DE1957357C3 - Coating binders based on siloxane curable by ionizing radiation and their use - Google Patents

Description

the weather. . . ,

Inventory status is one by ionizing Radiation-curable paint tapes from S.loxanbas.s "Combination with unsaturated polymers or resins and optionally unsaturated monomers, which consists of a mixture of ■ n 20 to 80 parts by weight of an olefinically un- '" saturate siloxane. which by reacting a "siloxane with 3 to 18 silicon atoms and at least two functional groups, namhch Hydroxyl groups and / or hydrocarbon oxy groups. with a hydroxy ester of a carboxylic acid which is olefinically unsaturated in the -position has been received. and

b ^l 80 to ^"1 O parts by weight of a oleiinisch un- 'sittiuten or epoxy resin and an olefinically unsaturated diurethane. that .'- position olefinically unsaturated carboxylic acid is obtained by reacting a diisocyanate with a hydroxy ester of an in." obtained.

The invention is in the field of paints based on siloxane. thanks to which the coated surfaces both have a high level of resistance to abrasion as well as a high resistance to the effects of the weather. the Coating compounds are for any commodity with external surfaces made of wood. Metal or synthetic polymeric solids suitable with the polymerisation product formed in situ film-forming paint binder solution applied to these surfaces and cured by ionizing radiation are coated.

There are already reaction products of siloxanes with unsaturated carboxamides and others unsaturated monomers known as coating compositions, which are cured or crosslinked with catalysts will. These coatings / inherent do not have sufficient resistance and, in particular, discolour Slightly due to bad weather, like most of them consists and optionally 10 to 200 parts by weight of vinyl monomers.

These paint binders are preferably used in a coating process an electron beam with an average energy of 100,000 to 500,000 eV.

The siloxane component is made by reacting a Siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups. with an ester containing hydroxyl groups and one which is olefinically unsaturated in the., / - position Carboxylic acid, preferably by reacting at least two molar proportions of the ester with a molar proportion of the siloxane. educated. The diurethane mono-interior is made by reacting these hydroxyl-containing ester with an organic Diisocyanate. preferably by converting two molar proportions of the ester prepared with a molar proportion of the diisocyanate. In a preferred The embodiment also contains the film-forming solution Vinv! Monomers.

The invention has numerous advantages. On the one hand is through the siloxane component Achieved weather resistance and outdoor use and the copolymerization by ionizing Radiation while the binder material is in the drawn-up state is a far simpler route. this Incorporating material than chemically combining with the resin prior to curing. It also enables a much better adaptation of the

Sjrhtis intended use reduces the amount of Siioxäii- by the epoxy component or the ure-.i. _to K _e! :!. andieil des Mar / es the riK'ryu «has a very low abrasion resistance in connection with a wedge resistant to weathering in the open air, which z. B. even uses in extremely stressed surfaces, for example for roller skating rinks, allowed. The coating compositions known to date do not show this favorable combination of essential properties. The application of these ingredients with ionizing Sirahiung. In particular, an electron beam, which can be copolymerized, also permits wide ranges of concentration ratios with regard to the individual parts of the land. The undercoating paint binder can also be used together with vinyl monomers and or together with all known. Paint binder resins curable by ionizing Strah-Ju ns can be used.

The expression "paint" or "paint" also includes a content of pigment and / or (ground-in filler in the binder solution, the binder solution without such a pigment and / or filler or only with a very low content thereof, whereby the binder solution can be colored if desired. thus, the binder solution, which may eventually ⁿ a permanent, to abrasion and weather resistant film is transferred in the open air, from the entirety or practically consist of the totality of the material used to form the film, or it can be used as carrier material for pigment and or particulate filler are present.

The siloxanes used to make the binder have reactive hydroxyl groups and or hydrocarbon oxy groups bonded to at least two of the silicon atoms. Of the The term "siloxane" here denotes compounds that form a bond

either (a) a monohydric hydrocarbon oil with I to S carbon atoms, preferably an alkylres! rp.'t! up to 4 carbon atoms, or (bj a monovalent Hydrocarbonoxy radical with 1 to 8 carbon atoms. preferably an alkoxy radical having 1 to 4 carbon atoms, or (c) a hydroxyl group or (di denotes a hydrogen atom, where at least two of the by a bond

X - Si - O - Si ~~ X

separate groups X either have the meaning IbI or (el.

The cyclic siloxanes which can be used for the production of the paint binder component in the context of the invention contain at least 3, preferably 6 to 12 and not more than 18 silicon atoms per molecule with the corresponding oxygen bonds. The cyclic polysiloxanes that can be used can be used in the form of one of the following typical formulas:

I. X ", Si" O ".,. where η is an odd positive number of at least 3. n ' the value of 2 »and n" the value; i. X either (a) a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms, or ( b) a monovalent hydrocarbon oxyresi with 1 to 8 carbon atoms, preferably an alkoxy group with 1 to 4 carbon atoms or (ei a hydroxyl group or (d) a hydrogen atom, at least two of which are denoted by a Bi ηdunü

35 X-Si-O-Si-X

- Si - O - Si -

- C - O - Si separate groupings X either the meaning (b) or (c), an example of which is given by the following formula:

45

contained, the remaining valences by a hydrocarbon radical. a hydrocarbon oxy group, hydrocarbon. Hydroxyl groups or oxygen atoms which connect the silicon atom having such a valence with another silicon itic.xn. AbcsattitM are.

Both cyclic and acyclic siloxane molecules can be used for the preparation.

The acyclic ones useful in making the paint binder ingredients according to the invention Si'oxane molecules contain 3 to 15 silicon atoms each Molecule with the corresponding oxygen bonds. The preferred siloxanes are as follows general formula reproduced:

Si

X-Si C) Si-X

II. X ₁₁ , Si ₁₁ C) ,,,,. where 11 is an odd positive number of at least 5. 11 'the value η + 3 and 11 "the numbers 6. 6 + 3 or 6 + a multiple of 3. X either (a) a monovalent hydrocarbon radical having 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (h) a monovalent hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms or (el a hydroxyl group or (dl a hydrogen atom, where at least two of the

X - Si - O -

Si - O

- Si - X

Si C) - Si X

χ ι χ I ₁₁

wherein / 1 has a value of at least 1 and X separate groupings X either mean

(b, or (C), an example of which is given by the following structural formula:

X — Si — O — Si

O X

\ / G O Si

/ \ O X

X-Si-O-Si

a hydrogen ^, where at least / wc. ^{which by cinc Binüun} t

i
X-Si-O-Si-X

"Separate groups X either the meaning fb) or (c), for which an example is given by the following structural formula:

'5

XX

III. X ", Si _n O"", where / i is the number 6 or a multiple of 6, n 'is the number 8. 8 + 6 or 8 + a multiple of 6, n" is the number 8, 8 + 9 or 8 + a multiple of 9, X either (a) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent carbon hydrogen oxyresl with 1 to 8 carbon atoms, preferably an alkoxyresi with 1 to 4 Carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom, at least two of which are represented by a bond

X-Si-

X —Si—
X

- Ο —Si-

- Ο —Si—

- Ο —Si - X

- Ο — Si-X

where m is the number 0 or a positive integer.

V. X ", Si" O where η is a straight positive gan / c

Number of at least 8, n ' the value of n + 2 and n' the numbers 11.11 +3 or 11 + a multiple- · of 3. X either (a) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbon oxy radical with 1 to 8 carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the bonds

35

X - Si - O - Si - X

X-Si-O-Si-X

separate groupings X either the meaning separate groupings X either the meaning Ib) or (c), an example of which by the 40 (b) or (c), an example of which by the the following structural formula is given:

the following structural formula is given:

O X

X X

Si-O-Si

/ i i

X O

Si O O Si

X O O X

Si - O - Si X X

45

50

55 Si

X O

Si O

Si

-O Si

-O-Si-

■ Q-Si

O X

O Si

O X

-O- Si

χ L ^χ

or a dimer formed by condensation with loss of water or alcohol. Trimercs and the like thereof.

IV. X ,,, Si ₁₁ O ₁₁ ,,. where η is an even positive number of at least 4. n ' the value of η -f 4 and n " the number 4. 4 -I 3 or 4 λ- a multiple of 3, X either la) a monovalent hydrocarbon! with 1 to N carbon atoms, preferably an alkyl residue with 1 to 4 carbon atoms, or (b) a monovalent hydrocarbon residue with 1 to 8 carbon atoms oiler (c | a hydroxyl group or (d) where w is a positive number.

A large number of processes are known for producing the siloxanes. This includes the regulated Hydrolysis of silane. the polymerization of a silicon oxane of low molecular weight, the reaction of silicon hydroxide with an alcohol etc. The manufacture of siloxane and its finishing in Organic Resins is described in U.S. Patents 3,154,597, 30 74 904, 30 44 980, 30 44 979. 30 1 5 637, 29 96 479, 29 73 287, 29 37 230 and 2 909 549 described

The ester containing hydroxyl groups is made preferably from a monohydroxyalkyl ester of a monocarboxylic acid which is olefinically unsaturated in the -i./i- position. The preferred hydroxyl-containing esters are acrylates and methacrylates because they are the contain olefinic unsaturation between the terminal carbon atoms and at relatively low levels Dosages of ionizing radiation are easily polymerizable. Examples of such acrylates and Methacrylates are listed below:

■>.

Hydroxyethyl acrylate or methacrylate.

Hydroxypropyl acrylate or methacrylate.

Hydroxybutyl acrylate or methacrylate.

Hydroxyoctyl acrylate or methacrylate.

Hydroxydodecanyl acrylate or methacrylate.

Hydroxy-3-chloropropyl acrylate or methacrylate, hydroxy-3-acryloxypropyl acrylate or methacrylate, hydroxy-3-methacryloxypropyl acrylate or methacrylate.

Hydroxy-3-allyloxypropyl acrylate or methacrylate.

Hydroxy-3-cinnamylpropyl acrylate or methacrylate.

Hydroxy-3-phenoxypropyl-acrylal or methacrylate.

Hydroxy-3- (o-chlorophenoxy) propyl acrylate or methacrylate, HydroxyO-lp-chlorophenoxyl-propyl-acrylate or methacrylate.

Hydroxy-3- (2.4-dichlorophenoxy) propyl acrylate or methacrylate, Hydroxy-3-acetoxypropyl acrylate or methacrylate.

Hydroxy-3-propionoxypropyl acrylate or methacrylate.

Hydroxy-S-chloroacetoxypropyl acrylate or methacrylate.

Hydroxy-3-dichloroacetoxypropyl acrylate or methacrylate.

Hydroxy-3-lrichloroacetoxypropyl acrylate or methacrylate.

Hydroxy-3-benzoxypropyl acrylate or -methaerylal.

Hydroxy-3- (o-chlorobenzoxy) propyl acrylate or methacrylate. Hydroxy-3- (p-chlorobenzoxy) propyl acrylate or methacrylate.

Hydroxy-3- (2.4-dichlorobenzoxy) propyiacrylate or methacrylate, Hydroxy 3- (3,4-dichlorobenzoxy) propylene acrylate or methacrylate. Hydroxy 3- (2.4.6-trichlorophenoxy) propyl acrylate or methacrylate. Hydroxy-3- (2.4.5-lrichlorophenoxy) propyl acrylic or methacrylate. Hydroxy-3- (o-phenoxyacetoxy) propylacryate or methacrylate, hydroxy-3-phenoxyacetoxypropyl acrylate or methacrylate, hydroxy-3- (p-chlorophenoxyacetoxy) propyl acrylate or methacrylate, Hydroxy 3- (2,4-dichlorophenoxyacetoxy) propyl acrylate or methacrylate. Hydroxy-3- (2,4,5-trichlorophynoxyaccloxy) propyl acrylate or methacrylate.

2-Hydroxy-3-crotonoxypropyl acrylate or

methacrylate.
2-hydroxy-3-cinnamyloxypropyl acrylate or

methacrylate.
3-acryloxy-2-hydroxypropyl acrylate or

-methacrylate,
3-allyloxy-2-hydroxypropyl-acrylal or

methacrylate.
3-chloro-2-hydroxypropyl acrylate or

-methacrylate,
3-crotonoxy-2-hydroxypropyl acrylate or

methacrylate.

In addition to these acrylates or methacrylates, one can also use the cinnamates and crotonates. use. The unsaturated diurethanes are made by reacting an organic diisocyanate with a hydroxyl-containing one Esters of the same kind as used for the preparation of the olefinic described above unsaturated siloxane was used, including the esters listed above fall. Further information on such reaction products can be found in the USA patent 3297 745.

The diisocyanates that can be used include: 2,4-toluene diisocyanate. 2,6-toluylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate. IS-naphthalene diisocyanate. m-phenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate. ¹ 3.3 '- dimethyl - 4.4' - diphenyl - methane - diisocyanate. 4.4 '- diphenylmethane diisocyanate, 3.3' - dimethylbiphenylene diisocyanate. 4,4'-biphenylene diisocyanate. 3.3-dimethoxy-4.4'-dimethyl-4.4'-biphenylene diisocyanate. Durene diisocyanate. l-phenoxy-2,4'-phenylene-

diisocyanate. 1-tert-butyl-2,4-phenylene diisocyanate and the like. In special fields of application it may be advantageous to use a halogenated diisocyanate. for example l-chlorine ^^ - phenylene diisocyanate. to use.

The ester which is olefinically unsaturated in the ".fi" position is preferably added in part to the diisocyanate with continued stirring. The ester may be in solution with an inert solvent, and the reaction mixture is preferred kept under an inert atmosphere such as nitrogen while the reaction is carried out will. The addition is preferably carried out at such a rate that the exothermic Heat development does not exceed a value of about 32 C. There is an implementation between the OCN groups of the diisocyanate and the HO groups of the hydroxyl ester. where the in (»./(- position unsaturation present to the carboxylate group remains unreacted. The reaction is exothermic and self-sustaining. The use of an excess of the ester is advisable or beneficial.

Epoxy resins are used in commercial coating compounds that have good chemical resistance to alkalis, excellent adhesion properties and both good hardness and also have flexibility. On the other hand, they have a pronounced tendency to «limescale» outdoors and their water resistance is mostly not good. Such coating compositions are usually by means of Crosslinked polyamines, organic acids or anhydrides. The curing times are between a few minutes and several hours. In contrast, according to the invention, the olefinic

unsaturated epoxy resins with the other olefinically unsaturated materials used within a few seconds at room temperature in the presence of ionizing radiation, especially electron beams, be networked.

According to a preferred embodiment of the invention, the olefinically unsaturated epoxy resins by reacting a diepoxide with a carboxylic acid which is olefinically unsaturated in the -!, / (- position. According to further embodiments, the unsaturation is achieved by reacting the diepoxide with an anhydride of a carboxylic acid which is olefinically unsaturated in the u./v'- position or a monohydroxy ester such an acid, which is advantageously used in excess. The production the specific diepoxides suitable for use in making the resins used herein are in Modem Surface Coatings, Paul NyIe η and Edward Sunderland. 1965, Interscience Publishers. John Wiley & Sons Ltd .. London - New York Sydney. Library of Congress Catalog. Card Number 65-28.-144, pp. 197 to 208. This as the starting material Serving polymers or prepolymers can either be of the epichlorohydrin-bisphenol type or epichlorohydrin polyalcohol type. A large number of such polymers are available commercially available.

The production of usable epoxy resins is also described in U.S. Patents 24 67 171, 25 38072, 25 58 969 and 26 94 694 and in many other places in the literature. Advantageously has the starting polymer has a molecular weight of at least about 320 and below about 10,000. preferably between about 380 and about 3800. The epoxy resins used in the context of the invention with Terminal unsaturation advantageously have molecular weights above about 370 ranging from about 500 to about 40 (X). and contain about 0.5 to about 5., preferably about 1 to about 3.5 olefinic unsaturation per 1000 units of molecular weight.

The term "vinyl monomers" here denotes monomeric compounds with a terminal group

HH

-C = C-H

H ₃ CH
-C = CH

allyl compounds are excluded. The preferred Vinyl monomers are esters of alcoholic alcohols containing 1 to 8 carbon atoms Acrylic acid or methacrylic acid, for example ethyl acrylate. Ethy'mcthacrylai. Butyl acrylate. Butyl methacrylate. Octyl acrylate. 2-ethylhexyl acrylate and the like alcohols with a higher carbon number, for example f> o with 9 to 15 carbon atoms, can also be used for Production of such acrylates and methacrylates can be used. Vinyl hydrocarbon monomers, for example styrene and alkylated styrenes such as yimlloluene. n-Methylsl \ rol and the like can be used individually << 5 or in combination with acrylates and / or methacrylates \ required. Furthermore, in combination with Acr.laten and / or methacrylate !!

and or vinyl hydrocarbon monomers, minor amounts of other vinyl monomers. for example Nitriles, e.g. B. acrylonitrile. Acrylamide. N-methylol acrylamide. Vinyl halides !!, for example vinyl chloride, or vinyl carboxylates. for example vinyl acetate, is used.

The film-forming material should have a sufficiently low Auflragungsviskosilät to a rapid application to allow to the substrate in substantially uniform depth, and a sufficiently high viscosity supply Auftn ^1.-. so that a film of at least 25 μ depth is kept on the vertical surface without the formation of drops. The coating films are usually applied at an average depth of about 2.5 to 100% with suitable adjustment of the viscosity and the method of application. The viscosity of the siloxane constituent can of course be varied through the choice of the siloxane and the hydroxyl ester used to produce the olefinically unsaturated siloxane constituent of the binder solution. In the same way, through the choice of the diisocyanate and the esters reacted with it, the viscosity of the diurethane and thus the binder solution and, in the same way, through the choice of the epoxy resin, its viscosity and thus also the binder solution, can be varied and adjusted. The type and amount of the vinyl monomers used in the binder solution in a preferred embodiment can also be selected so that the viscosity of the binder solution forms a suitable consistency for application by customary paint application methods, for example spraying. Rollers. Overlay and the like, can be adjusted. In the case of further application possibilities, the use of olefinically unsaturated resins in the binder, for example of polyesters such as vinyl resins, has an effect. Epoxy resins and the like, the viscosity of the binder. It is also within the scope of the invention to reduce the viscosity of the polymerizable binder by volatile solvents, for example xylene. Toluene. Methyl ethyl ketone and the like, which can be driven off before curing.

The unsaturated product of siloxane and in '(., / - position olefinically unsaturated ester and the unsaturated product from diisocyanate and in α., .'- Stüiung The olefinically unsaturated ester or the olefinically unsaturated epoxide are both homopolymerizable as well as with each other, with vinyl monomers and with unsaturated organic resins ^ polymerizable. In a first version they are one polymerizable components of the binder, the product of siloxane and unsaturated ester and the Product made from diisocyanate and unsaturated ester. In this embodiment, the binder contains, exclusively of solvents, about 20 to about preferably about 30 to about 70 parts by weight of the Product of siloxane and unsaturated ester and correspondingly from about 80 to about 20, preferably about 70 to about 30 parts by weight of the diisocyanate-unsaturated ester product.

In a second embodiment, the binder contains solvent as polymerizable components yinyl monomers additionally zr. the polymerizable components the first embodiment. In this embodiment, the binder solution contains about up to about 2 (M). preferably about 20 to about 50 percent of vinyl monomers. about 20 to about SE. preferably about 30 to about 70 weight parts

Product of siloxane and unsaturated ester and about 20 to about 80, preferably about 30 to about 70 parts by weight of the product of diisocyanate and unsaturated ester.

In a third embodiment of the invention If the binder solution also contains an unsaturated organic resin as a polymerizable component to the olefinically unsaturated siloxane and the olefinically unsaturated diurethane and / or olefinically unsaturated epoxy. In this embodiment, the olefinically unsaturated resin consists essentially made of carbon. Hydrogen and oxygen and has an average molecular weight above about 500 and below about 25,000. The molecular weight preferably being in the range from about KX) O to about 15,000 lies. In this embodiment, the Binder about 20 to about 80, preferably about 30 to about 70 parts by weight of the olefinically unsaturated Resin, about 20 to about 80, preferably about 30 to about 70 parts by weight of the product of siloxane and unsaturated ester and about 20 to about 80, preferably about 30 to about 70 parts by weight of the product from diisocyanate and unsaturated ester or from the unsaturated epoxide.

In a fourth embodiment, the binder solution contains any four or five of the polymerizable ingredients listed above. At this Embodiment, the binder solution contains about 10 to about 300, preferably about 20 to about 200 parts by weight of vinyl monomers. about 20 to about 80, preferably about 30 to about 70 percentages or the olefinically unsaturated organic resins, from about 20 to about 80, preferably from about 30 to about 70 parts by weight of the product of siloxane and unsaturated ester and about 20 to about 80. preferably about 30 to about 70 parts by weight of the product of diisocyanate and unsaturated ester and or of the unsaturated epoxy. Smaller amounts of other polymerizable monomers, for example Allyl compounds. can be used and make up the rest.

Furthermore, it is within the scope of the invention to use a binder solution in which the unsaturated Epoxy resin and the product of siloxane and unsaturated ester are the only polymerizable ingredients and this coating material is in solution, optionally together with a volatile solvent, for example those mentioned above, which can be evaporated before curing, is present.

If the binder is essentially based on the olefinically unsaturated epoxy resin and the olefinically unsaturated one Polysiloxane consists, the binder preferably contains about 20 to about 80, advantageously about 30 to about 70 parts by weight of the epoxy resin and correspondingly about 80 to about 20, advantageously c about 70 to about 30 parts by weight of the siloxane.

If the binder here contains substantial amounts of additional vinyl monomers, it contains Binder advantageously from about 10 to about 200, preferably from about 20 to about 100 parts by weight of vinyl monomers and the resinous ingredient which is about 20 to 80, preferably about 30 to 70 parts by weight of the unsaturated siloxane and about 20 to about 80, preferably about 30 to about 70 parts by weight of the Epoxy resin. Smaller proportions of other polymerizable monomers, for example allyl compounds. can optionally be used and make up the remainder.

In particular, however, the invention is concerned with those coatings in which the film-forming solution, apart from the vinyl monomers. essentially from the olefinically unsaturated diurethane and / or olefinically unsaturated epoxy resin as a binder resin and the product of siloxane and unsaturated Consist of esters, d. H. Coating compositions in which these ingredients are at least 85 percent by weight make up the! transforming binder material.

ίο Possess the paints obtainable according to the invention such weather resistance and resistance to abrasion. that they are even suitable for outdoor, hard-wheeled floors or even Let roller skating rinks and the like be used excellently.

The term "ionizing radiation" here means radiation of sufficient energy to generate the Effecting polymerization of the paint films described herein; d. H. an energy equivalent to about 5 (KX) eV or greater. The preferred method of curing films from the present coating compositions on substrates to which they have been applied consists in the fact that these films form a beam of polymerization causing electrons with an average energy in the range of about KX) OOO to about 500 00OeV. When using such a jet it is preferred a minimum of 25,000 eV per 2.5 cm distance between the radiation emitting source and the workpiece to be used if the space is filled with air. A setting can be made with regard to the relative resistance of the intermediate gas can be made, which is preferably from a oxygen-free inert gas such as nitrogen or helium.

consists. An electron beam is preferably used as ionizing radiation, which at the source a average enercie in the range of about 150,000 to about 500 0 (X) eV.

The films formed from the paints according to the invention are advantageous at relatively low levels Temperatures, for example between room temperature (20 to 25 C) and the temperature at which significant evaporation of the most volatile components begins, usually between 20 and 70 ° C networked and hardened. The radiation energy is in. Dosage amounts from about 0.1 to about 100 Mrad applied per second to a preferably moving workpiece, with the coating providing an overall dosage in the range of about 0.5 to about 100. common absorbs between about 1 and about 25, and most preferably between about 5 and about 15 Mrad. The electron beam makes the films tough, wear-resistant and weather-resistant coatings transferred.

The abbreviation »Mrad« here means 1 000 (HK) Rad. The term "Rad" here denotes such a radiation dose that the absorption of 100 Erg Energy per gram of absorbent, for example Coating film, results. The electron emission cleansing can consist of a linear electron accelerator that is used to supply a direct current potential is suitable in the range listed above. exist. In such a device, the Electrons are usually emitted from a hot wire and accelerated by a uniform voltage gradient. The electron beam that can have a diameter of about 3.2 mm at this point, is then pulled so that a funnel-

shaped beam, and then through a metal window, for example from a magnesium-thorium alloy. Aluminum, an alloy made from aluminum and a minor amount of copper and the like about 0.0075 cm thick on the coating.

The following examples serve to further illustrate the invention.

example 1

A radiation curable paint was made up of the following ingredients Way made:

a) Production of the unsaturated siloxane component

Action steps

Gcwichlslcilc

Rcaklionstcilnchmcr

2-hydroxyethyl methacrylate. . .

Toluylene diisocyanate monomer mixture) ')

(icwichlslcilc 08/44 27.00

') X (I "; 2.4-Toluene-diisocyanate.
20 "ι. I.fi-Toluene diisocyanal.

The diisocyanate was added dropwise to the methacrylate with stirring under a nitrogen gas atmosphere zugcsetzi, the rate of addition being regulated so that the exothermic the value of 32 C was not exceeded. Stirring was continued for one hour after the addition was complete continued and then the mixture was left to stand at room temperature for 16 hours.

c) Preparation of the paint binder solution

('Opolymcrisicrhare components

Unsaturated siloxane ester product cl

according to a)

Unsaturated diurethane according to b) ....

«!

25th
75

Acyclic siloxane with functional

Methoxy groups ¹ ) 178

Hydroxyethyl methacrylate 118

Tetraisopropyl titanate 0.32

Hydroquinone 0.06

') Commercially available methoxylic partial hydrolyzate of monophenyl and phenylmethylsilanes (largely condensed dimethyltriphenyltrimcthoxytrisiloxane) with the following properties:

Average molecular weight 751) «50

Average; Number of silicon atoms each

Molecule. 5 fi

Average number of Mcthoxv groups ie

Molecule ". 3 4

The siloxane, the methacrylate monomer and hydroquinone as a polymerization inhibitor were added 100 C in a Kolbei equipped with a barrel-type distillation receiver. heated. The titanate was added as a catalyst and the temperature increased to 150 "C over 3 hours, during this period the methanol was removed by distillation. The cooled reaction product had a viscosity of 0.6 Stoke at 25 C.

b) Production of the unsaturated diurethane

The polymerizable reactants were in solution with xylene on a metal base to form a average depth of about 25 μ applied. The xylene was evaporated and the coating on the The surface of the substrate is crosslinked by exposing the coating to an electron beam. The irradiation conditions were the following:

Electron beam potential 295 kV

Electron beam current strength 25 mA

Dosage 15 M rad

Atmosphere nitrogen

Excellent coated panels were obtained.

Example 2

The procedure of Example I was repeated, but 75 parts by weight of the unsaturated siloxane ester product and 25 parts by weight of the unsaturated diurethane is used.

Example 3

The procedure according to Example 1 was repeated, but 50 parts by weight of the unsaturated siloxane ester product. 25 parts by weight of the unsaturated Diurethane and 50 parts by weight of an equimolar mixture of styrene and methyl methacrylate are used, with the xylene omitted. The film was made on metal sheets. Wood and synthetic polymers applied, for example

SECTION. an acrylonitrile-butadiene-styrene copolymer. The movie was taken to an average depth of applied about 30 μ and by exposure to an electron beam using the conditions cured according to Example 1, the irradiation being continued until a non-tacky film was formed.

Example 4

The procedure of Example 1 was repeated, but 25 parts by weight of the unsaturated siloxane

ester product. 50 parts by weight of the unsaturated diurethane and 50 parts by weight of a vinyl monomer mixture from u-methylstyrene. Ethyl acrylate and butyl methacrylate used, the xylene being omitted. The film was made on documents

Metal. Wood and synthetic polymers, for example SECTION. an acrylonitrile-butadiene-styrene copolymer. applied. The film turned out to be a through average depth of about 30 μ applied unc by exposure to an electron beam untci Applying the conditions of Example 1 ge cured, the irradiation was continued, bii a non-tacky film was formed

Example 5

The procedure according to Example 1 was repeated, however, 50 parts by weight of the unsaturated siloxane ester-based products. 50 parts by weight of the unsaturated Di urethane and 50 weight with Mlr · rinrs vinyl monomer

Mixture of methyl methacrylate. Bulyl acrylate and 2-ethylhexyl acrylal were used, the xylene being omitted became. The film was made into one on the same bases as in the previous example average depth of about 20; x plotted and by exposure to an electron beam cured using the conditions of Example 1 with irradiation continued until a non-tacky film was formed.

The products of Examples 2 to 5 performed extremely well excessive documents.

Example 6

The procedure of Example I was repeated but with 50 parts by weight of the unsaturated siloxane ester product. 50 parts by weight of the unsaturated diurethane. 50 parts by weight of methyl methacrylate and 50 parts by weight of an in ./.,-'- position olefinically unsaturated Polyester resin used, the xylene being omitted. The film-forming solution was applied to the substrates listed above to an average depth of about 38; x and then by exposing the film to an electron beam using the conditions crosslinked according to Example 1, the irradiation being continued until a non-tacky film was formed.

The resin which is olefinically unsaturated in the. ^. 'Position. used here has been hcme.;: e! lt:

AusLMniismatenaliun (icwichlslcilc M alein sau rea η Ii vd rid 147 Phthalic anhydride 429 Neopentyl glycol 503

All reaction eggs were placed in a four-necked flask. the one with a stirrer. Thermometer. Nitrogen inlet tube and a 25 cm high Vigrcux column with a Barrctt trap to remove the Was equipped with condensation water. brought in. The reactants were slowly heated to 15C heated where the distillation of the condensation water began. Nitrogen was passed through the reaction mixture blown during implementation. The reaction temperature rose as that Water was continuously removed until a maximum temperature of 225 C "was reached. The column was then removed from the system. 3 percent by weight xylene for azeotropic water removal added and heating continued until the acid number reached 30. The product was on KX) C cooled and 0.03 percent by weight hydroquinone added as an inhibitor and the polymer up a content of 80% non-liquid components diluted with styrene.

Excellent coated documents were obtained.

Bc

s ρ ι c

The procedure according to example ft was repeated, but as a resin which is olefinically unsaturated in the "//" position a copolymer of vinyl monomers is used. That Resin was made in the following way:

Xylene

Methyl methacrylate ..

Ethyl acrylate

Glycidyl methacrylate.

Azobisisobutyronitrile

Hydroquinone

Methacrylic acid

Thiethylamine

Ucwichistcilc
WK)

196

333

71

0.12
42
0.96

The solvent used for the reaction, xylene, was added to a flask fitted with a stir bar. Addition funnel. Thermometer. Nitrogen inlet tube and condenser was installed. The amount of xyloI was equal to the total weight of the vinyl monomers to be added. The xylene refluxed heated. Nitrogen bubbled through the solution during the heat up and reaction. the mixed monomers and the initiator (azobisisobutyronitrile) were refluxed to the one Solution added evenly over a period of 2 hours. The initiator weight was 10 parts by weight on KXX) parts by weight of the vinyl monomers. The reaction solution was refluxed until conversion of the monomers in the polymer was greater than 97% (8 to 16 hours).

In a second stage, the hydroquinone was added as an inhibitor and then methacrylic acid was added, which reacted with the remaining epoxy groups of the polymer. Triethylamine was used as the catalyst used. This esterification reaction was carried out at reflux temperature until one 80% esterification was achieved. determined by the remaining acid number. The xylene was then through Vacuum distillation removed and the polymer dissolved in methyl methacrylate so that the weight ratio polymer to solvent was two.

Example 8

The procedure of Example 6 was repeated, but as in << .//- position olefinically unsaturated resin

ί; ο used an epoxy resin made in the following way became:

In a three-necked flask of 2 (X) 0 ml. The one with stirrer, dropping funnel, thermometer and nitrogen inlet was equipped. I mole of 2,3-butanediol (91.12 parts by weight) and 4 moles of epichlorohydrin (370 parts by weight) introduced. The temperature was kept at 110 ° C while adding 2 moles of sodium hydroxide (80 parts by weight) was added dropwise as a 30% aqueous solution. The rate of addition was regulated so that the reaction mixture remained neutral. After about 3 hours it was the organic layer separated, dried, distilled and recovered the polymer. 86 parts by weight of methacrylic acid were added to 210 g of these polymers.

theO. 1 parts by weight of hydroquinone was added. The mixture was heated to 140 ° C. for 20 minutes while stirring under a nitrogen atmosphere then to room temperature, d. H. 26 C cooled.

Example 9

The procedure of Example 8 was repeated, but using an epoxy resin, which by reaction an epichlorohydrin bisphenol epoxide> made with acrylic acid.

The products of Examples 7 to 9 were also excellent coatings on.

B e i s ρ i e 1! 0

The procedures of the preceding examples were repeated, but as the polysiloxane to prepare the unsaturated siloxane ester reaction product is a methoxylated partial hydrolyzate of monophenyl and Phenylmethylsilanes used that essentially consisted of Dimethyltriphenyltrimethoxytrisilüxan and had the following typical properties:

Average molecular weight! ... 470

Connection weight 155 _

Specific gravity at 25 C 1-105

Viscosity at 25 C. Centistokes ... 13

Example Il

The procedures of Examples I to 10 were repeated, however, an olefinically unsaturated siloxane was used, which consists of the following components in the was produced in the following manner:

Reuklionsieilnch.nier

Cydic siloxane with functional components

Hydroxyl groups ¹ )

Hydroxyethyl methacrylate

I I vdroquinone

Xylene (solvent)

Parts by weight

200
71
0.1
116

1 Commercially available polysiloxane with functional Ihdrowlgmppen and the following typical properties:

Ihdrowkehall. Dean Stark

Prevent condensable 5.5

Percent free 0.5

Average molecular weight IWX)

Connection weight 4 (X)

Refraction index 1,531 1,539

Softening point. Mercury method

Durran. (. 'y.1

At W) "ο l-estsloff in X;, lol

Spinal weight at 25 ° C 1,075

Viscosity at 25 C. Cenlipoiscs 33

Gardner H ο I dt Λ-1

A three-necked flask. the one with stirrer, thermometer. Equipped with nitrogen inlet and Barrett's trap was. was using the siloxane. the methacrylate. charged to the xylene and the hydroquinone. These Solution became reflux. 138 C. for 30 minutes heated. Nitrogen was bubbled through the reaction mixture throughout the procedure. The by-produced water was slowly removed and the temperature gradually rose 146 C. After 5 hours, 8.5 ml of water were collected, which indicates an almost complete implementation. The xylene was taken by distillation removed under reduced pressure and the product then to a content of 70 "" non-volatile substances with Meth \ Imethacr \ lat is thinned.

Example 12

The procedures of Examples 1 to 11 were repeated, however, in the production of the olefinically unsaturated one Siloxane is such an amount of the monohydroxy ester used to react with at least one functional hydroxyl or hydrocarbonoxy group of the siloxane was sufficient, however, to react with all such functional ones Groups of the siloxane molecules in the reaction ^. uemisch was not sufficient.

Example 13

The procedures of Examples 1 to 11 were repeated, but in the preparation of the olefinically unsaturated siloxane an amount of the ylonohydroxy ester used in excess of the amount required for reaction with all the functional hydroxyl and hydrocarbonoxy groups of the SiI oxane molecule in the reaction mixture.

Example 14

The procedures of Examples 1 to 11 were repeated, however, the hardening is carried out with a beam potential of 175,000 volts, with the workpiece 7.5 cm from the emitting point. and runs through 400,000VoIt at a distance of 25 cm. each working in a nitrogen atmosphere containing a small amount of carbon dioxide contained.

The products of Examples 10 to 14 also had excellent coatings on.

Example 15

A paint that is an unsaturated siloxane ester product Containing unsaturated epoxy resin and vinyl monomers, m manufactured in the manner listed below:

a) Manufacture of the siloxane component

Respondents

Acyclic siloxane with functional
Methoxy groups ¹ )

Hydroxyethyl methacrylate

Tetraisopropyl titanate

Hydroquinone

Ί See example 1.

(! i: \ Mchlsieile

17X

HS
0.32
0.06

The siloxane. the methaerylate monomer and hydroquinone as a polymerization inhibitor were added 100 C in one with a Distillalionsaufnahmegenit Barrett-type equipped flask heated. The titanal was added as a catalyst and the temperature increased to 150 ° C. for 3 hours, during which time the methanol was removed by distillation has been removed. The cooled reaction product had a viscosity of 0.6 Stoke 25 C.

bj production of the olefinically unsaturated
Epoxy resin

An epoxy polymer was prepared in the following manner: In a three-necked flask of 2000 ml

19 20

with stirrer, dropping funnel, thermometer and stick. The rate of addition was so slowed down was designed, 1 mol of 2,3-butane was provided so that the reaction mixture remained neutral. To diol (91.12 g) and 4 moles of epichlorohydrin (370.0 g) for about 3 hours, the organic layer was removed. The temperature was kept at 10 ° C., separated, dried, distilled and the polymer allowed 2 moles of sodium hydroxide (80 g) were obtained dropwise 5. This polymeric product is made by folin In the form of a 3 ()% aqueous solution, the structural formula is shown:

H-C

H H

H CH, H OH H

! I "!! I - o - c - c - o - c - c - ο

H ₃ CH

HHH H CH ₃ W
Ο — C — C — O — C — C

H ₃ CH HH

CH
H

86 g of methacrylic acid containing 0.1 g of hydroquinone were added to 210 g of this polymer. Under With stirring in a nitrogen atmosphere, the mixture was heated to 140 ° C. for 20 minutes and then up Room temperature, d. H. 26 C, cooled. The obtained unsaturated polyepoxide polymer is represented by the following Structural formula reproduced:

H CH, H OH H

H ₃ CH

H OH H

! I.

H — C — C — C

ι
OHH

C = O
C-CH ₃

Ii

CH ₂

Two coatings were made and as films of about 50 microns thick from metal plates of about 7.5 χ 12.5 cm of phosphatized sheet steel applied and then in Hardened nitrogen atmosphere.

c) Preparation of the paint

Ingredients Gcwichlstcile

H ₁ CH

H OH H

O — C — C — O — C — C — C O — C — C — O — C — C — C — H

HHH., H CH ₃ HO

C = O

C-CH ₃
CH ₁

Siloxane ester product according to a)
Formula 2 epoxy resin ....
Methyl methyl acrylate

H)

15th

Example 17

The procedure of Example 15 was repeated, however, such an amount of the monohydroxy ester in the preparation of the olefinically unsaturated siloxane used in excess over the reaction with all functional hydroxyl and hydrocarbonoxy groups the required amount of siloxane molecules was present in the reaction mixture.

Also those obtained according to Examples 16 and 17 Products showed excellent coatings.

This paint was applied to a metal base to an average depth of about 25 microns and cured to a hard film using the following irradiation conditions:

Electron beam potential 270 kV

Electron beam current level .... 25 mA

Dosage 15 Mrad

Atmosphere nitrogen

Distance. Workpiece to emitting point 25 cm

The products had excellent coatings. Example 16

The procedure of Example 15 was repeated, however, such an amount of the monohydroxy ester in the preparation of the olefinically unsaturated siloxane used to react with at least one functional hydroxyl or hydrocarbon oxy group of the siloxane was sufficient, however, to react with all such functional groups of the Siloxane molecules in the reaction mixture were insufficient.

Example 18

A pigmented paint was prepared by adding 75 parts by weight of the unsaturated siloxane ester product according to Example 15 with 150 parts by weight of a commercially available titanium dioxide pigment and 20 parts by weight Methyl methacrylate were premixed.

The mixture was shaken with a like Amount of glass beads ground in a standard paint shaker for 30 minutes. The premix was with a further 75 parts by weight of the unsaturated Siloxane ester product diluted and 65 parts by weight of the mixture obtained were with 35 parts by weight of an equimolar mixture of styrene and methyl methacrylate diluted. This mixture became 35 parts by weight of methyl methacrylate and 65 parts by weight of the olefinically unsaturated one Epoxy ester according to Example 15 was added.

The paint was on metal substrates. Wood and polymers (ABS. I.e. acrylonitrile-butadiene-styrene copolymers) applied to an average depth of about 3H μ and then with an electron (ion beam cured according to the procedures of the preceding examples.

Products with excellent coatings were obtained.

Claims (4)

"aienianspriiche: 1. Coating binder curable by ionizing radiation based on siloxane in combination with unsaturated polymers or resins and optionally unsaturated monomers, d a characterized in that it consists of a mixture of IO Uj 20 to 80 parts by weight of an olefinically unsaturated one Siloxane. which by reacting a siloxane with 3 to 18 silicon atoms and at least two functional Groups, namely hydroxyl groups and / or hydrocarbyl oxy groups with one Hydroxyester one in «., / - position olefinic unsaturated carboxylic acid has been obtained, and b) 80 to 20 parts by weight of an olefinically unsaturated one Epoxy resin and / or an olefinically unsaturated diurethane. that through Implementation of a diisocyanate with a hydroxy ester which is olefinically unsaturated in the “// position Carboxylic acid has been obtained. consists and possibly another 10 to 200 parts by weight of vinyl monomers. 2. Paint binder curable by ionizing radiation according to claim 1, characterized in that the olefinically unsaturated epoxy resin about 0.5 to about 5, preferably 1 to 3.5 units with olefinic «. / - unsaturation Has 1000 units of molecular weight. 3. Coating binder curable by ionizing radiation according to claim 1, characterized in that that the olefinically unsaturated diurethane by reacting a molar proportion of diisocyanate with two molar proportions of a monohydroxy ester the acrylic acid or methacrylic acid has been obtained. 4. Use of the paint binder according to claim 1 to 3 in a coating process under Application of an electron beam with an average energy of 100,000 to 500,000 eV. Coating compounds hardened with catalysts. on based on acyclic suloxanes or cyclic siloxanes.! in connection with unsaturated P »-> esters On ebaulc paint binders mixed with monomers are also known that from lom-merende Radiation curable. Masses for the formation of form deposits from aliphatically unsaturated Mushroom resins and acryloxysiloxane are the same Sans. The invention, however, is concerned with mn Paints, d. H. Binder solutions, which also interhear m in the form of a liquid film and applied to it by ionizing radiation, in particular with electron beams, be crosslinked and hardened. In contrast to the coating compounds discussed above the crosslinked coating shows both high resistance to abrasion and at the same time resistance to the influences