CA1134984A

CA1134984A - Acrylated urethane silicone compositions

Info

Publication number: CA1134984A
Application number: CA000363797A
Authority: CA
Inventors: Richard G. Carter; Walter P. Miller; Stuart L. Watson, Jr.
Original assignee: Union Carbide Corp
Current assignee: Union Carbide Corp
Priority date: 1979-11-26
Filing date: 1980-10-31
Publication date: 1982-11-02
Also published as: GB2067213A; JPS5686924A; JPS601886B2; DE3044301A1; GB2067213B

Abstract

ACRYLATE URETHANE

SILICONE COMPOSITIONS

ABSTRACT OF THE DISCLOSURE

Acrylated urethane silicone compositions are formed from the reaction of a silicone carbinol, a polyisocyanate and a hydroxy-functional acrylate. These compositions are useful as components of improved radiation-curable coating compositions.

S P E C I F I C A T I O N

Description

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:
~', ~ BACKG~OUND OF_T~E INVENTION
::
Coatings play a useful role in the manufac-ture of a great many articlecs which ind wide use in nearly all facets of contemporary life. Until recently, nearly all coatings were applied with the employment of a hydrocarbon based solvent which evaporated leaving a dried coating on the article which was to be coated. '~
This system met with increasing disfavor as the price of organic solvent increased and as the deleterious ;~ environmental effects of the evaporated solvent became better understood. Systems aimed at solvent recovery to reduce pollution and conserve solvent have generally , ,, ~
10 proven to be expensive and energy intensive. In response, those skilled in the art ha~e devised a class . ,~
of coatings termed radiation-curable coatings in which, upon exposure to radiation, virtually all of the liquid portion of the coating is converted to cured coating re- ;
sulting in little solvent emission. ~-Unfortunately many of the radiation-curable coatings which have been here~ofore manufactured are highly viscous and difficult to apply to the substrate requiring dilution of the coating material with volatile . "
~ 20 solvents. A radiation-curable coating which is of such i~ low viscosity so as to avoid the use of diluents would be ~` of great advantage.
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... . .
.., ' 12161 SUMMARY OF THE INVENTION

~: It has now b~en found that compositions formed . .
from the reaction of a silicone carbinol, a polyisocyanate and a hydroxy-functional acrylate can be incorporated in radiation-curable coatings and that the resulting coa~ings . are significantly less viscous than the heretofore avail-;f~ able coatings.

., ~ DESCRIPTION OF_THE INV~NTION
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:~,. The acrylated urethane silicone compositions of this invention are the reaction products of a ; 10 silicone havin~ at least one reactive hydroxyl group in the molecule (a silicone carbinol~, an organic poly-isocyanate and a hydroxyalkyl acrylyl compound; all as hereinafter defined.
.i The silicone carbinols useful are those having ,; : a plurality of hydroxyl groups in the molecule, and many ,~ ., ,~ are commercially available. Among those suitable ase those represented by the formula R(OH)n in which R represents a polysiloxane moiety and n is an integer having a value `~ of ~rom 2 to about 4. Basically two structures are known, the simple polydimethylsiloxy type and the grafted ,i"i.~ 20 copoly type.
The polydimethylsiloxy type can be represented by the foImula :
: 3 :

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CH3 CH3 ~ CH3 l I ,, HOR' - SiO SiO - - - SiR'OH
CH3 CH3 _ x C 3 and the copoly type o~ the formula (C~3)35iO t 5~ o ~ Si(C~3)3 (O CnH2n)yO

- .
wherein R' is an alkylene group having from l to 16 . ::
carbon atoms; n is an integer having a value of 2 or 3; x has a value of:from 1 to 1000, y has a value of from O to 15; and 2 has a value of from 1 to 6. ~.
;: The organic polyisocyanates are known com-: pounds and can be represented by tha general formula Q(NCO)m wherein m has a value of from 2 to 5 and Q is : ; the residual organic portio.n of the molecule to which : the isocyanato groups are attached. Among those suitable for use~in~this invention one can mention 3,5,5-~rim- :~
ethyl-l~isocyanato-3-isocyanato-methylcyclo~exana, di(2-isocyanatoethyl)'bicyclo [2,2,1]-hept-5-ene-2,3-di~
carboxyIate, 2,4-tolylene diisocyanate, 2,6-tolylene ~ -:

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diisocyanate, 4,4'-diphenyl- ~
methane diisocyanate, dianisdine diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, ~he m- and p-xylylene diisocyanates, tetra~et:hylene diisocyanate, di-cyclohexyl-4,4'-methane diisocyanate, cyclohexane-l, 4-diisocyanate, l,S-naphthylene diisocyanate,4,4' diisocyanate diphenyl ether, 2,4,6-triisocyanate toluene, 4,4',4"-triisocyanate triphenyl methane, diphenylene-4,4-diisocyanate, the polymethylene poly-phenylisocyanates, as well as any of the other organic isocyanates known to the average skilled chemist.
The hydroxyalkyl acrylyl compounds suitable for use in producing the acrylated urethane silicones are those of the formula CH2 = CCOOR"OH

wherein X is hydrogen or methyl and R'l is a linear or branched divalent alkylene having from 2 to about 5 carbon atoms. Illustrative thereof one can mention hydroxyethyl acryla~e, hydroxypropyl acrylate, hydroxypentyl acrylate and the corresponding methacrylates.
A si.mple representative formula for the acry-lated urethane silicones produced using an organic -diisocyanate and a silicone carbinol having two hydroxyl groups is the following: i 1 ' ' (CH2=CHCOOR"OOCNHQ~HCOO)2R ~ '~
- :;
-5- ;
, ;, . . . ~ , . . .. .. . . .. ... . . .. . . ..

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- ,, in which X, R and R" have the meanings previously in- ~~
dicated and Q is the polyvalenl: residue remaining after reaction of polyisocyanate and can be linear or branched alkylene having from 1 to 10 carbon atoms; arylene, alkarylene or aralkylene having from 6 to 12 carbon atoms;
cycloalkylene having from 5 to 10 carbon atoms, or bi-cycloalkylene having from 7 to 15 carbon atoms. Those skilled in the art can readily write the formulas for the products prepared using polyisocyanates and carbinols of other functionalities.
In producing the acrylated urethane silicones one initially produces a pr~polymer containing free ; isocyanato groups and then reacts the free isocyanato groups with a reactant containing a reactive hydrogen atom.
Thusj in one embodiment of the reaction, the silicone carbinol is reacted with a sufficient excess of organic polyisocyanate to permit reaction of all of the hydroxyl groups with isocyanato groups but still have unreacted at -least one free isocYanato equivalent per mole of pre-polymer produced,~ thereby producing an isocyanato terminated prepolymer. Thereafter this prepolymer is reacted with the hydroxyalkyl acrylyl compound. In a second embodiment ~ ~
of the reaction the prepolymer is produced by initially -reacting the organic polyisocyanate with the hydroxyalkyl ~ acrylyl compound and then reacting the prepolymer with ; the silicone carbinol.
~ In either mode of operation the reaction of .
~ the silicone carbinol, polyisocyanate and acrylate to form : :~

- ~ ~ 3 ~ ~ 4 the compositions of this invention can be carried out at a temperature of from OC to 125C. The preferred temperature is ambient.
The reaction can be carried out at subatmospheric, atmospheric or superatmospheric pressure; the preferred pressure is atmospheric.
The reaction time will vary according to the size of the batch, the temperature and pressure and the nature of the particular silicone carbinol, polyisocyanate and hydroxy-functional acrylate reactants being employed.
The reaction will proceed uncatalyzed, but a catalyst can be employed to expedite it. Such catalysts are well known in the art and include dibutyl tin dilaurate, stannous octoate, dioctyl tin diacetate, morpholine, triethylene diamine as well as any other suitable urethane cataLyst recognized in the art. The catalyst, if present, ~ can be in a concentration of from 0.01 to 1.0 weight per-; - cent, preferably from 0.05 to 0.2 weight percent, based on the total weight of the reaction mixture.
The acrylated urethane siLicone compositions of this invention can be used as coating compositions either alone or in mixture with other reactive monomers, solvents, pigments, fillers and other a~ditives. The ~ ;
coating compositions can be applied by con~entional means and cured by exposure to ultraviole~ light or to high energy radiation such as gamma-ray, alpha-particle, beta-particle and accelerated electrons or by heat. If ultraviolet Light is employed the coating composition ~-, . . . ~ . ,. . . , . ., . ,. . . .. . ~ : .. . . . . . . .

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preferably contains a photoinitiator. Illustrative of such photoinitiators one can namer~ di-S-butoxyaceto-phenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-acetophenone, benzophenone, p-methoxybenzophenone, aceto-phenone, m-chloroacetophenone, propiophenone, xanthone, benzion, benzil, benzaldehyde, naphthoquinone, anthra-quinone and the like. The photoinitiator may be used singly or in mixtures and is present in a concentration o from 0 to 10 weight percent preferably rom 0.5 to 5 weight percent based on the weight of the acrylated urethane silicone present.
When heat curing is employed there can be employed free radical initiators in a concentration of from about 0.1 to 10 weight percent, preferably from 0.5 to 5 weigh~
percent based on the weight of the acrylated urethane silicone present. Illustrative of such free radical initiators one can name di-t -butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, t-butyl peracetate, per-acetic acid, perbenzoic acid, benzoyl peroxide, dichloro-benzoyl peroxide, azobis(isobutyrontrile), dimethylazobis(isobutyrate) and the like.
The coatings can be applied to any acceptable substrate such as wood, metal, glass, abric, paper, fiber, plastic: that is in any form, e.g. sheet, coil, molded, -film, panel, tube, etc., by conventional means including spray curtain~ di~ pad~ roll-coating and brushing procedures.
In a typical embodiment isophorone diisocyanate , and dibutyl tin dilaurate as catalyst are charged to a flask, stirred and heated, whil.e a silicone carbinol is added dropwise. After completi.on of this reaction,

2-hydroxyethyl acrylate is added dropwise and the mixture is stirred and heated ~or an additional period to complete the reaction. The acrylated urethane silicone produced is stabilized with hydroquinone monomethyl ether. A
coating is produced by blending with 2-(N-methyl-carbamoyl) oxyethyl acrylate and.~,~ -di-S-buto~yacetophenone as photoinitiator. When applied to release paper and irradi-ated with ultraviolet light, the liquid cured to a polymerized film.
It was completely unexpected and unobvious to find that the reaction of a silicone carbinol, a poly-isocyanate and a hydroxy-functional acrylate would produce ; an acrylated urethane silicone which has a low viscosity :-so that it can be easily coated on substrates without the ~ ;
the use of diluents, and which can be employed in a radiation-cu~able composition. ~:
The acrylated urethane silicones are especially useful in the form~lation of low viscosity varnishes for application over conventional ink prints whLle the ink is still in the uncured state, with sub- -sequent curing of the varnish by exposure to radiation. -;
The unique properties of the acrylates urethane silicones such as a low viscosity/molecular weight ratio good flow-: ~ ',- , _g_ ~
:

3 ~

out performance, good wetting of the ink surface combined with minimal miscibility with t:he ink make them particularly good choices ~or this application in view of the fact that the commonly used organic acrylate materials, when used in thls application yield varnishes which do not provide the desired high level of gloss combined with good film properties, such as scratch resistance, flexibility and adhesion, a~ter the ink has cured to a solid state by the process of vehicle penetration into the substrate and oxidation of the contained drying oils.
The following examples serve to further illustrate the invention.
Example 1 There were charged to a 500 ml four-neck round-bottom flask, equipped with a mechanical stirrer, hea~ing mantle, air condenser, dropping funnel, thermometer and : dry nitrogen purge, 37 grams of isophorone diisocyanate ;
and 0.4 gram dibutyl tin dilaurate as catalyst. The mi~
;~ ture was heated with stirring to 40C and kept at the ~ 20 temperature while 200 grams of silicone polycarbinol was :: stirred in dropwise. The polycarbinol had the general formula ~ :
Me Me Me l l HOR- Si- O - Si o - - Si - ROH
1, I
Me Me Me ,: , ~ ..... . . . .

~ ~ 3 ~

It had an average hydroxyl equivalent weight of 1200 and a viscosity of 320 centistokes at 25C. T~hen the addition was completed, the mixture was stirred for another 15 minutes to complete reaction and formation of the isocyanato terminated prepolymer, after which 21 grams of 2-hydroxy-ethyl acrylate was added dropwise while the mixture was kept at 40C and stirred. After the addition of the acrylate the resulting mixture was stirred for 4 hours while the temperatures was kept between 40C to 50C. Titration with dibutylamine indicated that the free isocyanato content was less than 0.1 weight percent. After this, 0.05 gram of hydroquinone monomethyl ether was added to the acrylated urethane produced as a stabili7er and was stirred for fifteen minutes.
Seventy parts of the acrylated urethane silicone ~-produced was formulated with 30 parts of 2-(N-methyl-; carbamoyl)oxyethyl acrylate and 1 part ofz~ ,di-S-butoxy-acetophone as photoinitiator. The formulation was coated on release paper and irradiated by exposure for about 11.5 ;~
,~, seconds, under a nitrogen atmosphere, to ultraviolet light at a wavelength of about 3500 angstrom units. The liquid formulation cured to a dry ~ilm and was removed from the ;~
release paper.
The film was placed in a constant temperature/
humidity chamber overnight. The next day a 0.25 inch wide strip was cut and placed in a 1.0 inch gauge length cross-head of a stress strain testing machine. The film strip was 3 ~

stretched to breakage and the force at failure was used together with the width and thickness to calculate the force per unit area at failure. The ultimate elongation was calculated using the formula Ultimate Elongation % - ( L _ ~ 100 where L is the length at failure and Lo is the original gauge length. The film was found to have a tensile strength of 1200 psi and an ultimate elongation of 43 per-cent.
Example 2 The coating formulation produced in Example 1 was coated on a steel panel and then irradiated under a nitrogen atmosphere for about 1.9 seconds using ultra-violet light at a wavelength of about 3500 angstrom units.
The liquid cured to a solid film. A piece of paper towel was placed on the coating and saturated with acetone. The time until the coating was attacked was measured. The coating had a time rating of 153 seconds.
E ample 3 There were charged to the apparatus described in Example 1 46.5 grams of bis(4-isocyanatocyclohexyl) methane, 114. grams of 2-(N-methylcarbamoyl)oxyethyl acrylate ancl 0.4 gram o~ dibutyl tin dilaurate as catalyst.
The mixture was heated and stirred as in Exa~ple 1 and .

; , - . ~ . . . ~ .. .

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205 grams of the silicone polycarbinol used in Example 1 was added dropwise to produce an isocyanato terminated prepolymer. Fifteen minutes after the polycarbinol addition was completed, 21 grams of 2-hydroxyethyl acrylate was added dropwise followed by 0.05 gram of hydroquinone mono-ethyl ether as polymerization inhibitor. The resulting mixture was stirred for 5 hours while the temperature was ke~t at rom 50C to 55C. Titration with dibutylamine indicated that free isocyanato content was less than 0.1 weight percent. Thereafter 99 parts of this acrylated urethane silicone was combined with 1 part of ~ ,o~-di- ~ ~
S-butoxyacetophenone as photoinitiator. The resulting ~ ~;
mixture was coated on release paper and irradiated for about 1.9 seconds u~der a nitrogen atmosphere using ultra-violet light at a wavelength of about 3500 angstrom units.
The liquld coating cured to a dry film. The film had a tensile strength of 110 psi and an ultimate elongation of 43 percent.
. ,:
Example 4 There were charged to a 500 ml four-neck round-bottom 1ask, equipped with a mechanical stirrer, cooling . . .
water bath and dropping funnel, 11.1 grams of isophorone diisocyanate and 5 drops of dibutyl tin dilaurate as ~
catalyst. While the temperature was maintained at about ~ ;
20C to 25C with the cooling water bath, 7 grams of 2-hydroxyethyl acrylate was added dropwise with stirring.
When the addition was complete the mixture was stirred at , 3 ~

room temperature for about 16 hours to complete formation of the isocyanato terminated prepolymer. Thereafter 50 grams of silicone polycarbinol having a hydroxyl number of 200 mg.KOH/g, a specific gravity of 1.06 at 25C and a viscosity of 350 centistokes at 25C was added dropwise and the mixture was stirred at ambient temperature for about 24 hours. The silicone polycarbinol had the chemical formula H3 l _1H3 ~
(CH3)3Sio - SiO l -SiO - _Si(CH3)3 (OC2H4)7,50H_ 5,5 ~ ~, 'rhereafter 99 parts of this acrylated urethane silicone was mixed with 1 part of ~, ~-di-S-butoxyacetophenone as photoinitiator. The resulting mixture was coated on release paper and then irradiated for 2.88 seconds under a nitrogen atmosphere using ultraviolet radiation at a wavelength of about 3500 angstrom units. The liquid cured to a dry film; it had a tensile strength of 64 psi and an ultimate elongation of 19 percent.

Example 5 There were charged to the apparatus described in Example 4 11,1 grams of isophorone diisocyanate and 5 drops of dibutyl tin dilaurate as catalyst. ~hile the ., .

.. .. .

3 ~

temperature was maintained at 20C to 25C with the cooling -~
water bath 5.8 grams of 2-hydroxyethyl acrylate was added dropwise with stirring. When the addition was complete the mixture was stirred at room temperature for about 7 hours to complete formation of the isocyanato terminated pre-polymer. ThereaXter 50 grams of a silicone polycarbinol having a chemical formula of '~:
CIH3 ~ IH3 CH3 (CH3)3SiO - SiO - _ SiO _ _Ci~ ~ Si(CH3) 10C~3 - ~ l2H6 13~6 ~oC~H4)7 5o~1 ~OC2H4)7.50H ¦

were added dropwise. A~ter the addition the mixture was stirred at ambient temperature for about 15 hours and the acrylated urethane silicone composition was recovered.
Thereafter 99 parts of the above-described mixture was mixed with 1 part of ~ di-S -butoxyacetophenone as photoinitiator. The resulting mixture was coated o~
rele~se paper and irradiated for 2.88seconds under a nitrogen atmosphere using ultraviolet radiation at a wave-length of about 3500 angstrom units. The liquid cured to a dry film.

Example 6 ;
To 49;parts o~ the acrylated urethane silicone ~`
prepared in Example 4 there was added 1 part of ... .,.,.............................................................. :

~ ~3~

~ , O~-di-S-butoxyacetophenone as photoinitiator, resulting in a clear varnish having a viscosity at 25C of about 2000 cps. A sheet of coated offset paper was prepared by coating an ink film using a hand proofer with a large charge o black ink on its surface so as to obtain two com-plete roller revolutions down the center of the sheet from top to bottom then immediately applying the varnish over the ink film with another hand proofer equipped with a 180 line/inch quadragra wre engraved metering roll. The printed -and coated paper thus formed was then immediately passed through an ultraviolet curing unit delivering a flux of 160 watts per square foot, under a nitrogen atmosphere, over a path length of 2 feet. The conveyor belt speed was set at 275 ft.lmin giving an exposure time of about 0.44 second. Cure of the varnish was ~udged to be complete by virtue of its resistance of fingernail scratch. The -properties of the varnish over the ink film were evaluated 20 hours after curing. Flow-out and wet~ing were judged to be good using vi~ual comparative methods. Gloss level measured by a 60C gloss meter was 72 percent.

Example7_ There were charged to the apparatus described in Example 4~a.7 grams of an 80/20 mixture of 2,4-and 2,6-isomers of toluene diisocyanate and 5 drops of dibutyl tin dilaurate as catalyst. While the temperature was maintained at about ambient with the cooling water bath, 7 grams of 2-hydroxyethyl acrylate was added dropwise with stirring.
When the additLon was complete the mixture was stirred at room temperature for about 3 hours to complete the formation of the isocyanato terminated prepolymer. Thereafter 50 grams of the silicone poylcarbinol described in Example 5 was added dropwise. After this addition the mixture was stirred at ambient temperature for about 16 hours to form the acrylated urethane silicone composition; after which 0.01 gram of hydroquinone monomethyl ether was added as polymerization inhibitor. Thereafter 73 parts of the ~;
acrylated urethane silicone was formulated with 25 parts of the diacrylate derivative of the 4 mole ethoxylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy-propionate and 2 parts of ~ -di-S-butoxyacetophenone as photoinitiator. This formulation was applied to coated offset paper and cured using the procedure described in Example 6. The resultant dry film was glossy and free of surface tack.
Example 8 There were charged to the apparatus described in Example 4, 35.5 grams of isophorone diisocyanate and 5;~
drops of dibutyl tin dilaurate as catalyst. While the temperature was maintained at about ambient with the cooling water bath, 20.0 grams of 2-hydroxyethyl acryIate was added dropwise with stirring. When the addition was complete the mixture was stirred at room temperature for about 4 hours to complete formation of the isocyanato terminated prepoplymer. Thereafter 50 grams of silicone polycarbinol~ `
described in Example 4 was added dropwise. After thls addition the mixture was stirred at ambient temperature 3 ~

for about 16 hours to form the acrylated urethane silicone composition. Thereafter 73 parts of this acrylated urethane silicone was formulated wit~ 25 parts of trimethylolpropane triacrylate and 2 parts of,~ "~-di-S-butoxyacetophenone as photoinitiator. The formulation had a viscosity of 1010 cps at 25C. The mixture was appliçd as a varnish over uncured ink and cured following the procedure described in Example 7 resulting in a tack-free surface. After the varnish was cured, the sheet was aged for about 20 hours and evaluated using the tests used in Example 6. The results were as follows 60 gloss - 82% ~;
flow-out - fair to good wetting - good Example 9 There were charged to the apparatus described in Example 4, 10.5 grams of a mixture of 2,2,4- and 2,4,4-isomers of trimethyl hexamethylene diisocyanate and 5 drops o~ dibutyl tin dilaurate as catalyst. While the temperature was maintained at about ambient with the cooling water bath, 7 grams of 2-hydroxyethyl acrylate was added dropwise with stirring. When the addition was complete the mixture was stirred at room temperature for about 4 hours to form the isocyanato terminated prepolymer.
Thereafter 50 grams of the silicone polycarbinol described in Example 4 was added dropwise. After this addition the mixture was stirred at ambient temperature for about 1~

~13~L9~4 16 hours to complete production of the acrylated urethane silicone. Thereafter 73 parts of this acrylated urethane silicone was for~ulated with 25 parts of pentaerythritol acrylate and 2 parts of~vO~-di-S-butoxyacetophenone as photoinitiator. The formulation had a viscosity of 2300 cps at 25C. It was then applied over uncured ink and cured following the procedure described in Example 6 re-sulting in a clear tack-free film. After the varnish was cured, the sheet was aged for 20 hours and evaluated ~-using the tests in Example 6. The results were as follows~
60 gloss - 76%
flow-out - fair ' wetting - good `~ ;~
"''~, ..
Example 11 Four varnishes were prepared using the pro-cedure described in Example 6. For comparative purposes, ~-two other ~arnishes, representing the heretofore state of the art were produced and evaluated using the same pro- ~
cedures. The compositions of each varnish and the results~;
of the evaluation are shown in Table I. /~
' " .

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~34~8~

TABLE I
Varnish (parts by weight) A B C D E F
Acrylated Urethane Silicone of Example 4 39 50 42 17 - -Polyether Urethane Oligomer - - - 12 2~ -Caprolactone Polyol Urethane Oligomer ~ 8 10 Adduct of 1 mole ~-: Isophorone Diisocyanate and 2 moles 2-hydroxy-ethyl acrylate - - - 6 - 16 :~
, Trimethylolpropane triacrylate 61 - 53 60 66 44 Pheno~yethyl acrylate - - 5 5 5 12 , -di-S-butoxyaceto-:
phenone 2 2 2 ~ 2 2 2 Compound A
20 Compound B - 50 - - - -60 gloss 74 78 72 ~ 75 67 68 ~ Flow-out Good Good Fair Good Fair Good :~ : to to ::
Good Good ~ - -Resistance to cracking .: .-when folded Good Exc. Exc. Good Fair Fair ;. .-, ,-~ .

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Compound ~ - (CH3) 3Si4)S ~ OS (CH3) C3H6 ~2H4)~3~I603~ (CH3) Compound B - The diacrylate derivative of the 4 mole ethoxylate of 2,2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxypropionate This example demonstrates the superior properties of varnishes employing the acrylated urethane silicones of this invention over those of the heretofore present state o f the art.

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Claims

WHAT IS CLAIMED IS

1. Acrylated urethane silicone reaction products of the reaction of:
A - a silicone carbinol of the formula or wherein R' is an alkylene group having from 1 to 16 carbon atoms; n is an integer having a value of 2 or 3; x has a value of from 1 to 1000; y has a value of from O to 15;
and $ has a value of from 1 to 6;

B - an organic polyisocyanate of the formula Q(NCO)m wherein m has a value of from 2 to 5 and Q can be linear or branched alkylene having from l to 10 carbon atoms;
arylene, alkarylene or aralkylene having from 6 to 12 carbon atoms; cycloalkylene having from 5 to 10 carbon atoms; or bicycloalkylene having from 7 to 15 carbon atoms; and C - a hydroxyalkyl acrylyl compound of the formula wherein X is hydrogen or methyl and R" is a linear or branched divalent alkylene having from 2 to about 5 carbon atoms.

2. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said silicone carbinol has the formula

3. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said silicone carbinol has the formula

4. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said organic poly-isocyanate is isophorone diisocyanate.

5. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said organic poly-isocyanate is bis(4-isocyanatocyclohexyl)methane.

6. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said organic poly-isocyanate is toluene diisocyanate.

7. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said organic poly-isocyanate is trimethyl hexamethylene diisocyanate.

8. Acrylated urethane silicone reaction products as claimed in claim 1 wherein said hydroxy-alkyl acrylyl compound is 2-hydroxyethyl acrylate.

9. In a radiation-curable coating the improvement therein of formulating the radiation curable coating with acrylated urethane silicone reaction products of the reaction of:
A - a silicone of the formula or wherein R' is an alkylene group having from 1 to 16 carbon atoms; n is an integer having a value of 2 or 3;
x has a value of from 1 to 1000, y has a value of from O to 15; and ? has a value of from 1 to 6;

B - an organic polyisocyanate of the formula Q(NCO)m wherein m has a value of from 2 to 5 and Q can be linear or branched alkylene having from L to 10 carbon atoms;
arylene, alkarylene or aralkylene having from 6 to 12 carbon atoms; cycloalkylene having from 5 to 10 carbon atoms; or bicycloalkylene having from 7 to 15 carbon atoms;
and C - a hydroxyalkyl acrylyl compound of the formula wherein X is hydrogen or methyl and R" is a linear or branched divalent alkylene having from 2 to about 5 carbon atoms.

10. An improved radiation-curable coating as claimed in claim 9 wherein said silicone carbinol has the formula

11. An improved radiation-curable coating as claimed in claim 9 wherein said silicone carbinol has the formula

12, An improved radiation-curable coating as claimed in claim 9 wherein said organic polyisocyanate is from the group comprised of isophorone diisocyanate, bis(4-isocyanoeocyclohexyl)methane, toluene diisocyanate and trimethyl hexamethylene diisocyanate.

13. An improved radiation-curable coating as claimed in claim 9 wherein said hydroxyalkyl acrylyl com-pound is 2-hydroxyethyl acrylate.