DE1957358B2 - Radiation hardenable vinylic/siloxane resin binder for - paints - Google Patents

Abstract

UNSATURATED SILOXANE & VINYLIC COPOLYMER AS COATINGS HARDENABLE BY RADIATION. M1-. (a) Olefinically alpha, beta unsaturated siloxane formed from a siloxane containing at least 2 functional groups, chosen from -OH or hydrocarbonoxy groups reacted with a hydroxy-ester of an olefinically alpha, beta unsaturated carboxylic acid, and (b) a copolymer of olefinically alpha, beta unsaturated vinylic monomers are used as coating compositions hardenable by radiation. Vinylic monomers may be added to the composition. Coating with good weather resistance for wood, metal or solid polymers. The siloxane may have 3 to 18, preferably 3 to 12 Si atoms, and contains the links -Si-O-Si or -C-O-Si-. The hydrocarbonoxy groups are preferably alkoxy gps. with 1 to 4C atoms particularly -OCH3. The hydroxy ester is preferably an ester of acrylic or methacrylic acid and a dihydric alcohol of 2 to 8C atoms.

Description

55

60

The invention is concerned with ionizing radiation curable film forming paint binders based on unsaturated Siioxanes mixed with unsaturated polymers or polycondensates, which can be hardened in situ by ionizing radiation and excellent coatings on substrates result.

Such documents come everyday objects with outer surfaces made of wood; Metal or polymeric solids into consideration, ie by the polymerization product formed in situ the paint binder has a high resistance to weathering and wear; obtain.

Polymerization products made from monosilane with unsaturated polyesters, which are generally cured with peroxides as catalysts, are already known as materials for counter-molding, such as glass fiber layers or glass slabs. These monosilane polyester copolymers zei gen for use unzurei-reaching weathering resistance and a door outside the general use inadequate Abnützungs resistance if they exceed also an excellent Haf indicate Gfasmateriaiien and For the Herste} development of Glasfaserschichigebilden awarded ge acquired his love . With peroxides as catalysts, reaction products of siloxanes with acrylates or methacrylates with acid amides of unsaturated carboxylic acids are polymerized. On the one hand, catalysts and relatively high temperatures and long periods of time are required for this reaction, and on the other hand, the products obtained yellow, discolor or decompose, especially in the open air, when exposed to air and / or sunlight, they show inadequate weathering resistance.

The one from French patents 1505 416 15 20 402 known paint binders based on siioxanes with unsaturated monomers to be cured quickly and at normal temperature by ionizing radiation and also result in coatings of generally sufficient properties with regard to wear resistance only and weather resistance are not yet fully satisfactory.

Paint binders have now been found which, in combination, contain certain olefinically unsaturated siloxanes together with one in (/, // position olefinic unsaturated polyester and / or together with one terminally olefinically unsaturated in the side chain, Binder resin composed of vinyl monomers, so-called vinyl resin, for example from Monon sren of the acrylic type, and which in situ by ionizing radiation rapidly and at normal temperature are to be hardened.

This is the easiest way to incorporate both siloxanes into paint films and resistance to weathering of the coatings in the open air. This approach is because it is simpler and more flexible insofar as you can use any desired amount of the siloxane, since the two basic materials, optionally with the addition of vinyl monomers, by ionizing radiation, in particular electron beams. can be networked. A chemical combination of the siloxane with the acrylic resin or the polyester before curing is far more complicated and in terms of variability the concentrations are severely limited. According to the invention, excellent wear-resistant results and radiation cured weather resistant coatings such as those discussed above Defects such as yellowing or discoloration in the air and / or in sunlight, sierinue wit-

resistance to wear and tear, long-term heating during hardening and the like are avoided.

The subject of the invention is thus a paint binder curable by ionizing radiation on the Based on unsaturated siloxanes in a mixture with unsaturated polymers, which consists of a film-forming Solution

a) an olefinically unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups and with 3 to 18, especially 3 to 12 silicon atoms per molecule with a hydroxy ester of a carboxylic acid which is olefinically unsaturated in the u, / i position has been received, and out

b) a polyester which is olefinically unsaturated in the α, / tf position and has a molecular weight of 500 to 20,000 and / or a copolymer of vinyl monomers which is terminally olefinically unsaturated in the side chain and has a molecular weight of 1,000 to 50,000, each about 0.5 to 5, in particular have 0.5 to 3.5 units of olefinic unsaturation per 1000 units of the molecular weight,

consists.

The use of these paint binders in a coating process is particularly preferred Use of electron beams with an average energy of 100,000 to 500,000 OeV.

The term "paint" or "paint" used here includes both materials and pigments and / or contain finely ground fillers, the binder without pigment and / or filler or only with a very low content thereof, which material can be colored if desired. Thus, the Binder, which is finally converted into a permanent, weather-resistant film, consist of all or virtually all of the material used to form the film or it can act as a carrier for pigments and / or particulate filler material to serve.

The siloxanes used in the manufacture of the binder have reactive hydroxyl or hydrocarbonoxy groups, which are bonded to at least two of their silicon atoms. The term "siloxane" denotes compounds that form a bond

- Si - O - Si -

- C - O - Si -

contain, the remaining valences by a hydrocarbon radical, a hydrocarbonoxy group. Hydrogen, a hydroxyl group or an oxygen atom connecting the silicon atoms and yields such a valence with a further silicon alom, are satisfied.

Preferably the film-forming solution contains from about 20 to about 80, preferably from about 30 to about 70 parts by weight of the olefinically unsaturated siloxane and about 80 to about 20, preferably about 70 to about 30 parts by weight of that which is olefinically unsaturated in the α, / i-position Polyester or the terminally olefinically unsaturated copolymer in the side chain Vinyl monomers.

In a preferred embodiment, the film-forming solution additionally contains about 10 to about 200 parts by weight of vinyl monomers. In a further embodiment, the film-forming solution contains additionally a particulate pigment.

The acyclic siloxane molecules used to make the paint binder resins according to the invention are used contain 3 to 18 silicon atoms per molecule with the corresponding oxygen bonds. The preferred siloxanes are represented by the following general formula:

X

X - Si - O -
X

Si-O
X

-Si-X

. χ

where η is a number of at least 1 and 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 radical having 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms or (c) a hydroxyl group or (d) a hydrogen atom, where at least two of the groupings X are defined by a bond

X - Si - O - Si - X

are separated, consist of either a group (b) or (c).
The cyclic siloxanes which can be used to prepare the paint binder resins according to the invention contain at least 3, preferably 6 to 12, and not more than 18 silicon atoms with the corresponding oxygen compounds. The cyclic polysiloxanes used can be in the form of compounds according to the following formulas:

I. X ", Si" O "", where η is an odd positive number of at least 3, n ' the value of 2h and n " the value of n, 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 hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms, or (c) a hydroxyl group or (d) a hydrogen atom, in which at least two of the groups X that through a bond

X-Si-O-Si-X

are running, either the meaning (b 'or (c)

have, for which have the following formula as an example, for which the following structure is given as an example is: formula is given:

Si

/ \
XOOX

X-Si O Si-X

II. X ", Si" O ",,, where η is an odd positive number of at least 5, n ' the value η + 3 and n" the value 6, 6 + 3 or 6 + 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 hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms, or (c) a hydroxyl group or ( d) denote a hydrogen atom, where at least two of the groups X. by a bond

I I

X - Si - O - Si - X

are separated, have either the meaning (b) or (c), of which the following structural formula as an example is given:

X X

Si-O-Si

X O

\ /
Si O

/ \
XO

O X

O Si

/ \
OX

Si-O-Si

Χ — Γι — O — Si

X-Si-O-Si

III. X ", Si" O _n ", where η is the number 6 or a multiple of 6,"'the numbers 8,8 + 6 or 8 + a multiple of 6, n " the numbers 8,8 + 9 or 8 + Multiples of 9, 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 hydrocarbonoxy radical having 1 to 8 carbon atoms, preferably an alkoxy radical having 1 to 4 carbon atoms, or ( c) a hydroxyl group or (d) a hydrogen atom, in which at least two of the groups X. through a bond

X - Si - O - Si - X

or dimers, trimers and the like formed therefrom by condensation with loss of water or alcohol.

IV. X ", Si" O "", where η is an even positive

Number of at least 4, η the value of η + 4 and n " the value 4, 4 + 3 or 4 + a multiple of 3, X either (a) a monovalent hydrocarbon radical with 1 to 8 carbon atoms, preferably an alkyl radical with I to 4 carbon atoms, or

(b) a monovalent hydrocarbonoxy radical having 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms, or (c) a hydroxyl group or (d) a hydrogen atom, wherein at least two of the groups X, which are represented by a bond

I I

X - Si - O - Si - X

are separated, have either the meaning (b) or (c), of which the following structural formula as an example is given:

X-Si-

I. ο

X-Si-X

X \

-O — Si

I. ο

O-Si-X

-O-Si-X

I. ο

-O-Si-X

I.
χ

wherein m is the number 0 or a positive integer;

V. X _n , Si _n O _n ,,, where n is an even positive number of at least 8, n ' the value 11 + 2 and n " the value 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 hydrocarbonoxy radical with 1 to 8 carbon atoms, preferably an alkoxy radical with 1 to 4 carbon atoms, or (c) a hydroxyl group or ( d) denote a hydrogen atom, where at least two of the groups X. by a bond

I I

X-Si-C-Si-X

are separated, either the meaning (b) or (c) are separated, either the Bedeiilnno (hl nrW

have, for which the following structural formula is given as an example:

Si

Si—

C)

Si

O-Si
O

-O- Si

Si

O-Si O-Si

where m is a positive integer.

A variety of methods are known for the production of siloxanes. This includes the regulated Hydrolysis of silanes, the polymerisation of a SiI-oxane of lower molecular weight, the conversion of silicon tetrachloride with an alcohol, etc. The manufacture of siloxanes and their incorporation in organic resins is in U.S. Patents 3154 597, 30 74 904, 30 44 980, 30 44979, 30 15 637, 29 96 479, 29 73 287, 29 37 230 and 29 09 549.

To produce the unsaturated siloxane, preference is given to siloxanes with and / or hydroxyl groups Alkoxy groups with 1 to 4 carbon atoms, in particular Methoxygrupperuals starting material used.

The ester containing hydroxyl groups is preferably composed of a monohydroxyalkyl ester of an in «.// position of olefinically unsaturated monocarboxylic acid. The preferred hydroxy esters are the acrylates and methacrylates because they have olefinic unsaturation between the terminal carbon atoms and at relatively low dosages are easily polymerizable by ionizing radiation. The following is a list as an example such acrylates or methacrylates given:

2-hydroxyethyl acrylate or methacrylate,
2-hydroxypropyl acrylate or methacrylate.
2-hydroxybutyl acrylate or methacrylate.
2-hydroxyoctyl acrylate or methacrylate.
2-hydroxydodecanyl acrylate or methacrylate.
2-hydroxy-3-chloropropyl acrylate or

-methacrylate,
2-hydroxy-3-acryloxypropyl acrylate or

-methacrylate,
2-hydroxy-3-methacryloxypropyl acrylate or

methacrylate.
2-hydroxy-3-allyloxypropyl acrylate or

methacrylate.
2-hydroxy-3-cinnamylpropyl acrylate or

-methacrylate,
2-hydroxy-3-phenoxypropyl acrylate or

-methacrylate,
2-hydroxy-3- (o-chlorophenoxy) propyl acrylate

or methacrylate,
2-hydroxy-3- (p-chlorophenoxy> -propyl acrylate

or methacrylate,
2-hydroxy-3- <2,4-dichlorophenoxy> -propyl-

acrylate or methacrylate.

Hydroxy-3-acetoxypropyl acrylate or methacrylate,

Hydroxy-3-propionoxypropyl acrylate or -methacrylate,

Hydroxy-3-chloroacetoxypropyl acrylate or -methacrylal,

Hydroxy-S-dichloroacetoxypropyl acrylate or -melhacryiat,

Hydroxy-3-trichloroacetoxypropyl acrylate or -methacrylate,

Hydroxy-3-benzoxypropyl acrylate or methacrylate,

Hydroxy-3- (o-chlorobenzoxy) propyl acrylal or methacrylate,

Hydroxy-3- (p-chlorobenzoxy) propyl acrylate or methacrylate,

Hydroxy-3- (2,4-dichlorobenzoxy) propyl acrylate or melacrylate,

Hydroxy-3- (3.4-dichlorobenzoxy) propyl acrylate or methacrylate,
Hydroxy-3- (2,4,6-trichlorophenoxy) propyl acrylate or methacrylate,
Hydroxy-3- (2,4,5-trichlorophenoxy) propyl acrylate or methacrylate,
Hydroxy-S-fo-chlorophenoxyacetoxyJ-propyl acrylate or methacrylate,
Hydroxy-3-phenoxyacetoxypropyl acrylate or methacrylate,

Hydroxy-S-ip-chlorophenoxyacetoxyJ-propyl acrylate or methacrylate,
Hydroxy-3- (2,4-dichlorophenoxyacetoxy) propyl acrylate or methacrylate, hydroxy-3- (2,4,5-trichlorophenoxyacetoxy) propyl acrylate or methacrylate. Hydroxy-3-crotonoxypropyl acrylate. or methacrylate,

Hydroxy-3-cinnamyloxypropyl acrylate or -methacrylate,

Acryloxy-2-hydroxypropyl acrylate or methacrylate.

■ Allyloxy-2-hydroxypropyl acrylate or methacrylate.

■ chlorine-2-hydroxypropyl acrylate or -methacrylate,

Crotonoxy-2-hydroxypropyl acrylate or methacrylate.

In addition to the acrylates and methacrylates, the cinnates can also: - nate. Crotonates and the like are used will.

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

H H

or

C = C-H

H ₁ CH
-C = CH

however, does not include allyl compounds. The preferred vinyl monomers are esters of monohydric Alcohols with 1 to 8 carbon atoms with acrylic acid or methacrylic acid, for example ethyl acrylate, Ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, 2-ethylhexyl acrylate and the like with alcohols

509 517/385

⁹ ίο

higher carbon number, for example 9 to 15 carbon glycol, 1,3 - butylene glycol "> - butene - I 4 diol Ä £ Vr ^e ^ f ^{The erfi} " ^d "" ^ inäß to be used in the side

53SH

g E: = S £ == S2 = s = E

The expression "copolymers from vinyl monomers"" ^S StZt ^ eT vlnT '^' ^ ΤΤ ^

Beze.chnets polymers here, in which the larger resin wa 0 S hlZ ^Vin y ^| monomers. ⁿ built

part (above 50 percent by weight) of the built-in e wa Vi Finhii. ' _r ^VOrz ^ ^{swelse about} . ' ^bls

Monomers of two or more vinyl monons e en u ( mm F ^ t "/" μ ° ™ ^m f ^cher unsaturation

consists. Smaller amounts of allyl alcohol ΑΠνϊ 1 '«» Incorporation of the molecular weight; you can-

glycidyl acrylates or methacrylates,! ode? Glyri! ί will "^ ^ '^ ^{V n} ° ^{methods hergeStelit}

Acrylates or methacrylates can, as from the Rpi p'inpr δ ,, ^ μ r

following example _p! elen can be seen, einpolymerisie mo ^ merenAA ^ i ^^ in ^ Vu ⁸ ^ ¹ "

be. monomeric built-up copolymers (binder resin)

The invention used in,. // - Stellunu 2, £ ^ ° P "JJ '| nensation product of a smaller an

olefinically unsaturated polyester (binder resin) Ie 'η A .pü ^{G |} y ^cid y ^{| melh} acrylate and a larger one

Molecular Weight i Bh tt ^ lTf '™ * ^Vi "y' ^monomers " ^the

Qualified polyester (binder resin) Ieη A .pü g

Molecular weight in the range of about 0) b lTf'r ™ * ^Vi "y ' ^monomers " · ^die

20,000, preferably in the range from about 2000 to 2 L , p ^ ^G J, ^UPP " ^V °" ^Styro1 ' ^{esters of the}

about 10,000, and contains about 0.5 to about 5 weh Ip, η α i "of ^{the Metl} ™ acrylic acid, added about 1 to about 3.5 units mi, olefiniX ₃₀ c _vl iurT'l," ί ^ " ^acr y ' ^{acid or meth} "

«, // - Unsaturation to 1000 units of the molecular serstorTc Hp ^ i ^wlrc \ ^Other vinyl hydrocarbons

weight. Among the unmodified polyesters - u ^ ΐ ^ 'οηΖ-ΓηΤιΓ * W ^ · vinyltoluene

resins ie, those consisting essentially of carbon The An ^, ϊ ° ^{"Styro1 one be eselzt} g ·

material. Hydrogen and oxygen consist of ν on A ^ f - ^ ¹⁵⁰ ^ ^{6 ka} "" ^{also smaller amounts} the preferred resins from a polyvalent alkene 35 ^ ₁ J ^ ^U " ^{d / or} _A ^er methacrylic acid contain,

hol, one in "/," - position olefinically unSuiten Vinvlmö ^zwellen _f ^A " ^s educational form that becomes out

Dicarboxylic acid and a second polyvalent Ca "se 7 oZ ° ⁿ ° ^{meren on} built binder resin by conversion

Bonsic acid formed. The expression "olefin" Ϊρ η ^g , " ^{eS and} sesaltierten glycidyl ethers with two

-W -'- Unsaturation "here includes the strahlunusemn πΓ, ^ 1 ° ^hiedlichen vinyl monomers and

-sensitive olefinic Nichlsättioun "the" Sh Tnf ^ f i ^{of the initially} "suspended polymer with an all-vl due to the incorporation of maleic acid or ANSE '° Ä ^" _A ?;

Renal acids with corresponding unsaturation in the Vinvlm!

Polyester for the purpose of polymerization by Rp ^{V n} y ^{| mon} ° ™ ren built-up binder resin by re-

radiation results. ymensation by occupying an allyl alcohol with two or more different

The preferred dicarboxylic acid for the formation of the 4, eihähenpn ^ P ^ " ³ ' ¹ " ¹⁰ " ⁰¹¹¹ ^ ^{11 and implementation of the}

JJL, IT ^Pol > mer with an allyl glycidyl ether commits the desired olefinic light saturation

from maleic acid, which is preferably in "its · =" η Γι · λ

Anhydride is applied. Other acids and / or einuese zth AIM ΊΓ u * f ^{dr 'Uen Ausr "hrun} e ^sForm

Anhydrides used for this purpose ^ u Amyl alcohols are usually AIIyI-

can. include, without being limited to em ₅₀ ^ Αΐί ^ '° carbon atoms. exemplary

Fumaric acid. Itaconic acid. Chloromaleic acid. Dichlo ^ Γη ^ ίοίοΙ Λΐ ² -M ^eth -Vl-2-propene-1-oil. Cinn

maleic acid and similar amyl alcohol (3-phenyl-2-propene-I oil), 2-phenyl

The second polyvalent carboxylic acid, ie Dicar- AuJahJZ v? "' ^d f!',? ' ^e listed above

bonsäure or tricarboxylic acid is selected from acids se- 1, rrl, ', 7, ^Alk have yl substituent, WO

chooses. which have no additional olefinic ^ / - non- _S5 bkhinä.ff ^ "f ff ^{carbon atoms} per molecule

Supply saturations, and the relative amounts of the D 1 T, ^{4 a} T ^{gen can}

Both acids are adjusted so that the r 1 production of the above

Desired concentration of unsaturation in Kwohn ^ Tri ^ T ⁶ , - ^ ^{11 A1} 'y'g>yc> dylether are

Form of the anhydrides results. To level anhy ^ nlich Glycdylather with 6 to 13 carbon

Thirds for this purpose include phthalic acid. Tetra- 60 emKn Γ ^ Γη ^each * u ° ^{h 3Uch 17} carbon atoms

hydrophthalic acid. l ^ -Benzenetricarboxylic acid (Tri- _Ε 'ίί2 \ a "- ^{s der} .?« ^{made from} a C ₁₄ alcohol and

mellitic acid) and similar acids tpicniornydnn was formed. These include

The polyhydric alcohol is preferably! SKhW ^ ^'11 "' 1-butene glycidyl-

from a diol. Triols and other polyvalent alcohols? In 1 1? Ϊ́ ^ u ^{from the above} ™ ^{ '

hole can be used, however it is advisable 6 ₅ lönn ™ hS ί ?? ^{WERE BLOLDED} - ^{THESE ETHERS}

these alcohols in smaller quantities compared to the alcohols ™ f F ^ f g ^Umset2un such

To use diols. Suitable diols include iamson Svmh ^Ep ' ^chlorh y ^dnn «which according to the WiI-

without being limited to this. ÄthylenglvkolI Pm- "Tn" ^{Synthesis he} _A ^r are provided.

y ngiyKoi. rro _{In a fourth} embodiment it consists of

f ^: "

Binder resin composed of vinyl monomers from a copolymer of two or more vinyl monomers, including at least one hydroxyl-containing monomer component which reacts with an acyl halide was implemented.

In a fifth embodiment, the binder resin composed of vinyl monomers is reacted of a styrene-allyl alcohol copolymer with melhacrylyl chloride or acrylyl chloride.

In a sixth embodiment, the binder resin composed of vinyl monomers is reacted a partially hydrolyzed polyvinyl acetate, styrene-vinyl acetate copolymers or ethylene-vinyl acetate copolymers made with methacrylyl chloride or acrylyl chloride.

It can be seen that in the above embodiments, the one made up of vinyl monomers Binder resin has a skeleton or a basic carbon-carbon chain which is composed essentially of vinyl monomers, the side chains having a terminal unsaturation. This olefinic unsaturation between the terminal carbon atoms of the side chain is from the basic carbon-carbon chain through at least one ester bond or ether bond separated.

The film-forming material should have an application viscosity that is low enough to to allow rapid application to the substrate at a practically uniform depth and high enough so that a film at least 25 μ thick is held on a vertical surface without seeping away will. The films are usually at an average depth of about 2.5 to 100 μ with more suitable Adjustment of viscosity and application method applied. Of course you can the choice of siloxane and hydroxy esters in making the olefinically unsaturated siloxane component of the binder solution, the viscosity of the silicon oxane component can be varied. Also the molecular weight of the polyester and / or the vinyl binder resin can be varied to adjust the viscosity of the binder solution. Also the type and Amount of vinyl monomers in the binder solution can easily be adjusted to a suitable consistency the application by customary paint coating processes, for example spraying on, drawing on, roller application and the like. It is also within the scope of the invention, the polyester or the vinyl copolymer and the reaction product of siloxane and unsaturated ester as the only polymerizable Components of the binder in solution with a volatile solvent, for example toluene, xylene and the like, which can be removed after calling and before hardening.

If the binder consists essentially of the polyester, which is olefinically unsaturated in the "," - position and consists of the olefinically unsaturated polysiloxane, the binder contains about 20 to about 80, advantageously about 30 to about 70 parts by weight of the polyester; and about 80 to about 20, advantageously about 80 to about 30 parts by weight of the siloxane.

If the binder contains a significant amount of vinyl monomers, it advantageously contains about 10 to about 200, preferably about 20 to about 100 parts by weight of the vinyl monomers and a resinous one Ingredient comprised of about 30 to 70 parts by weight of the polyester and about 70 to 30 parts by weight share the siloxane. Smaller amounts of other polymerizable monomers, e.g. wise allyl compounds can be used if desired and make up the remainder dung applies in particular to those coatings where the the film-forming solution, excluding the vinyl monomers, consists essentially of the unsaturated Polyester and the product of siloxane and unsaturated ester, as described here

ίο d. H. Coating compositions, in which these ingredients min make up at least 85 percent by weight of the film-forming binder.

If the binder consists essentially of the oils finically unsaturated, made from vinyl monomers bf.uicri binder resin and the olefinically unsaturated Polysiloxane consists, the binder contains about 20 to about 80, advantageously about 30 to about 70 parts by weight of the vinyl binder resin and about 80 to about 20, preferably about 70 to about. 30 parts by weight of the siloxane.

If the binder contains significant amounts of vinyl monomers, the binder advantageously has about 10 to about 200, preferably about 2C to about 100 parts by weight of vinyl monomers and the resinous ingredient, which is from about 20 to 80, preferably from about 30 to about 70 parts by weight of the vinyl resin and about 80 to 20, preferably about 70 to about 30 parts by weight of the Siloxane is made. Smaller amounts of other polymerizable monomers such as allyl compounds may be used if desired and make up the remainder. The invention is particularly concerned those coatings in which the film-forming solution, excluding the vinyl monomers, im essentially from the binder resin composed of vinyl monomers and the product made from siloxane and unsaturated esters as described herein; d. H. Coating compositions, in which this Ingredients make up at least 85 percent by weight of the film-forming binder.

The term "ionizing radiation" used here denotes radiation with sufficient radiation Energy to cause the paint films described herein to polymerize, i.e. H. equivalent to an energy to about 5000 eV or greater. The preferred method of curing the films from the above Painting on substrates, on which these are applied, consists in the fact that these films are a Beam of polymerization initiating electrons with an average energy in the range of about 100,000 to about 500,000 OeV. at Using such a beam, it is preferred, a minimum of 25,000 eV per 2.5 cm distance to apply between the radiation emitting source and the workpiece if the gap is through Air is ingested. An appropriate setting can be made with regard to the relative resistance of the intermediate gas are made, which preferably consists of an oxygen-free Inert gas, such as nitrogen or helium. An electron beam is preferably used, which at its emission source has an average energy in the range of about 150,000 to about 50,000 OeV. The films formed from the paints according to the invention are advantageously at relative low temperatures, for example between room temperature (20 to 25 ° C) and the temperature, in which a significant evaporation of the volatile

Most constituents begins, usually hardened ^{between 20 and 7O 0 C.} The radiant energy is applied to a preferably moving workpiece in dosages of about 0.1 to about 100 Mrads per second, with the coating having a total dosage in the range of about 0.5 to about 100, usually between about 1 and about 25, and most preferably Receives between 5 and 15 Mrad. The electron beam transforms the films into tough, wear-resistant and weather-resistant coatings.

The abbreviation »Mrad« means 1000,000 rads. The term »Rad« denotes the dose of radiation that an absorption of 100 ergs of energy per gram of absorber, for example coating film, results. The electron emitting device may be a linear electron accelerator used for training a direct current potential in the range listed above is suitable. With such a The electrons are usually emitted from a hot filament and through a uniform device Accelerated stress gradients. The electron beam, which has a diameter of about 3.2 mm at this point, is then distorted so that a funnel-shaped beam results, and then through a metal window, for example made of a magnesium-thorium alloy, aluminum, an alloy of aluminum and a minor amount of copper and the like about 0.0075 cm thick guided.

The following examples serve to further illustrate the invention.

example 1

a) Production of the Siioxane constituent

Respondent

Weight lcile

Acyclic siloxane with functional

Methoxy groups ¹ ) 178

Hydroxy ethyl methacrylate 118

Tetraisopropyl titanate 0.32

Hydroquinone 0.06

') Commercially available methoxylated partial hydrolysis of monophenyl and phenylmethylsilanes (largely condensed dimethyltriphenyltrimethoxytrisiloxane with the following properties:

Average molecular weight 750 850 Average number of silicon atoms each

Molecule 5 J,

Average number of methoxy groups each

Molecule 3 4

b) Production of the polyester resin

This resin contains about 1.5 units of Finnish «, / unsaturation per 1000 units Molecular weight.

'5

40

45 oils de

Initial painting

Maleic anhydride
Phthalic anhydride.
Neopentyl glycol

Parts by weight

147 429 503

All reactants were placed in a four-necked flask equipped with a stirrer, thermometer, Nitrogen inlet tube and a Vigreux column " of 25 cm was equipped with a Barrett's trap to remove the condensation water. The respondents was slowly heated to 165 ° C where the distillation of the condensation water began. Nitrogen was passed through the reactants blown during implementation. The reaction temperature rose when the water was continuous was removed until a maximum temperature of 225 "C was reached. The column was then removed and 3 weight percent xylene was added for azeotropic water removal and heating continued, until the acid number reached 30. The product was cooled to 100 "C and 0.03 percent by weight Hydroquinone added as an inhibitor and the polymer to a content of 80% non-volatile Components diluted with styrene.

A paint made of an unsaturated polyester and the product of siloxane and unsaturated Ester was prepared from the following ingredients in the manner indicated:

c) binder solution

Siloxane ester product according to a)

Polyester resin according to b)

Methyl methacrylate

Parts by weight

10 12.5 5

The binder solution was applied to metal sheets with a rod wrapped with a # 30 wire was. spread and hardened under the following conditions:

Electron beam potential 270 kV

Current strength 25 mA

Dosage 15 Mrad

Atmosphere nitrogen

The films produced in this way showed the following properties:

The siloxane, the hydroxyethyl methacrylate monomer and the hydroquinone as a polymerization inhibitor were heated to 100 ° C. in a flask equipped with a Barrett-type distillation trap. The titanate was added as a catalyst and the temperature increased to 150 ^° C. over 3 hours, during which time the methanol was removed by distillation. The cooled reaction product had a viscosity of 0.6 Stoke at 25 ° C.

Film thickness (//)

Pencil hardness

Solvent resistance ")

40.6 H 6

27.9 H 15

") Rubbed by hand using a soft cloth dipped in 2-butanone.

Excellent coatings were obtained.

Example 2

The procedure according to example 1 was repeated! However, the polyester component is made in the following way from the following components:

Reaklionieilnchmer

Parts by weight

Maleic anhydride I4.7

Tetrahydrophthalic anhydride 72.3

Neopentyl glycol 75.0

Dibutyl tin oxide, catalyst 7.06

The reactants were placed in a reaction vessel and then heated to about 170.degree and held at this temperature for one hour. The temperature of the charge was then increased to 227 ° C. and held there until the acid number of the resin obtained is below about 20 lay. The excess of glycol and water was removed in vacuo and after the acid number below was about OK. 14.5 g of hydroquinone were added. The feed was allowed to cool to about 82 ° C and then added 37.0 parts by weight of styrene.

Excellent coatings were obtained.

Example 3

The procedure of Example 2 was repeated, but an equivalent amount of 1,2-cyclohexenedicarboxylic anhydride was used instead of tetrahydrophthalic anhydride (4 - cyclohexene -1.2 - dicarboxylic acid anhydride) used in the manufacture of the polyester component.

Example 4

The procedure of Example 2 was repeated, but using an equivalent amount of trimellitic anhydride instead of tetrahydrophthalic anhydride in the manufacture of the polyester component used.

Example 5

The procedure of Example 2 was repeated, except that the polyester component was prepared replaced one fifth of the neopentyl glycol with an equivalent amount of pentaerythritol.

Example 6

The procedure of Example 2 was repeated, except that the polyester component was prepared an equivalent amount of ethylene glycol is used in place of the neopentyl glycol.

constituent an equivalent amount of 1,6-hexamethylene glycol used in place of neopentyl glycol.

Example 9

The procedure of Example 2 was repeated, except that the polyester component was prepared an equivalent amount of fumaric acid is used in place of the maleic anhydride.

Example 10

The procedure of Example 2 was repeated, except that the polyester component was prepared an equivalent amount of chloromaleic anhydride in place of maleic anhydride used.

The products of Examples 3 to IC also showed excellent coatings.

Example Il

The procedure according to Example 1 was repeated, However, the polyester component is made from the following components in the following way:

Action participants

Maleic anhydride

Tetrahydrophthalic anhydride
Neopent \ lglycol, ..

Parts by weight

353.0

973.8

1458.1

A melt conversion of tetrahydrophthalic anhydride and the neopentyl glycol was stirred for a period of 23 hours. Water passed over at 165 C and a maximum temperature of 180 C was reached. The resin obtained had an acid number below 15 and was cooled to room temperature, whereupon the maleic anhydride together with 1.39 parts by weight of hydroquinone and 330 ecm of xylene was added. The feed was fed to an acid number of 10 heated, the water passed at about 140 C and reached a maximum temperature of 180 C. became.

Example 12

The process according to Example 1 was repeated, but the polysiloxane was a methoxylated partial hydrolyzate used by monophenyl and phenylmethylsilanes, consisting essentially of dimethyltriphenyltrimethoxytrisiloxane existed and had the following properties:

Example 7

The procedure of Example 2 was repeated. however, in the manufacture of the polyester component an equivalent amount of 2-butene-1,4-diol glycol used in place of neopentyl glycol.

Example 8

The procedure of Example 2 was repeated, except that in the preparation of the polyester average Molecular weight 470

Connection weight 155

Specific weight at 25 C 1.105

Viscosity at 25 C. Centislokes .... 13

The products of Examples I, I and 12 also gave excellent coatings.

B e i s ρ i e I 13

A coating paint made from the reaction product of siloxane and unsaturated ester was made the following components manufactured in the specified manner:

Reaction participants

Functional cyclic siloxane

Hydroxyl groups ¹ )

Hydroxyethyl methacrylate

Hydroquinone

Xylene, solvent

Weight parts

200
71
0.1
116

¹ I Commercially available cyclic polysiloxane with functional hydroxyl groups and the following typical properties:

Hydroxyl content. Dean Stark

Percent, condensable 5.5

Percent, free 0.5

Average molecular weight 16Of)

Link weight 400

Refractive index 1,531-1,539

Softening point. Mercury process according to

Durran. C 93

10

At 60% solids in xylene

Specific weight at,! 5 C
Viscosity at 25 C. Ccnli poise
Gardner-Holdt

1,075

33

A-I

A three-necked flask with a stirrer, thermometer. Nitrogen inlet and barrel trap, was using the siloxane. charged with hydroxyethyl methacrylate, xylene and hydroquinone. This solution was heated to reflux, 138 ° C. for 30 minutes. Nitrogen was passed through the reaction mixture blown throughout the procedure. The by-product water was slowly removed, and the temperature gradually rose to 146 ° C. After 5 hours, 8.1 ml of water had been collected, which indicates an almost complete implementation. The xylene was distilled off under reduced pressure and then diluting the product to 70% nonvolatiles with methyl methacrylate. 100 parts by weight of this solution and 30 parts by weight of the polyester prepared according to Example 1 were mixed and gave the first paint binder. 100 parts of this solution and 70 parts by weight of the Polyesters prepared according to Example I were mixed and gave the second paint binder.

These coatings were pigmented and put on backing made of metal, wood and polymeric materials (ABS, i.e. acrylonitrile-butadiene-styrene copolymer) and then with an electron beam as in the previous examples at one dose hardened by about 20 Mrad. <, r>

There were excellent coatings on the documents obtain.

Example 14

The procedures of Examples 1, 12 and 13 were followed idhl jd i M

55

repeated, but with a lot of the monohydroxycster of those olefinically unsaturated in the «, // position Monocarboxylic acid used, which was sufficient to with at least one functional hydroxyl or hydrocarbonoxy group of the siloxane react, but not enough to react with all such Groups of the siloxane molecules to react in the reaction mixture.

B e i s ρ i e I 15,

The procedures of Examples 1. 12 and 13 were followed repeated, but such an amount of the monohydroxy ester that is olefinically unsaturated in the ", // - position Monocarboxylic acid used, which is in excess over the saturation of all functional Hydroxyl and hydrocarbon oxy groups of the siloxane molecules required in the reaction mixture Amount was present.

Also here were excellent coatings obtain.

Example 16

A pigmented paint was prepared. by adding 75 parts by weight of the product of siloxane and unsaturated ester according to Example 12 to 150 parts by weight a commercial titanium dioxide pigment and 20 parts by weight of methyl methacrylate premixed became. The mixture was made by shaking with an equal amount of glass beads in one conventional paint shaker ground for 30 minutes. The premix was additionally with further 75 parts by weight of the product of siloxane and unsaturated ester and 65 parts by weight of the resulting mixture were diluted with 35 parts by weight an equimolar mixture of styrene and methyl methacrylate. This mixture was added to 35 parts of methyl methacrylate and 65 parts by weight of the polyester according to Example 1.

The paint was applied to substrates made of metal, wood and polymeric materials (ABS, i.e. acrylonitrile-butadiene-styrene copolymers) applied to an average depth of about 38 μ and cured thereon with an electron beam as in the previous examples.

Excellent abrasion and weather resistant coatings resulted.

Example 17

A paint was made of a diisocyanate modified polyester and a product made from siloxane and unsaturated ester in the following way:

a) Production of polyester A

Reaction participant

Succinic acid

Tetrahydrophthalic anhydride
1,2 propanediol

Parts by weight

340.1
1387.6
1004.4

The monomers were mixed with 200 ecm xylene, while heating in the solvent subjected to a period of 10 hours, during which the temperature was gradually increased to 260 "C. The resin obtained had an acid number of about 5.7. The xylene was separated from the resin.

b) Production of the polyester B

Response participants

Resin A

Tolylene diisocyanate

Styrene

Weight partc

200
17.4
86

The diisocyanal grew slowly and slowly was added to the solution of styrene and resin A and charging continued for a period of time of 5.5 hours, whereby Resin B was formed.

c) Production of the polyester C

13 parts by weight of 2-hydroxyethyl methacrylate were added to the reaction mixture containing resin B added slowly and gradually and the feed continuously over a period of Stirred for 25 hours and resin C was obtained.

d) Preparation of the paint

Components

Resin solution C

Product made from siloxane and unsaturated
Ester according to example la)

Parts by weight

55
35

This paint was applied to the backing with a wire wrapped rod and dried with an electron beam. The above approach was here with 10, 25 and Diluted 50 parts by weight of methyl methacrylate. The masses obtained were applied to substrates and cured thereon by an electron beam as in the previous examples.

Excellent coated documents were obtained.

Example 18

A modified siloxane paint was made from the following components:

Components

Weight lcile

25th
75

Product made from siloxane and unsaturated

Ester according to example la

Solution of the product from siloxane

and modified polyester ')

') The solution of the product of siloxane and modified polyester in Vip.yl monomers was prepared as follows:

70 parts by weight of neopentyl glycol were placed in a reaction vessel. 10 parts by weight of xylene and 35 parts by weight of that used in Example 13 introduced cyclic polysiloxane with functional hydroxyl groups. The load was set to about 174 ° C heated for 2.5 hours, whereupon 13.7 parts by weight of maleic anhydride, 54.2 parts by weight of tetrahydrophthalic anhydride and 0.22 parts by weight of dibutyltin oxide were added. the The temperature of the feed was slowly increased to about 221 ° C. and maintained at that temperature until the resin obtained had a Acid number of about 10. Part of the XyIoIs and the The water formed in the reaction was removed during the boiling and the excess was then removed in vacuo. To the Charge was added 0.027 parts by weight hydroquinone and the charge cooled to 82.5 "C and 40 parts by weight Diluted styrene.

The paint was applied to and on substrates cured with an electron beam as in the previous examples. I received excellent, withdrawn documents.

Example 19

The process of Example 1 was repeated, but curing with a beam polarity of 175,000 volts at a distance of the workpiece of 7.5 cm from the emitting source and with 400,000 volts carried out at a distance of about 25 cm, each working in a nitrogen atmosphere containing small amounts of carbon dioxide.

Excellent coatings were obtained.

Example 20

The siloxane / unsaturated ester products of Examples 1, 12 and 13 were used along with the Polyester resins of Examples 1 and 2 used and diluted to spray consistency with xylene. These solutions were applied to substrates made of wood, metal and synthetic solid polymers and how cured in the previous examples after ίο the xylene had been driven off.

Excellent coatings were obtained.

Example 21

Paint compositions were prepared by adding 60 parts by weight of the product of siloxane and unsaturated Esters according to Example 1 and 160 parts by weight of the polyester resin according to Example 1 were mixed, this mixture was divided into two equal parts and one of these parts with 100 parts by weight of methyl methacrylate and the other was diluted with 200 parts by weight of methyl methacrylate.

The film-forming solutions obtained were applied to metal substrates and then with a Electron beam as in the previous examples. networked.

Example 22

Initial masses were made by adding 40 parts by weight of the product of siloxane and unsaturated ester according to Example 13 and 40 parts by weight of the Polyester resin according to Example 2 were mixed, this mixture was divided into equal parts and one of these parts with 10 parts by weight of methyl methacrylate and the other part with 20 parts by weight Methyl methacrylate was diluted.

The film-forming solutions obtained were applied to metal substrates and crosslinked thereon with an electron beam, as in the preceding examples.
Excellent coatings were also obtained in Examples 21 and 22.

Example 23

A paint that is a product of a siloxane and an unsaturated ester and an unsaturated vinyl resin was prepared from the following ingredients in the manner indicated:

a) Production of the siloxane component

Action participants

Acyclic siloxane with functional

Methoxyl groups ¹ )

Hydroxyethyl methacrylate

Tetraisopropyl titanate

Hydroquinone

Parts by weight

178

118
0.32
0.06

') See example I.

Siloxane, hydroxyethyl methacrylate monomer and hydroquinone as a polymerization inhibitor were heated to 100 ° C. in a flask equipped with a Barrett-type distillation receiver. Titanal as a catalyst was added and the temperature was increased to 150 ^° C. over a period of 3 hours, during which time the methanol was removed by distillation.

cooled reaction product had a viscosity of 0.6 Stoke at 25 "C.

b) Production of the binder resin composed of vinyl monomers

Raw materials

Xylene

Methyl methacrylate ..

Ethyl acrylate

Glycidyl methacrylate.
Azobisisobutyronitrile

Hydroquinone

Methacrylic acid

Triethylamine

Weight

600

196

333

71

0.12
42
0.96

The solvent for the reaction, xylene, was added to a flask equipped with a stir bar, addition funnel, Thermometer, nitrogen inlet tube and condenser. The amount of xylene was the same as the total weight of vinyl monomers to be added. The xylene was heated to reflux and Nitrogen bubbled through the solution during the warm-up and reaction. The United Monomers and the initiator (azobisisobutyronitrile) were added to the refluxed solution added evenly over 2 hours. The weight of the initiator was 10 parts by weight 1000 parts by weight of the vinyl monomers. The reaction solution was refluxed until the Conversion of the monomers to the polymer was greater than 97% (8 to 16 hours).

In the second stage, hydroquinone was added as HemmslOiT and then methacrylic acid to Reaction with the remaining epoxy groups of the polymer added. Triethylamine was used as the catalyst used. This esterification reaction was carried out at reflux temperature until 80% Esterification was achieved (determined by the remaining acid number). The xylene was then through Vacuum distillation removed and the polymer diluted in methyl methacrylate so that the weight ratio from polymer to solvent was 2.

c) Preparation of the paint

Components

Product of siloxane and ester according to a)

Acrylic resin according to b)

Methyl methacrylate

important parts

10
15th

2.5

Example 24

The process of Example 23 was repeated, but the polymer made up of vinyl monomers made from the following ingredients in the following way:

Ethyl acrylate

Methyl methacrylate
Allyl glycidyl ether.
Benzoyl peroxide ...
XvIoI

Parts by weight

38.8

23.2

37.0

1.0

solvent

In a reaction vessel equipped with a condenser, thermometer, stirrer and dropping funnel an amount by weight of xylene equal to that of the reactants to be added in the first reaction stage was added. The xylene was reduced to about Heated 100 to 120 C. The vie "· respondents were mixed thoroughly and slowly added with a dropping funnel to the heated xylene over 4 hours admitted. The reaction was completed at this temperature for 1 to 2 hours Allow the addition to continue and the mixture was cooled to room temperature.

The binder polymer was formed in a second reaction stage from the following materials:

Copolymer from stage I.

Allyl alcohol

Potassium hydroxide

Parts by weight

69.4

30.4

0.2

A solution of allyl alcohol and potassium hydroxide was added to the copolymer at room temperature. The mixture was then heated to a temperature of 100 to 120 ⁰ C. This temperature was maintained for about 7 hours and then cooled. The reaction mixture of binder and polymer was heated to about 60 ° C. and xylene and excess reactants were removed by vacuum distillation.

At a temperature of about 60 ° C, styrene and hydroquinone were added to the polymer and get a film-forming solution with the following composition:

55

The paint was applied to a steel base _p . _# " _F,.

with a rod wrapped with a No. 30 wire ' ^{olvrneres aus aiuIe} '

was applied and made to a hard film under styrene

Use of the following irradiation conditions- Hydroquinone

hardens:

Parts by weight

66.66

33.27
0.07

Electron beam potential ... 270 kV
Current strength of the electron beam 25 niA

Dosage 15 Mrad

Atmosphere nitrogen

Distance from workpiece to

Emitting point 25 cm

Example 25

The process of Example 23 was repeated, but the polymer made up of vinyl monomers made from the following ingredients in the following way:

Ethyl acrylate

Methyl methacrylate

Allyl alcohol

Benzoyl peroxide ...
Xylene

Parts by weight

39

24

36

solvent

A reaction vessel equipped with a condenser, thermometer, stirrer and dropping funnel was placed in a The same amount of xylene by weight as the reactants to be added in the first stage were introduced. The xylene was heated to about 100-120 ° C. The four respondents became thorough mixed and slowly added with the dropping funnel into the heated xylene over 4 hours. The reaction was held at this temperature for 1 to 2 hours after the addition had ended. then it was cooled to room temperature.

The binder polymer was produced in a second reaction stage from the following materials:

Copolymer from stage 1

Allyl glycidyl ether

Potassium hydroxide

Parts by weight

69
30.8

0.2

A solution of the allyl glycidyl ether and potassium hydroxide was added to the copolymer at room temperature. The mixture was then heated to a temperature of 100 to 120 ⁰ C. This temperature was maintained for about 7 hours and then cooled. The reaction mixture of binder and polymer was ^{heated to about 60.degree.} C. and xylene and excess reactants were removed by vacuum distillation.

At a temperature of about 60 ° C, styrene and hydroquinone were added to the polymer and get a film-forming solution with the following composition:

Parts by weight

Respondents

Methyl methacrylate

Ethyl acrylate

Hydroxyethyl methacrylate

toluene

Benzoyl peroxide

Parts by weight

400

400

195

1000

30th

Parts by weight 500
33.8
30th

Polymer from stage II 67

Styrene 32.93

Hydroquinone 0.07

Example 26

The process of Example 23 was repeated, but the polymer made up of vinyl monomers made from the following ingredients in the following way:

Level I.

The benzoyl peroxide was dissolved in a solution of methyl methacrylate, ethyl acrylate and hydroxyethyl methacrylate and one half of the toluene. This solution was portionwise added to the remaining toluene S at reflux temperature for a period of 7 hours, eventually forming a pot temperature reached about 138 to 140 ⁰ C. The heating at reflux was maintained for an additional 3 hours and the solution then cooled.

Stage II
Respondents

Solution from stage 1

Acrylic chloride

toluene

The solution from step I was heated to 6O ⁰ C and a solution of acrylic chloride, and toluene was added dropwise over 4 hours added, the temperature rose to about 90 ° C. After heating for an additional 2.5 hours, standard infrared analysis of the solution indicated about 14% hydroxyl groups remaining. The solution was obtained with a Gardner-Holdt viscosity of B - C. This solution was subjected to a vacuum of less than 10 mm Hg at 7O ⁰ C and recovering the acrylic polymers.

Example 27

The process of Example 23 was repeated, but the polymer made up of vinyl monomers made from the following components in the following manner:

100 parts by weight of a styrene-allyl alcohol copolymer with a content of 21.4 percent by weight allyl alcohol and with an average molecular weight of about 1620 and 0.1 part by weight of hydroquinone were dissolved in toluene and ^{heated to 90 0} C and 41.8 parts by weight of methacrylyl chloride in toluene dropwise during one hour added. Heating was continued and the temperature allowed to rise to the reflux temperature of the toluene until, after a further 5 hours, the evolution of gas had virtually ceased. Infrared analysis showed about 10% remaining hydroxyl groups. The solvent was removed using the water pump.

Example 28

The procedure of Example 23 was repeated, but the polymer made up of vinyl monomers was repeated from the following components in the following

55, way made:

250 parts by weight of a solution with 25% non-volatile substances from a polymerized in solution Polyvinyl acetate supplied in a mixture of about 85% toluene and 15% methanol was used placed in a 1-1 flask going to the distillator was equipped for stirring and for dropwise addition of solvent. The polyvinyl acetate was hydrolyzed so that it contained about 3.5% hydroxyl group. The methanol was an azeotrope m:

Toluene removed and additional toluene added to maintain volume. After finished Removal of methanol, the solution was refluxed and 16 parts by weight of methacrylyl chloride i

509517/3

/ rf

20 parts by weight of dry dioxane added dropwise over ¹ liter for ₁ hour. Heating was continued for an additional 5 hours. Toluene was added during the distillation and then the excess of acid chloride and the excess of toluene were removed using the water pump.

Excellent coatings were also obtained from the products of Examples 23 to 28.

Example 29

The procedures of Examples 23-28 were repeated except that the vinyl monomer content persisted the paint binder solution made from a mixture of styrene and methyl methacrylate and was about 10 percent by weight the solution.

Example 30

The procedures of Examples 23-28 were repeated except that the vinyl monomer content persisted the paint binder solution from a mixture of methyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate and was about 60 percent by weight the solution.

Example 31

The process of Example 23 was repeated, but using the olefinically unsaturated copolymer and the olefinically unsaturated siloxane in the absence of vinyl monomers, the viscosity being brought to spray consistency with toluene, which was stripped off before curing.
Excellent coatings were also obtained here.

Claims (5)

5 claims: 1. Paint binders curable by ionic radiation based on unsaturated Siioxanes mixed with unsaturated polymers, characterized in that it consists of a film-forming solution a) an olefinically unsaturated siloxane, which by reacting a siloxane with at least two functional groups, namely hydroxyl groups and / or hydrocarbonoxy groups, and with 3 to 18, in particular 3 to 12 silicon atoms per molecule with a hydroxy ester in a and / or position olefinically unsaturated carboxylic acid has been obtained, and from b) one which is olefinically unsaturated in the «,, / - position Polyester having a molecular weight of 500 to 20,000 and / or one in the side chain terminally olefinically unsaturated copolymers of vinyl monomers with a molecular weight of 1,000 to 50,000, the in each case about 0.5 to 5, in particular 0.5 to 3.5 units of olefinic unsaturation to 1000 units of molecular weight, consists. 2. Radiation-curable paint binder according to claim 1, characterized in that the film-forming solution from about 20 to about 80, preferably from about 3 to about 70 parts by weight of the olefinically unsaturated siloxane and about 80 to about 20, preferably about 70 to about 30 weight lines that which is olefinically unsaturated in the, // position Polyester or the copolymer which is terminally olefinically unsaturated in the side chain Contains vinyl monomers. 3. Radiation-curable paint binder according to Claim 1 or 2, characterized in that that the filmbi'dende solution additionally about 10 to about 200 parts by weight of vinyl monomers contains. 4. Radiation-curable paint binders according to Claims 1 to 3, characterized in that that the film-forming solution is also a particulate Contains pigment. 5. Use of the paint binder according to claims 1 to 4 in a coating process Application of an electron beam with an average energy of 10C) (K) O to $ 00,000 eV.