Hg at 110 ⁰ C).

The acrylic siloxane Sk resin prepared in the foregoing manner, 'was dissolved in.200 parts by weight of methyl methacrylate. A film of this solution was drawn onto a steel plate and irradiated with an energy of 8 Mrad with an electron beam of 275 kilovolts and 25 milliamps in a nitrogen atmosphere. The film was HB pencil hardness, withstood 10 rubs with a sponge soaked in methyl ethyl ketone, and had good adhesion to the metal.

Example 2

An acrylic-siloxane resin was prepared according to the method of Example 1 with the difference that it was functional equivalent amounts of different acrylic resins and ™ functional cyclic hydroxylsiloxanes instead of the in Example 1 used acrylic resins and siloxanes was used. . ; . -,

The acrylic resin used here was made by copolymerization of 8.0 mol-96 ethyl acrylate, 10 mol - ^. Hydroxyäthylacrylat and 10 moles of glycidyl methacrylate. The copolymerization was carried out by adding the monomers dropwise together with 1.5% by weight of azobisisobutyronitrile

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the equivalent weight of refluxed xylene. When the reaction was complete, it became acrylic acid in an equimolar ratio to the glycidyl methacrylate added and reacted with the resin.

The siloxane used consisted of a commercially available one hydroxyl functional cyclic polysiloxane (Dow Corning Z-6018) with the following properties:

Hydroxyl content according to Dean Stark: ^

fo condensable 5.5

° / o free. 0.5

Average molecular weight 1600

Link weight 400

Refractive index 1.531-1.539

Durran softening point

Mercury process, ⁰ C ( ⁰ F) 93 (200)

at $ 60 pesticide in xylene

specific weight at 25 ⁰ C 1.075

Viscosity at 25 ⁰ C (centipoise) 33

Gardner-Holdt A - 1st

Example 3

The process according to Example 1 was repeated, but as the hydroxy acrylate in the first stage 2-hydroxyethyl methacrylate used,

Example 4

The process of Example 1 was repeated, but as the hydroxy acrylate used in the first stage 2-Hydroxybutyl acrylate used.

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Example 5

The process according to Example 1 was repeated, but "2-hydroxybutyl methacrylate was used as the hydroxy acrylate in the first stage and an average depth of the applied and cured film of about 0.5 Ά was used.

Example 6

The process according to Example 1 was repeated, but using 2-hydroxyoctyl acrylate as the hydroxy acrylate in the first stage and about 100 η as the average depth of the applied and cured film.

Example 7

The procedure of Example 1 was repeated, however as Hyujfoxylaerylat in the first reaction stage 2-Hydroxyoctylmethacrylat used.

In Examples 2 to 7, too, excellent results were obtained.

Example 8

The procedure of Example 1 was repeated, however the paint binder solution contained 80 parts by weight of the acrylic-siloxane resin and 20 parts by weight of methyl methacrylate, the backing was made of glass and curing was achieved by exposure to an electron beam of 295 kilovolts and 25 milliamps.

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Example 9

The procedure of Example 1 was repeated, however the paint binder solution contained 20 parts by weight of an equimolar mixture of methyl methacrylate, styrene, iithylacrylate, butyl acrylate and 2-ethylhexyl acrylate, the The backing was made of wood and curing was achieved by exposure to an electron beam of 325 kilovolts and 25 milliamps.

Example 10

The procedure of Example 1 was repeated, but the paint binder solution contained 35 parts by weight of the Acrylic-siloxane resin and 65 parts by weight of a mixture from 2 molar portions of methyl methacrylate, one molar portion of ethyl acrylate, 1/2 molar portion of vinyl toluene, 1/2 molar portion of divinylbenzene, 1/2 molar portion Vinyl acetate and 1/2 molar proportion of putyl methacrylate and as a base was a polymeric Peststoff, namely an acrylonitrile-butadiene-styrene copolymer is used.

Example 11 i

The procedure of Example 1 was repeated, however the vinyl monomer component consisted of a mixture of 4 molar proportions of methyl methacrylate, 1 molar proportion Vinyl acetate, t / 2 molar proportion of 2-hydroxyethyl acrylate and 1/2 molar portion of vinyl chloride, while the backing consisted of a cotton cloth.

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Example 12

The procedure of Example 1 was repeated, however was the paint binder solution with particulate! Pigmented titanium dioxide.

In Examples 8 to 12, too, excellent results were obtained.

The subject of the invention are thus objects of use, consisting of a base and an adhesive attached to it Coating of a paint on an external surface thereof, the coating being that formed in situ Polymerization product of a film-forming solution of 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight of one which is olefinically unsaturated in the α, β-position Acrylic-siloxane resin which has been applied to and on the surface as a paint film by exposing the film to ionizing radiation was crosslinked, the "acrylic-siloxane resin through."

(1) Reaction of a molar proportion of a siloxane with at least two functional groups per molecule in the form of hydroxyl groups and / or alkoxyl groups with a hydroxy acrylate made from C ^ - to C ^ monohydroxyl esters of dihydric C ₂ - to Cg alcohols and acrylic acid or Methacrylic acid in sufficient quantity so that at least one molecule of the acrylate reacts with a functional group on each molecule of the siloxane, and

(2) Reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5 molar proportions of a copolymer aus'Vinylmonomere, the copolymers

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(A) at least one monomer as a component of the same in the form of a C ₁ - to Cjo-monohydroxy ester of a dihydric Cp- to Co-alcohol and acrylic acid or methacrylic acid and

(B) a larger proportion by weight of the constituent monomers thereof in the form of esters of a monohydric C ₁ - to C _Q alcohol and acrylic acid or methacrylic acid and

(c) about 0.2 to about 2 hydroxyl groups in 1000, ^ Having units of molecular weight, ™

was obtained.

The base is preferably made of wood, a synthetic polymeric solid, glass, a cloth or a Metal.

The paint compositions according to the invention consist of a particulate pigment and a film-forming solution which consists essentially of 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight of an acrylic-siloxane resin and is applied to the surface as a paint film and on top by exposing the film to d

ionizing radiation is crosslinked, the acrylic-siloxane resin by

(1) Implementation of a molar proportion of a siloxane with at least two functional groups per molecule in Form of hydroxyl groups and / or alkoxyl groups with a hydroxy acrylate from 0, - to C-p-monohydroxyl esters of divalent Cp- to C ^ -alcohols and the Acrylic acid or methacrylic acid in sufficient quantity, so that at least one molecule of the acrylate reacts with a functional group of each molecule of the siloxane, and

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(2) Reaction of the resulting acrylate-siloxane with

about 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer

(a) at least one monomer as a component thereof in the form of a Cc to Cjg monohydroxy ester of a dihydric Cp to Cn alcohol and acrylic acid or methacrylic acid and

(b) a greater proportion by weight of the constituent monomers the same in the form of esters

™ of a monohydric Cj to Cg alcohol and the

Acrylic acid or methacrylic acid and

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

was obtained.

The method according to the invention for coating a substrate, the surface of the substrate being applied to an average in the range from about 0.25 to about 100 liters. a film-forming solution which "practically consists of 20 to 80 parts by weight of vinyl monomers and 80 to 20 parts by weight of an α, β-olefinically unsaturated acrylic ^ siloxane resin, is applied and the vinyl monomers and the resin the surface are crosslinked by exposure of 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) conversion of a molar proportion of a Siloxanes with at least two functional groups per molecule in the form of hydroxyl groups and / or alkoxyl groups with a hydroxy acrylate made from Ce to C ^ 2- ^monol y & poxyl esters of dihydric C ₂ - to C _Q alcohols

Acrylic acid or methacrylic acid in sufficient ^ close, so that at least one molecule of the acrylate with a functional group of each molecule of the siloxane reacts, and

(2) Reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer Ca) having at least one monomer as a component thereof in the form of a Gj- to Sp-monohydroxy ester of a divalent C ₂ - to Cg alcohol "

and acrylic acid or methacrylic acid and

(B) a larger proportion by weight of the constituent monomers thereof in the form of esters of a monohydric C ₁ - 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,

was obtained.

The acrylic-siloxane resins according to the invention are produced by (1) reacting a molar proportion of a siloxane with at least two functional groups per A

Molecule as hydroxyl groups and / or alkoxyl groups with Cc to C ₁ 2- ^{monohydroxyl es} * ^{erns of} dihydric C ₂ ^{to Cg alcohols as hydroxy} acrylate and acrylic acid or methacrylic acid in sufficient quantity to react with at least one molecule of the acrylate a functional group in each case of a molecule of the siloxane and (2) reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5 molar amounts of a copolymer from vinyl monomers, the copolymer from

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. _20th 2063123

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

(Td) a larger proportion by weight of the constituent monomers consists of esters of a monohydric C ₁ - to C _R alcohol and acrylic acid or methacrylic acid, and

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

The process according to the invention for the production of these acrylic-siloxane-Karze consists in that (1) a molar proportion of a siloxane with at least two functional groups per molecule as hydroxyl groups and / or alkoxy groups with a Cp- to Cp- ^ onohydroxylester of bivalent Cp- to Cg- alcohols as hydroxy acrylate and acrylic acid or methacrylic acid in sufficient quantity to convert at least one molecule of the acrylate with a functional group of one molecule each of the »siloxane- and (2) the resulting acrylate-siloxane with about 0.5 to about 1.5 molar amounts of a copolymer of vinyl monomers, the copolymer of Bf (a) at least one monomer as a component of a dihydric C _{1 to C Q} alcohol and acrylic acid or methacrylic acid,

(b) a larger proportion by weight of the constituent monomers consists of esters of a monohydric C ₁ - to Cg alcohol and acrylic acid or methacrylic acid and

(c) about 0.2 to about 2 hydroxyl groups for every 1000 one. . units of the molecular weight, is implemented »

BAOORIGtNAi. 109847/1805

In this case, the siloxane is preferably used with one to react with the greater part of the functional groups of the siloxane sufficient amount of the hydroxy! acrylate implemented. The siloxanes used are preferably siloxanes with functional hydroxyl and / or methoxyl groups. Preferred siloxanes are those with 2 to 5 functional groups used per molecule, the functional groups consist of hydroxyl groups and / or methoxyl groups,

Furthermore, corresponding acrylic-siloxane resins (1) by reacting a molar proportion of a siloxane with at least two functional hydroxyl groups and / or Alkoxyl groups with about 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer ' the end

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

(b) a greater proportion by weight of the monomer component s 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 having 5 to 12 carbon atoms of a divalent one Alcohol with 2 to 8 carbon atoms and acrylic acid or methacrylic acid in a sufficient amount Amount for reaction with at least a substantial proportion of the unreacted hydroxyl or alkoxyl groups of the siloxane

are made or consist of it.

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Claims (1)

_ 22 - Claims 1. Utility item, consisting of a base and a coating of a paint adhered thereon on an outer surface thereof, 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 of an α, β-position olefinically unsaturated acrylic siloxane resin, which was applied to the surface as a paint film and was crosslinked thereon by exposure of the film to ionizing radiation, characterized by the fact that the acrylic siloxane resin penetrated (1) Implementation of a molar proportion of ines siloxanes with at least two functional groups per molecule in the form of hydroxyl groups and / or alkoxyl groups with a hydroxy acrylate composed of C - to Cj p ~ monohydroxyl _{esters of dihydric C 2} - to Cg alcohols and acrylic acid or Methacrylic acid in sufficient quantity so that at least one molecule of the acrylate is finer functional group P of each molecule dts siloxane reacts, and (2) Use of the resulting acrylate-siloxane with approx 0.5 to about 1.5 solar fractions of a copolymer from vinyl monomers, where the copolymer (a) at least one monomer · as a component of the same in the form of a Ce * to C ₁₂ monohydroxy ester of a zwtiwsrtigsn C ₂ - to C ₈ alcohol and acrylic acid or methacrylic acid and (B) a larger Gewientsantsil the Beetandteilsmonomere the same in the form of esters one 109847/1805 monohydric C ^ - to Cg alcohol and acrylic acid or methacrylic acid and (e) about 0.2 to about 2 hydroxyl groups per 1000 - '■' ■■: ■ ' units of molecular weight was obtained; 2. commodity according to claim 1, characterized in that the siloxane with a for reaction with. the greater part of the functional groups of the siloxane sufficient Kenge of the hydroxylacrylate has been implemented. ~ · -. 3 »commodity according to claim 1. or. 2, characterized in that siloxanes with functional hydroxyl and / or methoxyl groups were used as the siloxane / - 4. Utility object.nach claim 1 to 3, characterized in that as. Siloxane those with 2 to 5 functional groups per molecule were used, with the functional groups consisting of hydroxyl groups and / or methoxyl groups exist,. ^ 5. commodity according to claim 1 to 4, characterized in that the base consists of wood. 6. commodity according to claim 1 to 4, d adurch ι that the base consists of a synthetic polymeric solid. , 7. commodity-according to claim '1 to 4, characterized in that the base consists of glass. 10984771805 8. commodity according to claim 1 to -4, characterized in that :? the base consists of a cloth. ■ 9. commodity according to claim 1 to 4, characterized in that the base consists of a metal. 10. Paint composition consisting of a particulate φ pigment and a film-forming solution, which consists essentially of 20 to 80 parts by weight of Vinylmonnmere / n and 80 to 20 parts by weight of an acrylic-giloxane resin and applied to the surface as Paint filet applied and crosslinked on it by exposure of the film to ionizing radiation, characterized in that the acrylic-siloxane resin by - (1) Reaction of a molar proportion of a siloxane with at least two functional groups per molecule in the form of hydroxyl groups and / or Al> oxylsrurpen with a hydroxy acrylate from G ₁ - to C ₁₀ - J'C- i-ionohydroxyl star of zv / eiovalent Cp- to Cp-alcohols and acrylic acid or kethacrylic acid W in sufficient quantity, so that at least one Molecule of the acrylate reacts with a functional group of each molecule of the siloxane, and (2) Reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5 molar proportions of a copolymer of vinyl monomers, the copolymer (a) at least one monomer as a component DES ¹ the same in the form of a C ^ - to Op-monohydroxy ester of a dihydric G ₂ - to Cg alcohol and acrylic acid or methacrylic acid and IÖ9847 / T805 (b) a larger proportion by weight of the constituent monomers thereof in the form of esters of a monohydric C ₁ - to Cg alcohol and acrylic acid or methacrylic acid and (c) has about 0.2 to about 2 hydroxyl groups per 1000 units of molecular weight, was obtained. 11. Paint composition according to paint 10, characterized in that the siloxane has been reacted with an amount of the hydroxyacrylate sufficient to react with a larger proportion of the functional groups of the siloxane. 12. A coating composition according to claim 10 or 11, characterized in that siloxanes with funfctionel Ien hydroxyl and / or methoxyl groups were used as the siloxane. 13. A coating composition according to claim 10 to 12, characterized in that those having about 0.5 to about 1.5 hydroxyl groups per 1000 units of molecular weight were used as the copolymer. 14. Claim composition according to 10 to 13, characterized in that the yinyl monomers used were practically esters of acrylic acid or methacrylic acid with alcohols having 1 to 8 carbon atoms. 15. A coating composition according to 10 to 13, characterized in that the vinyl monomers are mixtures of Cg- to G-jq-vinyl hydrocarbons and esters of acrylic acid 109847/1805 or methacrylic acid with C ^ - to Cg alcohols used became. 16. A coating composition according to 10 to 15, characterized in that the film-forming solution consists practically of 35 to 65 parts by weight of the acrylic-siloxane resin and 65 to 35 parts of the vinyl monomers. 17. A method of covering a substrate, whereby the surface of the substrate is approached. an average "en depth in the range from about 0.25 to about 100 μ a film-forming solution, which practically consists of 20 to wt. 3iloxane resin is applied and the Yinyimonomeren and the resin on the surface are 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, characterized in that the acrylic siloxane Resin through (1) Reaction of a molar proportion of a siloxane with at least two functional groups per molecule in the form of hydroxyl groups and / or alkoxyl groups with a hydroxy aerylate of C ₁ to C ₁ ? Monohydroxyl esters of dihydric Cp to Cq alcohols and acrylic acid or Methacrylic acid in sufficient quantity so that at least one molecule of the acrylate reacts with a functional group of each molecule of the siloxane, and (2) Reaction of the obtained acrylate-siloxam with about 0.5 to about 1.5 molar proportions of a copolymer 109847/1805 from vinyl monomers, the copolymer (A) at least one monomer as a component thereof in the form of a C ₁ - "to C ^ monohydroxy ester of a dihydric C ₂ - to Cg alcohol and acrylic acid or methacrylic acid and (b) a greater proportion by weight of the constituent monomers the same in the form of esters, one monohydric C, C, alcohol and acrylic acid or methacrylic acid and (c) has about 0.2 to about 2 hydroxyl groups per 1000 units of molecular weight, was obtained. Acrylic Uilcxan resin, produced 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 _K - to C,. «- monohydroxyl esters of dihydric Cp to Cg alcohols as Hydroxylacrylate and acrylic acid or methacrylic acid in sufficient quantity to react with at least one molecule of the acrylate with a functional group of one molecule each of the siloxane and (2) reaction of the resulting acrylate-siloxane with about 0.5 to about 1.5 molar amounts of one Copolymers from Yinylmonoreren, the copolymers from
(A) at least one monomer as a component of a divalent Cp- to C ^ -alcohol and the Acrylic acid or methacrylic acid, ("b) a greater proportion by weight of the constituent monomers from esters of a monovalent Cj bis SAO ORIGINAL 109847/1805 Cg alcohols and acrylic acid or methacrylic acid and (o) has about 0.2 to about 2 hydroxyl groups per 1000 units of molecular weight. ι 19. A method for producing an aeryl-siloxane resin according to claim 18, characterized in that (1) a molar proportion of a siloxane with at least two functional groups per molecule as hydroxyl groups and / or alkoxyl groups with a Ce to CLp monohydroxyl ether of dihydric Cg to C «alcohols as hydroxy acrylate and acrylic acid or methacrylic acid in sufficient quantity to react at least one molecule of the acrylate with a functional group of one molecule of the siloxane and (2) the resulting acrylate-siloxane with about 0.5 up 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 C ₂ - bit Cg alcohol and acrylic acid or methacrylic acid, (b) a larger proportion by weight of the constituent monomers consists of esters of a monohydric C ₁ - to Co alcohol and acrylic acid or methacrylic acid and (o) about 0.2 to about 2 hydroxyl groups per 1000 Has units of molecular weight, is reacted. 0 9847/1805; _ ₂₉ . 2063139 20. The method according to claim 19, characterized in that the siloittn is umgf eetxt with a sufficient amount of the Hydroxyleerylfctes to react with dta larger part of the functional groups of the siloxaase. 2t. Method according to claim 19 or 20, characterized I agree that the siloxane Siloxam «with fimfctio® € 13» fl Hydrcapyl * and / or methootyl groups are used will be 22. Method according to Amspruch 19 to 31, thereby as Siloaegiae solelie with 2 t> i «5 functional groups | e molecule eineee-fcEt w * r4em, - '«äfetfl idie fxEB3tli®nstll * n <Jru> ip« n iams and / ader ^ Metho3Eylgruppen ORiQtNAL INSPECTED