CA1246785A - Blends of cyclic vinyl ether containing compounds and a poly(active hydrogen) organic compound - Google Patents

Abstract

BLENDS OF CYCLIC VINYL ETHER
CONTAINING COMPOUNDS AND A POLY
(ACTIVE HYDROGEN) ORGANIC COMPOUND

ABSTRACT OF THE INVENTION

Described herein are compositions suitable for photocopolymerization comprising a cyclic vinyl ether containing compound and a poly(active hydrogen) organic compound. Photocurable coatings can be prepared from such composition and such coatings have improved flexibility and impact resistant properties.

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

Description

,., -- 1 --iZ4~'785 BLENDS OF CYCLIC VINYL ET~ER
~coNTaINING COMPOUNDS AND a POLY
(ACTIVE ~YDROGEN) ORGANIC COMPW ND
~AC~GROUND OF THE INVENTION
It l~ well ~nown that coating~ play a u-eful role in the manufacture of a wide variety of u-eful article-. Until recently, nearly all coatings ~ere formulated and applied by employment of an organic olvent, which often compri~ed a ma~or portion of the total formulated coating After the coating is applied to the article to be coatcd, the organic olvent i- evaporated leav$ng the dried coating on the article to erve ~t~ decoratlve or functional purpo-e This coating ~ystem has met with increasing ai-favor as tbe co-t of energy needed to evaporate the ~olvent at the rate required by industry increased, as the price of the ~olvent increased, and as the deleterious environmental effect~ of the evaporated solvent became better understood. In addition, governmental regulations have placed ever increasing restrictions on the amount~ and types of solvents or organic volatiles permieted to escape into the atmo~pher- fro~
coatiAgs compo~itions. Systems aimed at ~olvent recovery to reduce pollution and conserve solvent have generally proven to be energy inten-ive and expensive.
Consiaerable effort- have been expended by those killd ln the art to develop coating composition~ having a minimal amount of volatile organic component- and thi~ ha~ l d to development of powder coatlngs, radiation-curable coatings, water borne coatings and high solids coatings In these recent development~, the amounts of organic ~ olvents present are minimal and con~equently there is i little or no atmo-pheric pollution ~ .
~ - D-13,833 ~`~` 2 124~785 A~ong the new eoating ystems, radiation-curable eoatings, usually eurea with ultraviolet light or electron beam radiation, offer a variety of aavantages They require only mini~al energy to effect cure -- change from liquid to solid ~tate -- th-y aO not conta~n olvents, and thu~ ~o not eause deleteriou~ effects to the environment, an~ they are eost effective, ~ince effectively all of the applied liguld i~ eonvertea to a solid eoating an important disadvantage of photocurable ystems i8 the frequent reguirement that the euring process be eonauetea in an inert atmosphere beeause of the inhibiting effeet of oxygen Responding to ueh problems, those ~killed in the art have devised photocurable eoatings which eure through a mechani~m termed cationic polymerisation In these ~y~tems, the starting materials are mixed with eatalysts which form aeids when exposed to ultraviolet lights the ~tarting materials are therefore polymerized via cationic eataly~is Epoxy resins, linear vinyl ethers, and cyclic vinyl ether~ have been shown to be suitable ~tarting materials for photocure via eationic polymerization, as diselosed in, for example, U S
Patent 3,794,576~ the publication ~New Monomers for Cationie UV-Curing~, Conference Proceedings, Radiation Curing VI, page~ 4-28, September 20-23, 1982; ana Brlti-h publication GB 2,073,760A
~ owever, a photoeurable coating compo~ition that can be curea by cationic polymerization and having increased toughness over compositions as are currently known would be highly desirable .

D-13,833 :
.

~ ~2~7~5 TH~ INVENTIO~
It has now been found that photocurable coatings can bc prepared from blends of cyclic vinyl ether containing compounds and a poly(active hydrogen) organic compound. These photocurable coat~ngs can be cured by cationic polymerization.
These novel photocurable compositions cure to give coatings with markedly improved flexlbility ana ~mpact resistaDt properties. The blend can optionally contain an cpo~ide and/or a linear vinyl ether compound.
The cyclic vinyl ethers suitable for use in this invention incluae dihydropyranyl and/or di-~dihydropyranyl) compounds.
The ai- ~dihydropyranyl) compounds employed in the present invention co~pri~e two 3,~-dihydro-2H-pyranyl rings which are interconnected by a linking chain bonded at either end to the 2-position of the respective pyranyl rings. In simplified form, the preferred compounds for use in the present invention have the following general Pormula A:

S - ~-X -O,-X ~-s wherein:
. Z and Z " when Z and Z' are defined herein the aefinition includes Z2 and Z'2) each represents hydrogen or an alkyl group having from 1 to 10, and usually no more than 6, carbon atoms;

D-13,833 lZ~;785 X ~n~ X' are ~ember~ of the cla--con~isting of a bivalent saturated hydrocarbon group, R, having the tructure, ~Cn~2n wherei $s an integer having a value of from 1 to 10; an oxy radical, -O-: and a carbonyl group, -C(O)-; and, in addition X' may be a carbonyloxy group, -O~O)C-, the carbon atom of which $B bonded to the 2-position of the dihydropyranyl ring; X and X' may be the same or different prov$ded that taken together they contain either ~ero or 2 oxygen atoms;
a has a value of from zero to 1, a being rero only when X' i8 the aforesaid carbonyloxy group;
Q i- a member of the class consisting of the aforesaid R group; a dioxylakylene group, -ORO-, wherein R i- as defined aboves a dicarboxylate group, -OC-(O)-R'-C~O)O,- wherein R' iQ the nucleus of a dicarboxylic acid; and a polycarbamate group ~uch as the dicarbamate group, -OC(O)NH-R~-NH-C(O)O-, wherein R~, as illustrated, is the nucleu~ of a aiisocyanate: and X, X' and Q taken together is such that the linking chain, -X-Q-X'-, containQ an even number of oxyger ~toms from two to four, provided tha~ wben X
and X' are both oxy radical~, the linking chain contains no other oxygen atom_ (that is, Q or R), and when X and X' are both carbonyl groups, the linking chain contains four oxygen atoms ~that is, Q
$8 -ORO-) Among the uitable di-(dihydropyranyl) compoun~- wh$ch are useful $n accordance with the teachings of thi~ $nvention are the following classes of compounds designated by Formulas A-l through A-6 below D-13,833 _ 5 _ 1. 3,~-aihydro-2~-pyran-2-methyl(3~-aihydro-2H-pyran-2-carboxylates) having the formula:

¢~C82 - O - C ~
wherein Z and Z' are a~ above-defined. Preferably a total of from 5 to 7 of the re~pective Z and Z' group~ are hydroqen and corre~pondinqly, from 3 to ero are alkyl group~. When Z and Z' are alkyl groups, they are usually bondea to the 2- and/or 5-po~ition of the respective ring~. Typical example~ of thi~ clas~ of reactants arc:
3,~-dihydro-2-B-pyran-2-methyl(3,4-dihydro-2H-pyran-2-c~rboxylate) and corresponding alkyl-~ub~tituted compounds uch as 3,~-dihydro-2,5-dimethyl-2H-pyran-2-methyl(3,4-dihydro-2,5-dimethyl-2H-pyran-2-carboxylatels 3,~-dihydro-2,5-dii~obutyl-2B-pyran-

2-# thyl(3,~-aihydro-2,5-aii~obutyl-2H-pyran-2-carboxylate): 3,~-dihydro-2,5-dihexyl-2~-pyran-2-methyl (3,4-aihydro-2,5-dihexyl-2H-pyran-2-carboxylate)s and 3,~-dihydro-2,5-aidecyl-2B-pyran-2-methyl(3,~- dihydro-2,5-diaecyl-~-pyran-2-carboxyl~te). The 3,~-aihydro-2B-pyran-2-methyl-(3,4-dihyaro-2B-pyran-2-carboxylate) which i~
commonly referred to as acrolein tetramer i~
preferred ana has the ~tructures C~2 o ~1~

2.
Alkanedioxy-bis(3',4'-dihydro-2'B-pyran-2'-carbonyl) compounas having the structure:

D-13,~33 .

~ C - - ~Cnh20) ~ 2l wherein Z and Z' are as above-di~cus8ed, and n is an integer from 1 to 10, preferably from 1 to ~ .
Typichl examples of such compounds which are ~uitable in the practice of this invention are:
1,2-ethanedioxybis-(3',~'-dihydro-2'~-pyran-2'-carbonyl)t 1,2-ethanedioxybis-(3',~'-dihydro-5'-methyl-2'H-pyran-2'-carbonyl), and corresponding 1,2-i60propanedioxy and 1,4-butanedioxy compounds.
Such compounds can be prepared by the reaction of an alkylene dihalide, X~ -(CnH2n)-X~, wherein n is as aforesaid, and X~ iB halogen, particularly iodine, chlorine or bromine, with the cilver ~alt of a

3,~-dihydro-2H-pyran-2-carboxylic acid. ~he latter ~alts are in turn prepared by the oxidation of 3,4-dihydro-2H-pyran-2-carboxaldehyde in the ~resence of a silver salt 6uch as silver oxide, preferably in an anhydrous medium containing an organic solvent ~uch as benzene, as described in U.S. Pat. No. 2,514,172.
3. Bis-~3',4'-dihyro-2'H-pyran-2'-oxy)alkanes having the formula:

~CnH2n) ~~0 3 wherein Z, 8' and n have the significance discussed above. Illu~trative compounds of this group of di-(dihydropyranyl) compounds are: 1,2-bis-~3',~'-D-13,833 ,, lZ4~785 _ 7 -~ihydro-2'~-pyr-n-2'-oxy)ethane5 1,2-bis~3',~'-dihydro-5'-methyl-2'a-pyran-2'-oxy)ethane; 1,3-bis (3',~'-dihydro-5'-methyl-2'B-pyran-2'-oxy)propane ~nd 1,~-bi~3',~'-dihydro-2'a-pyran-2'oxy)butane.
Such compounds are prepared by Diels-Alder addition reaction~ of divinyl bi~-ethers such a~ the divinyl ether~ of alkylene glycol~, with alpha, beta-un~aturated aldehydes such a~ acrolein, methacrolein, and crotonaldehyde under conditions described, for example, by Curtis W. Smoth et al., Journal of the american Chemical Society, Vol. 73, 5267 ~1951). For example, the reaction between a mole of ethylene ~lycol divinyl ether and 2 moles of acrolein provides 1,2-bis(3" ,~'-dihydro-2'8-pyran-2'-oxy) ethane.
~ . Bi~-(3',~'-dihydro-2'H-pyran-2'-al~oxy) alkanes having the formula:

~(Cn82n)-0-(Coll2n)-o-(cn~(2n) ~
a-4) wherein ~, Z' and n are as defined hereinabove.
Typical exa~ple~ of thi- type of reactant are:
1,1-bi~(3',~'-dihydro-2'8-pyran-2'-methoxy)ethane;
1,1-bi~(3',~'-dihydro-5'-methyl-2'8-pyran-2'-methoxy)ethane; and 1,2-bi~(3',~'-dihydro-2'H-pyran-2'-methoxy)ethane. Such compounds are prepared by the addition of alpha, beta-unsaturated aldehyde~
~uch a~, for example, acrolein and methacrolein) to the corre~ponding bis-un~aturated ethers.
5. Bi~-~3',~'-dihydro-2'H-pyran-2'-alkyl) carboxylates having the general formula:

D-13,833 -~ - 8 - 12~785 (Cn~2n)-0-C-R-~~o tCn~2n) ~ Z2 ~A-5) wherein Z, 8' and n are as above-defined; ana R' is the nucleus of a dicarboxylic acid and may be a bivalent aliphatic, cycloaliphatic or aromatic nucleus including corresponding halogen-substituted nuclei. Thus, R' may be: a bivalent alkylene group, ~tCn- ~2n-)~~ wherein n is an integer of from 1 to 10 a~ in the ~aturated acyclic dibasic acid series, BOOC-(CH2)n--COOH, an alkenylene group baving from 2 to 10 carbon atoms as in maleic acid and itaconic acid; dimer or trimer acids, or mixtures thereof; an arylene group as in phthalic, i~ophthalic and terephthalic acids; an aralkylene nucleu~ a~ in homophthalic acid; cycloaliphatic nuclei as in the hydrophthalic acids including di-, tetra-, and hexa-hydrophthalic acids, and bicyclol2.2.11hept-5-ene-2,3-dicarboxylic acid; and corresponding halogenated nucli as in chloromaleic acid, tetrachloro- and tetrabromophthalic acids and chlorobicyclo[2.2.11-hept-5-ene-2,3-dicarboxylic acids such as chlorendic acid. Specific examples of thiC
cla~s of compounds are: bis-t3,~-dihydro-2~-pyran-2-methyl)--uccinate, -adipate, -azelate, -~ebacate, -tetrachlorophtha- late, -tetrabromophthalate and -chlorendate. Thi~ type of reactant i~ prepared by the conden~ation of 3,~-dihydro-2a-pyranyl-2-alkanols with the dibasic acid or acid halide of the dibasic acid.
6. Poly-t3',~'-dihydro-2'a-pyran-2'-alkyl) carbamates which compri~e the reaction products D-13,833 : .

g_ 12~785 formed by con~en-ation of 3,4-dihydro-2~-pyranyl-2-carbinols ana an orqanic polyi-ocyanate uch as tho~e described below Among the suitable polyi~ocyanates which may be used in the preparation of such mono~ers for u~e in the present invention are those having thc formula, R~NC0)~, wherein i is an integer of two or more and R~ is an organic radical having the valence of i R~ can be an ~llphatic, cycloaliphatic or aromatic radical which ~ay be unsubst~tuted hydrocarbyl groups or hydrocarbyl groups ~ubstituted, for example, with halogen or alkoxy groups Thus, when i is two, for example, R~ is a bivalent substituted or un-ubstituted hydrocarbon group such as alkylene, cycloalkylene, arylene, alkyl--ubstituted cycloalkylene, alkarylene, aralkylene ana like groups ~ypical examples of such polyisocyanates arc: 1,6-hexamethylene ~iisocyanate;
l,~-tetramethylene diisocyanate;
l-methyl-2,~-diisocyanatocyclohe%ane;
bist~-isocyanatophenyl)methane; phenylene diisocyanates uch as ~-methoxy-1,3-phenylene-diisocyanate, 5,6-dimethyl-1,3-phenylenedii~o-cyanate, 2,~-and 2,6-tolylene diisocyanates, tolylene dii-ocyanate, 6-isopropyl-1,3-phenylene-diisocyanate, durylene dii-ocyanate, triphenyl-aethane-~ -triisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl-isocyanate, or ~,~'-dicyclohexyl-methylene diisocyanate and many other oranqic polyisocyanates that are known in the art such as thoae aisclo~ea in an article by Siefkin, Ann 565,75 tl949). Also included as useful in the preparation of the carbamate monomers employed in this invention are the polyi~ocyanates of the aniline-formaldehyde poly-aromat~c type wbich are produced by phosgenation of the polyamine D-13,B33 12~785 obtained by acid-catalyze~ condensation of aniline with formaldehyde Polyphenylmethylene polyisocyanates of this type are a~v~ilable commercially unaer uch ~trade ~ a~ PAPI, AFPI, Mondur MR, Isonate 390P, NCO-120 and NCO-20. The products are low viscosity ~50-500 centipoises at 25-C.) liquid~ having average i-ocyanato functionalities in the range of about 2 25 to about 3.2 or higher, depending upon the pecific aniline-to-formaldehyde molar ratio used in the polyamine preparation Other useful polyisocyanates are combinations of diisocyanates with polymeric isocyanates containing ~ore than two isocyanate groùps per molecule Illustrative of such combinations are: a mixture of 2,~-tolylene diisocyanate, 2,6-tolylene diisocyanate and the aforesaid polyphenylmethylene polyisocyanates; and a mixture of isomeric tolylene diisocyanates with polymeric tolylene diisocyanates obtained as residues from the manufacture of the diisocyanates When the isocyanate which is reacted with the 3,~-dihydro-2H-pyran-2-carbinol contains two i~ocyanato functions, bis-(3',~'-dihydro-2'H-pyran-2-alkyl)dicarbamates are formed having the general formula:
(cHDH2nt-crc-NH R--~H~ ~CnH2n) ~ 2 ~A-6) wherein Z, Z' and n are as defined hereinabove; and R~ corresponds to the R~ nucleus of the i~ocyanate reactant, R~NCO)i when i is two It is to be ~' .
~ D-13,833 , .

12~6785 -- 11 -- .

under~tood that when the ~socyanate ha~ an i~ocyanato function greater than two, the pyranyl monomer will have a corresponding average number of carbamate groups and the general formula:

C5(Z)2 ~cn~2nt-oc~o~-NH R~ [ NHCtO~ O
(CnE{2nt~5~Z' t2~

wherein C5(Z)20 and C5(Z')20 are the re6pective 3,~-dihydro-2H-pyranyl rings. ~ypical examples of this cla~s of di-(dihydropyranyl) compounds are toluene-2,~-(or 2,6)-(bis-3', ~'-dihydro-2'H-pyran-2'-methyl) carbamate, ~nd the reaction products of 3,~-dihydro-2'~-pyranyl-2-carbinol with the aforesaid polymeric liguids having an average isocyanato function of about 2.2S to about 3.2.
It is, of cour~e, understood by those skilled in the art that when such nitrogen containing compounds are used with photoinitiators, only minor amounts of basic organic nitrogen containing compounds may be u~ed 80 a~ not to interfere with the polymerization reaction.
Additional cyclic vinyl ether compounds include the following:

~ CH20H ; ~ CH
Rl Rl ~ H20X ; ~ OR
Rl wherein Rl is hydrogen or methyl, Rl'" is alkyl -of 1 to 10 carbon atoms, and X i6 6elected from D-13,833 ~2~L6785 ~~CB2-CIH-O)n B 5 -~-Rl' or -[~ C)-0-1-Rl R3 wherein n has a value of from 1 to 50 and wherein Rl' is the residue of a carboxylic acid and can be - ~1) bydrogen, (2) alkyl which is substituted with any ~ub~tituent which does not unduly interfere with the polymeriration, or unsub~tituted, linear or branched, containing up to 20 carbon atoms, ~uch as methyl, ethyl, isopropyl, decyl, eico~yl and the li~e, and ~3) aryl ~hich ~ ~ubstitutea with any ubstituent which doe~ not unduly interfere with the polymerization or, which i~ unsub~tituted, having 6 to 10 ring carbon atoms, uch as phenyl, naphthyl, benzyl, penethyl, and the li~e.
Another group of compounds which are u~eful in the compositions of this invention are the alkylene oxide adduct~ of 3,4-dihydropyran-2-methanol of the general formula:

~ ~ ~CH~O(CH2-CHO)n 11 .~ Rl wherein Rl and n are as hereinbefore defined.
Shis cla~s of compound~ ~8 prepared by the ethoxylation or propoxylation of 3,~-dihydropyran-2-methanol with a base cataly~t uch a~ pota~ium or sodium metals. The cataly~t concentration can be from 0.1 weight percent to 0.4 weight percent, preferably from 0.2 weight percent to 0.3 weight percent ba~ed on the weight of the ~ final product. The reactlon can be carricd out at a ; temperature of from about 75-C to about 150-C, preferably from about lOO-C to about 120-C.

:
~ D-13,833 t 124~7~5 -- ~3 --Another group of compounds which can be u~ed in the composltions of this invention are the lactone adduct- of 3,~-dihydropyran-2-methanol of the general formula:

~CH20tC--(C )--01~

wherein R3 i- hydrogen, alkyl, alkoxy, aryl, cycloalkyl, alkaryl, or aralkyl group having up to 12 carbon atom~ and at lea~t ~2X-3) of tbe R3 groups are hydrogen atoms, x has a value of 2 to 12, and R
ana n are as hereinbefore ae~cribed This class of compounds 1~ prepared by reactlng a lactone with 3,~-aihydropyran-2-methanol at a temperature of lOO-C to 200-C a cataly~t ~uch as ~tannous octanoate on ~ibutyl tin ailurate and the like ~an be used to facilltate the polymerization ~he lactones that can be used are epsilon-caprolactone, epsilon-methyl-epsilon-caprolactone, gumma-methyl-ep~ilon caprolactone, beta-propiolactone, deta-valerolactone, seta-enantholactone, gamma-ethyl-ep5 ilon-methJl-epsilon-caprn;actone, and the like These lactone adduct- of 3,~-dihydropyran-2-methanol may be reacted with alkylene oxide~ ~uch a~ ethylene oxide or propylene oxiae to fro~ alkyleneoxide adduct~ of the lactone adducts of the general formula:

olc-~cilio~ cH2-c~o)--nR

wherein Rl, R3, n, and x are as hereinbefore describea :' D-13,833 .

12~6q8;5 Incluaed ln thi~ class of compounds would be the lactone adducts of the ~lkylene oxide adducts of 3,~-dihydropyran-2-methanol of the general formula:

~C1120(CH2-CH o)~c (J),~o]~

wherein Rl, R3, n, and x are as hereinbefore - -described.
Still another qroup of compounds which can be u~ed in the composition~ of this invention are the esters of at least one organic carboxylic acid and 3,4-dihydropyran-2-methanol corresponding to the , formula:

2CRl wherein Rl and Rl' are as hereinbefore defined.
These compounds are prepared by conventional esterification or transesterification procedures with a uitable cataly~t and can conta:n substituent~ in the molecule provided they do not unduly interfere with the reaction. ~hese procedures and catalysts are well known to those rkillea in the art and reguire no further elaboration. In the transesterification, the lower alkyl e~ters of organic acid~ are preferred sources of the acid ~oiety.
Another group of compounds which can be used are reaction products of the following:
10~3~
Rl .

D-13,833 ' - 15 - lZ~785 whereln Rl ~s a- previously defined with compounds such as pentaerythritol, formaldehyde, other aldehydes ~uch as isobutyraldehyde to yield cyclic vinyl ether products such as:
~C~3C-c3 ~C~

CH20~

The poly~active hydrogen) organic compounds of this ~nvention include any compatible organic compounds containing two or more active hydrogen atoms per molecule; The poly(active hydrogen) organic compounds are well known to those ~killed in the art and include, for example, organic polyols and the like.
Substantially any of the organic polyols previously used in the art to make coating compositions can be used and are preferred as the poly(active hydrogen) organic compounds in this invention. Illustrative of the polyols useful in producing coating composition~ in accordance with this invention are the polyether polyols such as polyhydroxyalkanes and polyoxyalkylene polyols, the acrylic and vinyl polyols, the polyester polyols, the polycaprolactone polyols and other lactone polyols such a8 polyvalerolactone polyols, poly-methyl-caprolactone polyols, etc., the D-13,833 ~Z4~785 polymer/polyolo, and the like Among the polyether polyols which can be employed are those selected from one or more of the following classes of compositions, alone or in admixture, known to tho~e ~killed in the art:
(a) Alkylene oxide adducts of polyhydroxyalkanes;
~ b) Alkylene oxide adducts of non-reducing ougars and sugar derivativ-s;
(c) Alkylene oxide adducts of phosphorus and polyphoQphorus acids;
~ a) Alkylene oxide adducto of polyphenols;
~ e) The polyol~ from natural oils such as castor oil, and the like Illustrative alkylene oxide adducts of polyhydroxyalkaneo incluae, among others, the alkylene oxide adducto of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5-, and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6-, and 1,8-dihydroxyoctane, l,10-dihydroxydecane, glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane, l,l,l-trimethylol-thane, l,l,l-trimethylolp-opane, pentaerythritol, polycaprolactone, xylitol, arabitol, orbitol, mannitol, and the like A
preferred class of alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, adducts of trihydroxyalkanes A further claso of polyether polyolo which can be employed are the alkylene oxide adducts of the non-reducing sugars, wherein the alkylene oxides have from 2 to 4 carbon atoms Among the non-reducing ougaro and ougar derivatives contemplated are ucrooe, alkyl glycosides uch a9 D-13,833 ethyl glucoside, ethyl glucosiae, and the like, glycol glycos~des ~uch as ethylene glycol gluco~ide, propylene glycol gluco~ide, glycerol glucoside, 1,2,6-hexanetriol glucoside, and the like, as ~ell as the alkylene oxide adducts of the alkyl glycosides a~ et forth in U.S. 3,073,788.
The alkylene oxide adducts of phospho NS
and polyphosphorus acids are ~nother useful class of polyether polyol~. Ethylene oxide, 1,2-epoxypropane, the epoxybutanes, 3,-chloro-1,2-epoxypropane, and the like are preferred alkylene oxides. Phosphoric acid, phosphorus acid, the polypho-phoric acids uch as tripolyphosphoric acid, the polymetaphosphoric acid~, and the like are de~irable for use in this connection.
A till further u~eful clas~ of polyether polyols i- the polyphenols, and preferably the alkylene oxide adduct~ thereof wherein the alkylene oxides have from 2 to 4 carbon atoms. Among the polyphenol~ which are contemplated are, for example, bi~phenol A, bi~phenol F, condensation products of phenol and formaldehydej the novolac resins, condencation product~ of variou~ phenolic compounds and acrolein; the ~implest member of this class beinq the 1,1,3-tristhydroxyphenyl) propanes, condensation products of various phenolic compounds and glyoxal, glutaraldehyde, and other dialdehydes, the ~implest member~ of thi- class being the 1,1,2,2,-tetrakislhydroxyphenol) ethanes, and the like.
The polyether polyol~ described hereinabove can have hydroxyl numbers which vary over a wide range. In general, the hydroxyl numbers of the above de~cribed polyols employed in thi~ invention ~,' D-13,833 `~ 12~L678S

can r-ng- from about 15, and lower, to about 900, and higher $he hydroxyl number is defined as the number of milligram~ of potas~ium hydroxide reguired for the complete neutrali~ation of the fully phthalated derivative prepared from 1 gram of polyol The hyaroxyl number can al~o be defined by the equations OH 56 1 x 1000 x f ~.w.
where OB - hydroxyl number of the polyol;
f - functionality, that is, average number of hydroxyl groups per molecule of polyol;
and m.w - molecular weight of the polyol $he polyether polyol~ described hereinabove can be prepared by conventional method~ and are commercially available from a number of manufacturer~
he polycaprolactone polyols, alone or in admixture, that can be used to prepare the coating compositions of thi- invention include any of the known polycaprolactone polyols that are commeraially available and that are fully described, for example, in U.S. Pat No 3, 169,9~5 a~ ae~cribed in thi~
patent the polycaprolactone polyols are produced by the catalytic polymeri~ation of an excess of a caprolactone ana an organic polyfunctlonal initiator having as lea~t two reactive hydrogen atoms The organic functional initiator~ can be any polyhydroxyl compound as i~ hown in U.S Pat No 3,169,g45 Illu-trative thereof are the diol~ such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propylene glycol, polyethylene glycol, polypropylene glycol, poly~oxyethylene-oxypropylene) glycols, ana imilar polyalkyl-ne glycols, either D-13,833 12~785 blocked, capped or heteric, containing up to about 40 or more alkyleneoxy units in the molecule, 3-~ethyl-1-S-pentanediol, cyclohexaned$ol, ~,~'-~ethylene-bis-cyclohexanol, 4,4'-isopropylidene bis-cyclohexanol, xylenediol, 2-~4-hydroxymethylphenyl) ethanol, 1,4-butanediol, 1,6-hexaneaiol and the like; triols ~uch as glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, trii~opropanolamine, and the like:
tetrols ~uch as erythritol, pentaerythritol, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylene diamine, and the like.
When the organic functional initiator is reacted witb the caprolactone a reaction occurs that can be represented $n its ~implest form by the equation:
O R
R~ OB)x~ O-~c~R5) ~HR'~ R~ 1 oc~l ~ CHR5 - ~ - mOH ) x 0~ ¦ R5 In this equation the organic functional initiator is the R4 (OH)X compound ~nd the caprolactone is the O ~ ~ R5 -' I~
compound; thi~ can be caprolactone itself or a ubstituted caprolactone wherein R5 is an alkyl, alkoxy, aryl, cycloalkyl, alkaryl or aralkyl group having up to twelve carbon atoms and wherein at least six of the R' groups are hydrogen atoms, as ~hown in U.S. Pat. No. 3,169,9~5. The polycaprolactone polyols that are used are shown by the formula on the right hand ide of the equation;

D-13,833 , - 20 - ~24~7~5 they can have an average aolecular weight of from 200 to about 6,000. The preferred polycaprolactone polyol compound~ are those having an average molecular weight of from about 290 to about 6,000, aost preferably from about 290 to 3,000. The aost preferred are the polycaprolactone diol compounds having an average molecular weight of from about 290 to about 1,500 and the polycaprolactone triol and tetrol compouods having an average molecular weight of from about 290 to about 3,000; these are most preferred becau~e of their low vi~co~ity propertie-. In the formula m i~ an integer representing the average number of repeating units needed to produce the compound having said molecular weights. The hydroxyl number of the polycaprolactone polyol can be from about 15 to 600, preferably from 200 to 500; ana the polycaprolactone can have an average of from 2 to 8, preferably 2 to ~, hydroxyl group~.
Illustrative of polycaprolactone polyols that can be used in the coating compositions of this invention, one can mention the reaction products of a polyhydroxyl compound having ab average from 2 to 6 hydroxyl groups with caprolactone. The manner in which these type polycaprolactone polyol~ i6 produced is ~hown in U.S. Pat. No. 3,169,945 and aany such compositions are co ercially available.
In the following table there are li-ted illustrative polycaprolactone polyols. The first column lists the organic functional initiator that is reacted with the caprolactone ana the average molecular weight of the polycaprolactone polyol is shown in the second column. ~nowing the molecular weights of the initiator and of the polycaprolactone polyol one can readily aetermine the average~number of aolecule~ of caprolactone ~CPL Units) that reacted to produee the compounds; this figure is shown in the thir~ coluan.

D-13,833 - 21 - 12~6~85 PO~YCAPROLACTONE POLYOLS
average averaqe No.
MW of of CPL units Initiator polyol in molecules 1 Ethylene glycol 290 2 2 Ethylene glycol 803 6.5 3 Ethylene glycol 2,114 18 ~ Propylene glycol 874 7 5 Octylene glycol 602 4 6 D-calene glycol 801 5.5 7 Diethylene glycol 527 3.7 8 Diethylene glycol 847 6.5 9 Diethylene glycol 1,2~6 10 10 Diethylene glycol 1,998 16.6 11 Diethylene glycol 3,526 30 12 Triethylene glycol 75~ .
13 Polyethylene glycol~MW 200)~ 713 4.5 14 Polyethylene glycol~MW 600)~ 1,398 7 15 Polyethylene glycol(MW 1500)~ 2,868 12 16 1,2-Propylcne glycol 646 17 1,3-Propylene glycol 988 8 18 Dipropylene glycol ~76 3 19 Polypropylene glycol~MW 425)~ 83S 3.6 20 Polypropylene glycol~MM 1000)~1,684 6 21 Polypropylene glycol~MW2000)~ 2,~56 4 22 Rexylene glycol 916 23 2-Ethyl-1,3-he~anediol 602 4 24 1,5-Pent~nediol- ~46 3 2S l,~-Cyclohexanediol 629 4.5 26 1,3-9is(hydroxyethyl)-benzene 736 5 27 Glycerol S48 28 1,2,6-~exanetrio' 476 3 29 Trimethylolpropane S90 4 30 TrimethylolpropaDe 7S
31 Trimethylolpropane 1,103 8.5 32 Tricthanolamine 890 6.5 33 Erythritol 920 7 34 Pentaerythritol 1,219 9.5 35 1,~-9ut~neaiol 5~6 ~.0 36 Neopentyl glycol 674 5.0 ~Average molecular weight of glycol.
The ~tructures of the compounds in the above tabulation ~re obvious to one a~illed in the art based on the information given. The structure of compound No. ? i~s D-13,833 .

O~(C~2)5CO~rCH2CH20CH2C~2[0~(CE12)5~oH
wherein the variable r is an integer, the ~um of r +
r has an average value of 3.~ and the average ~olecular weight 1~ 527. The structure of compound No. 20 i~:
O O
~~C~2)5CO ~ C3~60t-nc3~6~oc(C~2)S~r ~herein the ~um of r ~ r has an average value of 6 and the average aolecular weight i~ 1,684. ~hi~
explanation makes explicit the ~tructural formulas of compounds 1 to 3~ ~et forth above.
Polycaprolactone hexol~ suitable for use in the present invention can be prepared by the catalytic polymeri~ation of an excess of polycaprolactone polyols and a cycloaliphatic epoxide. Illustrative polycaprolactone polyols u~eful in the preparation of polycaprolactone hexols include polycaprolactone diols, polycaprolactone tr$ol~ and the like including mixtures thereof.
Many of the~e polycaprolactone polyols are commercially d~ailable from Ur.fon Carbide Corporation. Cycloaliphatic epoxides suitable for use in prepar$ng the polycaprolactone hexols include 3,~-epoxycyclohexylmethyl-3,~-epoxycyclohexane carboxylate, bi- ~3,~-epoxycyclohexylmethyll adipate, vinyl cyclohexane dioxide and the li~e.
Many of the~e cycloaliphatic epoxides are commercially available from Union Carbide Corporation. A ~uitable polymerization catalyst is diethylammonium triflate which is,,commercially available from the 3M Company as ~ ~hon4J
;

D-13,833 ~Z4~785 A preferred method for preparation of the polycaprolactone hexols compri~es aaaing one or more polycaprolactone triols to a reactor, heating the polycaprolactone triols to a temperature of ~bout lOO-C and adding the catalyst using a nitrogen sparge as soon as the polycaprolactone triols are molten. The polycaprolactone triols and catalyst mixture is then heated to a temperature of from about 150C to about 200C and a cycloaliphatic epoxide is added to the mixture. The reaction is carried out for about one hour to about three hours or until the oxirane content has been reduced to a nil or almost a nil value. A modification of this process can involve initially adding all of the ingredients into the reactor. A further modification of this method can involve a vacuum treatment of from 10 to 30 minutes after the catalyst addition and/or the use of a vacuum during the heating of the polycaprolatone triols to a molten state. Preferred polycaprolactone hexols suitable as ingredients ~n the coatina compositions of thi~ invention have an average molecular weight of from about 600 to about 1500.
The polymer/polyols that can be used to prepare the coating compositions of this invention are known materials. 8uch polymer/polyols can be produced by polymerizing one or more ethylenically unsaturatea monomers dissolved or dispersed in a base polyol in the presence o~ a free radical catalyst. The production of polymer/polyols is more fully described in U.S. Patent Reissue 28,715, U.S.
Patent Reissue 29,116, U.S. Patent 3,652,639, U.S.
Patcnt Reissue 29,014, U.S. Patent 3,950,317, U.S.
., D-13,633 ~ ' ^ 24 -Patent 4,208,314, U.S. Patent 4,104,236, U.S. Patent

4,172,825 and U.S. Patent 4,198,488.
Wh$1e polytoxypropylene) polyols are preferred, substantially any of the polyol~
previously used in the art to make polymer/polyols can be u~ed a5 the base polyol. Illustrative of the base polyols useful ~n producing polymer/polyol compositions are the polyether polyols such as polyhydroxyalkanes and polyoxyalkylene polyols, or the like. Among the base polyols which can be employed are those ~elected from one or more of the following classes of compositions, alone or in admixture, known to those skilled in the art and described more fully hereinabove:
(a) Alkylene oxide adducts of polyhydroxyalkanes;
~ b) Alkylene oxide adducts of non-reducing sugars and sugar derivatives;
~ c) Alkylene oxide adducts or phosphorus and polyphosphorus acids;
(d) ~lkylene oxide adducts thereof of polyphenols;
(e) The polyols from natural oils such as castor oil, ~nd the like.
The most preferred base polyols employed in the polymer/polyols which are u~eful as ingredients in the coat~ng compositions of this invention include the poly(oxypropylene) polyols. It should be nppreciated that a blend or mixture of more than one base polyol can be utilized, if desired, to form the polymer/polyol.
Conceptually, the monomers used in preparing the polymer/polyols can comprise any ethylenically unsaturated monomer or monomers. A

D-13,833 124~785 variety of monomer~ are disclosed in the patents relating to polymer/polyols previously referred to.
The selection of the monomer or monomers used will depend on considerations such as the relative cost of the monomer~ and the product characteristics required for the intended applic~tion.
The preferred monomer and monomer mixture used to make the polymer portion of the polymer~polyols i~ acrylonitrile and a mixture of acrylonitrile and styrene respectively. The relative weight proportions of acrylonitrile to styrene can range from about 80:20 to about 20:80.
It may be desirable in ~ome applications to utilize, with acrylonitrile, a comonomer other than styrene.
Representative examples of suitable comonomers include methyl methacrylate, vinyl chloride;and ` vinylidene chloride.
The polymer and polyol content of the polymer/polyols can vary within wide limits, depending upon the requirements of the anticipated end use applica:ion. In general, the polymer content will vary from about 10 to about 50 percent, based upon the weight of the polymer/polyol. The polyol content of the polymer/polyols varies from about 50 to about 90 percent, based upon the weight of the polymer/polyol.
-- The polymer/polyols may, if desired, be blendcd with other conventlonal polyols described hereinabove to reduce the polymer content to the level de~irable for the particular end use applicatlon~ Blends in which the resulting polymer content 18 as low as 4 percent of the total weight of the blend or even less m~y be useful in the coating compositlons of this invention.

D-13,833 ;
.

` -- 26 --2~G785 The moat preferred classes of~~oryol~
employed in the coat~ng compos~tions of tbi~
invention are the polycaprolactone polyols ~uch as TONE-0200*and TONE-0305*commercially available from Un$on Carbide Corporation, the dihydroxyl funct~onal polytetramethylcnc ox~de polyols such as Polymeg*
650, 1000 and 2000 co~mcrc~ally available from Quaker Oats Company, thc polymer/polyols such as NIAX Polymer Polyol 31-23 and 34-28 commerc$ally available from Union Carbidc Corporation, and of course the ethylene oxide and propylene oxide adducts ~ncluding ethylene glycol, diethylene glycol, the polytoxyethylene) glycols, the polytoxypropylene) glycol , triols and higher functlonality polyols uch as L~T-67,*L~T-112,*and ' ~G-56*commcrcially available from Union Carbide Corporatlon. A prcfcrred alkylene oxide derlv d polyol ~uitable for use in the coating compo~itions of thi~ invention ha~ thc follow~ng formula:
R6 ~ (C~2 ~H ~n 3 C~3 wherein R6 ~ alkane of 3 to lQ carbon atoms, prcfcrably 3 carbon ato~s, and n is an intcger of from about 10 to about 25. ~hese polyols also include polytoxypropylene-oxyethylene) polyols;
however, de~irably, the oxyethylene content ~hould comprise les~ than 80 percent of the total and preferably les~ than 60 percent. The ethylene oxide when used can be incorporated in any fa~hion along the polymer chain. Stated another way, the ethylene oxide can be incorporated either in internal blocks, a~ terminal blocks, such as the propylene oxide polyols capped witb ethylene oxide, i.e., NIAX
- * Trade marks D-13,833 .
~"

124~785 7 ff~
A Polyol~1-27 an~ 11-34 and E-474, commercially available from Union Carbide Corporation, or may be randomly distributed along the polymer chain. As is well known in the art, the polyols that ~re most preferred herein contain varying small amount6 of unsaturat~on. Un~aturatlon in ltself does not affect in any adverse way the formation of the coating compositions $n accordance with the present invention.
Other preferred representative examples of organic polyols that may be employed in the coating compositions of this invention include copolymers of hydroxypropyl ~nd hydroxyethyl acrylates and methacrylates ~ith other free radical-polymerizable monomers such as acrylate esters, vinyl halides, vinyl acetate or ~tyrene; copolymers containing pendent hydroxy groups formed by hydrolysis or partial hydrolysi6 of vinyl acetate copolymers, polyvinylacetal resins containing pendent hydroxyl groups; modified cellulose polymers such as hydroxyetbyl~ted and hydroxypropylated cellulose:
hydroxy terminated polyesters and hydroxy terminated polyalkadienes. The polyester polyols are the reaction products of polyfunctional organic carboxylic acids and polyhydric alcohols and include, for example, poly(hexamethylene adipate), poly(ethylene adipate), poly(butylene adipate) and the llke. Many of these organic polyols can be prepared by conventional methods and are commercially available from a number of manufacturers such as polyvinylacetal reslns commercially available ~from Monsanto Chemical Company as Butvar~B-7,2~, B-73, B-76, B-90 and B-98 and as Formvar~7/70 !12/85, 7/95S, 7/95E, 15/95S and D-13,833 lZ4~785 15/9SE; an allphatic polyester diol ~ er ~ ~y available from Rohm and Haas a~ Parap ex1U-14 ;
aturated polye~ter polyols commercialLy avai~able from Mobay Chemical Company as Mu~tro~ ~- ,~ P-12A, R-16, R-18, R-38, R-68, and R-7~s a hydroxypropylated cellulose having an eguivalent ~eight of approx~mately 1~ ~ merci ~ ly available from ~ercule~, Inc. as ~lucel ~ an cellulose acetate butyratc ester having a hydroxyl eguivalent weight of approx~mately ~00 commercially available from Eastman ~odak as Alcohol Soluble Butyrate.
The poly(àctive hydrogen) organic compounds utilized ~n the coating compositions of this invention can be mixture~ or blends of organic polyols. For example, when utilizing a polycaprolactone polyol, lt may be desirable to mix or blend one or more of a propylene oxide polyol, a propylene oxide polyol capped with ethylene oxide, a polytetramethylene oxide polyol or a polymer/polyol therewith. Other mixture~ or blends may similarly be used if desired.
The epoxides which may be used herein contain at least one epoxy group having the formula:

--C C--I
The epoxy groups can be terminal epoxy groups or internal cpoxy groups. The epoxides are primarily cycloaliphatic epoxides. ~hese cycloaliphatic epoxide resins may be blended with minor amount6 of glycidyl type epoxides, aliphatic epoxides, epoxy cresol novolac resins, epoxy phenol novolac resins, polynuclear phenol-glycidyl ether-derived re~in~, aromatic and heterocyclic glycidyl amine resin~, hydantoin epoxy resins, and the li~e, and mixtures thereof. ~he cycloaliphatic epoxide re~ins may al~o ~ ' .

D-13,833 124~78S
be blcnded with minor amounts of cycloaliphatic epoxides having a viscosity of less than 200 centipoise such a-:
~ or~

Further, such cycloaliphatic epoxides may be blended ~ith and other epoxides described above.
These epoxiaes are ~ell known in the art and many are commercially available.
Suitable cycloaliphatic epoxide resins for purposes of this ~nvention arç those having an average of two or more epoxy groups per molecule.
Illustrative of auitable cycloaliphatic epoxides are the following:
FOR~ULA 1 Diepoxides of cycloaliphatic esters of dicarboxylic acids having the formula:

R7 ~ CH2O _ ~R ~ OC~

~--Rll R20 Rl/~13 R2~23 wherein R7 througb R24 can be tbe same or different, are bydrogcn or alkyl radicals generally containing one to nine carbon atoms inclusive, and preferably containing one to three carbon atoms, inclusive, as for example ~ethyl, ethyl, n-propyl, n-butyl, D-13,833 12~4~7~5 n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl and the like; R is a valence bond or a divalent hydro carbon radical generally containing one to twenty carbon atoms, inclu~ive, and preferably, containing four to ix carbon atom~, inclusive, a~ for example, alkylene radicals, uch as trimethylene, tetra~ethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octametbylene, nonamethylene, hexadecamethylene and the like; cycloaliphat$c radical~, uch a~ cyclohexane, 1,3-cyclohexane, 1,2-cyclohexane, and the li~e.
Particularly desirable epoxides, falling within the cope of Pormula I, are those wherein R7 through R24 are hydrogen and R is alkylene containing four to ~ix carbon atoms.
_ Among specific diepoxides of cycloaliphatic esters of dicarboxylic acids are the following:
bi~(3,4-epoxycyclohexylmethyl)oxalate, bis(3,~-epoxycyclohexylmethyl)adipate, bi~3,~-epoxy-6-methylcyclohexylmethyl) adipate, bi~3,4-epoxycyclohexylmethyl)pimelate, and the like.
Other uitable compounas are described in, for example, U.S. Patent No. 2,750,395.
FORNULA II
A 3,~-epoxycyclohexylmethyl-3,~-epoxycyclo-hexane carboxylate having the formula:
~ ~0 R9 p6 ~16 R17 ; D-13,833 ~246785 whereln Rl through R18 which can be the same or aifferent are as aefined for R7 to R24 in Formula I. Particularly desirable compounds are those wherein Rl through R18 are hydrogen.
Among ~pec~fic compounds falling within tbe cope of Formula II are the following: 3,4-epoxy-cyclohexylmethyl-3,~-epoxycyclohexane carboxylate;
3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexane carboxylate: 6-metbyl-3,4-epoxy-cyclohexylmethyl-6-methyl-3,~-epoxycyclohexane carboxylate; 3,~-epoxy-3-methylcyclohexylmethyl-3,~-epoxy-3-methylcyclohe~ane carboxylates 3,4-epoxy-S-methylcyclohexylmethyl-3,~-epoxy-5-methyl-cyclohexane carboxylate. Other suitable compounds are aescribed iQ, for example, U.S. Patent No.
2,890,19~.
ORMULA III
Diepoxides having the formula:

R ' Rg' R16 Rl;
R7 ~ o-ca2 ~

l; 2 R ~

wherein the R'-, which can be the same or aifferent, are monovalent ~ubstituents such as hydrogen, halogen, l.e. cblorine, bromine, iodine or fluorine, or ~onovalent hydrocarbon radicals, or radical~ as further defined in U.S. Patent No.
3,318,822. Particularly, desirable compounds are those wherein all the R'~ are bydrogen.
, D-13,833 ';

~" ~Z9L~785 Other suitable cycloaliphatic epoxides are the following:

~ ~2-------CH2--C \ ~ cH2 and the like.
The preferred cycloaliphatic epoxides are the following:
3,4-Epoxycyclohexylmethyl-3,4-Epoxy-cyclohexane carboxylate ,~e-O~H2 C
Bis~3,4-Epoxycyclohexylmethyl)adipate ~CH2_o - c - c4E

2-(3,4-Epoxycyclohexyl-S,S-spiro-3,4-epoxy)cyclohexane-meta-dioxane ~W
or mixtures thereof.
Epoxides with ~ix ~embered ring 6tructures may also be used, such a~ diglycidyl esters of phthalic acid, partially hydrogenated phthalic acid or fully hydrogenated phthalic acid. A

D-13,833 ~29!~785 representative aiglycidyl e~ter of phthal$c ~cid is the following-:
O f~
. ~ CocH2cH C 2 a2c~-c~Fl2 O O
Diglycidyl esters of hexahydrophthalic acid~ being preferred.
The glycidyl-type epoxides are preferably diglycidyl ethers of bisphenol A which are derived from bisphenol A and epichlorohydrin and have the following formula:

CH2- CHCH2 ~ C~3 OCH2CHcH2- I n ~- r ~ C ~ OCH 2C~ --~H 2 :~ CH3 The cresol-novolac epoxy resins are multifunctional, solid polymers characterized by low ionic and hydrolyzable chlorine impurities, high chemical resistance, and thermal performance.
The epoxy phenol novolac resins are generally of the following formNla:

~H~

; D-13,833 - 34 - ~24~7~5 The polynuclear phenol-glycidyl ether-derived resins are generally of the formul~:

(O~N ¦ O~ 0 Among the aromatic and heterocyclic glycidyl ~mine resins which may be included herein are the following: tetr~glycidylmethylenedianiline derived resins of the following formula:

~ 2 / HCN ~ N ~ CN2 Triglycidyl-p-~minophenol derived resins, triazine based resins ~nd hydantoin epoxy resins of the formula:

~/\0~\~

R'2~-CN3 D-13,833 ~, ' ~2~Çi785 It i- of cour~e understood by those killed in the art that when a photoinitiator $8 used only oinor amounts of ba~ic organic nitrogen containing epoxiae compound~ aay be u~ed o a~ not to interfere with the photocopolymerization reaction The composition of thiR invention aay include linear vinyl eth-r~
The linear vinyl ethers are well known in the art na many are commercially available The ~` vinyl ethers include the alkyl vinyl ethers, aryl vinyl ethers, aivinyl ether~ and B-substituted v~nyl ethers and functionally ubstituted vinyl ethers The alkyl vinyl ether monomers include aethyl ethyl i~opropyl n-butyl i-obutyl -butyl t-butyl n-amyl i~oamyl 1,2-ai~ethylpropyl n-hexyl 1,2,2-trimethylpropyl 2-ethylbutyl 1,3-dimethylbutyl 2,2-aimethylbutyl dii-opropylmethyl n-octyl 2-ethylhexyl l-oethylheptyl 2,2-dimethylhexyl n-decyl 2,2-dimethyloctyl D-13,~33 lZ~785 2,2-aimethylaecyl n-tetradecyl 2,2-dimethyldodecyl n-hexadeeyl 2,2-dimethyltetradecyl n-octadecyl oleyl The ~ryl vinyl ether monomers include:
phenyl o-cre~yl p-eresyl p-ehlorophènyl 2,~-diehlorophenyl 2,~,6-triehlorophenyl -naphthyl - ~-naphtbyl The divinyl ethers include the following:
CH2--CB-O~CB2 )~0-CH--CH2 CH2~CH-O~CH2 ~O-CH--CH2 CH--CH2-0-CH2-CH2-CH-O-C~l--CH2 CH2-CH-O- ~CH2 )~0-CH-CH2 CH2'CH ~-C~2-C}~2 ) 2-0-CH~CH2 C~2'CH- (-CH2-CH2 ) 3-O-CH~cH2 C112--CH-O-(CH2)4-0-CH~CH2 CH2.CH-O-~CH2)2-0-~CH2)4-0 ~CH2)2 2 ; CH2~CH-O-CH2 ~ CH2-0-CH~CH2 (CiB and trans) eaterdiol divinyl ether~
The ~- ana B- ~ub~tituted vinyl ethers inelude the following:
methyl ~-methylvinyl ether methyl B-ehlorovinyl ether -~ methyl ~-methylvinyl ether ~ci-) ' ~trans) D-13,833 ,~

Z~7~5 .
~ethyl ~-chlorovinyl ether ethyl a-ethylv~nyl ether ethyl -methylvinyl ether (C~8) (tr~ns) ethyl -phenylvinyl ether $~opropyl ~-methylvinyl ether (cia) (trans) n-butyl-a-methylvinyl ether (C~8) (trans) isobutyl-a-methylvinyl ether (c~s) (trans) t-butyl-a-methylvinyl ether (cis, tr~ns) Functionally substituted vinyl ethers are of the formula:
CH2'cHoR
wherein R is selected from:
CH2cH2oH
C~2CB2CH
cH2cH2cl CF(CF3)2 CF(cF3)~cF2cl) CF(cF2cl)2 CH2cH2ocH2cH2oH
CH2cH2cHoHcB3 CB2cH2ocH2cH2ocR3 CH2cH2ocH2cB2oc2H5 CH2cH~cR2 D-13,833 ` `~` 124~785 ~ he cyclic vinyl ether containing compound is u6ed in amount~ of from about 30 to about 99, preferably from about 50 to about 95 weight percent, and the poly~active hydrogen) organic compound ~-used in amounts of from about 1 to about 70, preferably from about 5 to about 50 weight percent.
The photoinitiators whiCh may be used herein include one or more of a metal fluoroborate and a complex of boron trifluoride, as described in U.S. Patent 3,379,653; a bis~perfluoroalkylsulfonyl) methane metal salt, as described in U.S. Patent 3,586,616s an aryldiazonium compound, aQ described in U.S. Patent 3,708,296; an aromatic onium ~alt of Group VIa elements, as de~cribed in U.S. Patent ~,058,~00; an aromatic onium 6alt of Group Va , elements, as described in U.S. Patent 4,069,055; a dicarbonyl cheleate of a Group IIIa-Va element, as de~cribed in U.S. Patent ~,086,091; a thiopyrylium ~alt, as described in U.S. Patent ~,139,655; a Group VIa element having an MF6 anion where M is selected from P, As and Sb, a8 de~cribed in U.S. Patent 4,161,478; ~ triaryl~ulfonium complex ~alt, as described in U.~. Patent 4,231,951; and an aromatic - iodonium complex ~alt and an aromatic sulfonium complex salt, as de~cribed in U.S. Patent 4,256,828. Proferred photoinitiators include triaryl~ulfonium complex salts, aromatic ~ulfonium or iodonium salt~ of halogen-containing complex $ons, and aromatic onium salts of Group IIIa, Va and VIa element~. Some of ~uch salt~ ~re cgmmercia~ly A availablc, such as ~ ~ ~8 ~nd ~C- ~ va ~ b ~ from Minn~esot~ Mining, ~nd Manufacturing Company), and UVE-101 ~ avail ~ e from General Electric Company).
The photoinitiators are u~ed in conventional amounts in the compositions of this invention such a~ in amounts from about 0.1 to 30 parts by weight per 100 part~ by weight of the epoxides.

D-13,833 - 39 - 12~Ç;785 The eompositions herein may inelude additives ~uch as 01l8, particularly silicone oil, urfaetants ~ueh as ~ilicone-alkylene oxide eopolymçrs,and acrylie polymer~, ~ueh a6 the Modaf~ows~ ob~ain~ from Monsanto Chemieal Co ), ~ilieone oil containing aliphatic epoxide groups, fluoroearbon urfaetant-s low molecular weight aleohol~s eello~olve6, ~ueh as butyl cellosolve;
earbitols, ueh as butyl carbitol and diethylene-glycol, and the like If de~ired, one may include in the eompo~itions of thi- invention various conventional non-basic filler~ ~e g ! ~ilica, talc, glass beads or bubbles, clays, powdered metal such as aluminum, ilver, zinc oxide, etc ) and other additives such as viscosity modifiers, rubbers, taekifying agents, pigments, and the like The photoeopolymeri~able compositions are particularly ~uitable in a variety of applications in the fields of proteetive coatings and graphic art6 due to their flexibility, impact resistance, abrasion-re~istance, hardness and adhesion to rigid, resilient a d flexible substrates ~uch as metal, plastie, rubber, glass, paper, wood, and ceramic6 The eomposition may include a reactive ai luent which is an unsubstituted or a substituted cycloaliphatic monoepoxide The unsubstituted eycloaliphatic monoepoxide6 include cyclohexene monoepoxiae, and the like The ~ubstituted cycloalyphatie aonoepoxide $~ ~ubstituted with alkyl of l to 9 earbon atoms, halogen, oxygen, ether, hydroxy, ester or vinyl radieals Preferably, the ~ub6tituted eyeloaliphatie monoepoxide is vinyl ~ubstituted eycloaliphatie monoepoxide and is preferably ~elected from one or more of the following D-13,833 ' .
.

1%~785 (1) 4-vinyl cyclohexane monoepoxide having the formula: ..
K

~_C ~ CH2, (2) norbornene monoepoxide having the formula:

~ C ~ C~2, or (3J llmonene monoepoxide having the formula: ~H~
Ç1' C ~ CH2 I

Another preferred substituted cycloaliphatic epoxide i5 hydroxyl ~ubstituted cycloaliphatic monoepoxide of the following formula:
,~
W~
The photopolymerization of the compositions of the invention occurs upon exposure of the compositions to any source of radiation emitting actinic radiation at ~ wavelength within the ultraviolet and visible spectral regions. Suitable sources of radiation lnclude mercury, xenon, carbon arc lamps, ~unlight, etc. ~xposures may be from less than about 1 second to 10 minutes or more depending upon the amounts of particul~r polymerizable materials and photoinitiator being utilized and depending upon the radiation source and distance from the source and the thickness of the D-13,333 lZ4~785 eoating to be cur~d. The compositions may also be photopolymeri~ed by exposure to electron beam irradiation. Generally speaking the dosage neCe8~arY 1B from less than 1 megarad to 100 megarads or more.
The compositions of this invention may be prepared ~i~ply by mixing the formulation ingredients together, preferably under ~afe light~
conditions when the photoin~tiator i~ incorporated.

EXAMPLES
The following Examples serve to give pecific illu-tration of the practice of this invention but they are not intended in any way to act to limit the cope of this invention.
The following designations uffed in the Examples have the following meaniDg:
E~oxY 1: 3,~-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.
E~oxv 2: Bis (3, ~-epoxycyclohexylmethyl ) adipate.
Polvol 1: A trihydroxyfunctional polyc~prolactone polyol with an average hydroxyl number of 310 and an average molecular weight of 540 (TONE-0305 obtained from Union Carbiae Corporation).
Polvol 2: A aihydroxyfunctional polycaprolactone polyol with an average hydroxyl number of 212 and an average molecular weight of 530 (TONE-0200 obtained from Union Carbide Corporation).
Pol~ol 3s A propylene oxide polyol that has been capped with 15 percent ethylene oxide. It has a hydroxyl number of 28 which corresponds to an equivalent weight of 2004.
Ig~y~ s A polymer polyol based on a propylene ox~de polyol that contains 10 percent .
:
D-13,033 , . .

` 12~i785 -- ~2 --polyacrylonitrile ln a ai-persed olid pha-e. It has a hydroxyl-number of 23 which corre~ponas to an eguivalent weight of 2~39.
Polyol 5s A polymer polyol based on a propylene oxide polyol that contains 21 percent of a styrene/acrylonitrile copolymer in a di~per~ed olid pha-e. lt has a hydroxyl number of 28 which corresponas to an equivalent we~ght of 2004.
PolYol 6s A propylene ox$de polyol that has been capped with ethylene oxide. It has a hydroxyl number of 27 ~h~ch corresponds to an eguivalent weight of 2,078.
Polvol 7s A dihydroxyfunctional polytetrametbylene oxide polyol with an average hydroxyl number of 160-187 and an average molecular weight of 650.
Pol~ol 8s A dihydroxyfunctional polytetramethylene oxide polyol with an average hydroxyl number of 107-118 and an average molecular weight of 1000.
PolYol 9: A propylene oxide polyol that has been capped with 17 percent of ethylene oxide.
It ha~ a hydroxyl number of 39 which correspands to an equivalent weight of 1~39.
Polvol 10: Poly(tetramethylene oxide).
Setramer:

I~CH20C 1`3 O

Dimer:

~ HO
~' .
~ , D-13,833 i24Çi785 - ~3 -Monoepoxiaes vinyl cyclohexene monoepoxide.
Surfactant 1: A silicone surfactant with the structure ~H3t3slolsioyLio~i(c~ 3 ! lC~3~ 1 (C~2 ~ C2H~)7 5-5 Surfactant 2: A fluorinated alkyl e~ter of the nonionic type obtained from Minnesota Mining and Manufacturing Co., a~ FC-171) Photoinitiator 1: UVE-1014, a solution of a triarylsulfonium hexafluoroant~mony salt with a specific gravity of 1.39 and a ~rookfield viscosity of 74 centipoise ~obtained from General Electric Co., ) .
Photoinitiator 2: FC-508, a solution of a triaryl~ulfonium hexafluorophosphate with a specific gravity of 1.33 and a Brookfield vi~cosity of about ~,000 centipoise at 25-C (obtained from Minnesota Mining and ~anufacturing Company).
The procedures used to test coatings cured ~ith the compositions of this invention were a~
followss Solvent Resistance (Double Acetone Rubs):
a measure of the resistance of the cured film to attack by acetone in which a film coating ~urface was rubbed with an acetone ~oaked cbeese cloth back and forth witb hand pre~sure. A rub back and forth with hand pre~ure over the film coating surface with the acetone soaked cheesecloth was designated as one ~double acetone rub~. The effect that a certain number of double acetone rubs had on the film coatlng urface was reported by a number ln ' D-13,833 .

-- 124~785 -- ~4 --parenthesin following the number of double acetone rubs. The rating ~ystem for evaluating acetone re~i~tance for a given number of double acetone rubs was as follows:
Number in Parenthes$s After Number of Rubs (1) No change in coating appearance.
~2) Scratched surface.
~3) Dulled, marred, ~ome coating removed.
~) Breaks fn coating appearance.
~5) About one-half of the coating removed.
Pencil Hardness - ASTMD-3363-7~
The rating system for pencil hardness was as follows:
6B-SB-4B-3B-2B-B-EB-F-~-2H-3H-4H-5H-6H
Softer ~arder Crosshatch adhesion - refers to a test using 10 parallel, single-edge, razor blades to scribe test films with 2 set~ of perpendicular lines ln a crosshatch pattern. Ratings are based on the amount of film removed after applying and sub6equently pulling a contact adhesive tape ~Scotch Brand 606) away from the surface of a scribed coating at a 90 degree angle in a fa~t, rapid movement. It i6 important to carefully apply and press the tape to the scribed coating to eliminate air bubbles and provide a good bond because adhesion is reported as the percent of film remaining on the substrate with a 100 percent rating indicating complete adhesion of the film in the ~ubstrate.
Reverse or face imDact resistance - measures the ability of a given film to resist rupture from a falling weight. a Gardner Impact Tester using an eight-pound dart iB u6ed to te~t the films cast and ; cured on the ~teel panel. The dart is raised to a D-13,833 ' ~24~785 -- 4s --given height in inches ana dropped onto the reverse or face ide of a coated metal panel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing is recorded as the rever~e or face impact resiQtance of the film.
Control A; Examples 1 and 2 Thi~ oxample describes the combination of Tetramer with Polyol 1, a photoinitiator and a urfactant. She ~ixture 1~ activated with ultraviolet light.
The amount~ of Tetramer, Polyol 1, photoinitiator and ~urfactant shown in Table I were placed in amber bottles and mixed while working under a yellow l~ght ource.
The ~ystem were coated onto Bonderite 37 ~teel plates ~ith a No. 20 wire-wound rod and cured with one pa~s under a 100 wat per inch medium pressure energy vapor W source at 30 feet per ~inute. The properties are ~hown in Table II.
TABLE I
Inqreaients ExamPles (Parts by Wel~2t~

Tetramer 23 918 o 17 5 Photoinitiator 1 - - 0.5 Photoinitiator 2 1.01.0 8urfactant 1 0.10.1 0.1 TABLE II
Propertie6 1 A Ex 1 2 Double Acetone Rub6 100100 100 Pencil ~ardne~s H H H
Cros~hatch Aahesion ~) 100 0 0 Reverse 15 55 >232o D-13,833 .

12~6785 -- ~6 --TABLE II (Continuea) Properties Examples Control A 1 2 Post Cured (150-C for Double Acetone Rubs - 100 100 Pencil Hardness - 4H
Crosshatch Adhesion (~) - 100 100 Gardn r I~Pact (in.lbs.) 25 150 Rever-e - <5 50 Examples 3 to 5 These examples describe a blend of Tetramer, polyols and epoxides.
The ingredients listed in Table III were blended, coated and cured as described in Example Control A and ~xample- 1 and 2. The coating thickne~s waff about 0.8 mil.
The properties ~re given in Table IV.

TABLE III
InqredientsExamPles (Part4s bY WeiahC) pOlyO ;138.0 38 0 38 0 Pbotoinitiator 24 0 ~.0 4.0 ~urfactant 10.~ 0.4 0.4 ..
The cured composition~ were tack free wben warm immediately fter W expo-ure.
.

D-13,833 ~: .

- ~7 - iZ46785 . TAB~E IV
ProDerties SxamPles Acetone Double Rubs 1-2 hour~ ) 10011) 100(1) 1 day 75(~) 100(1) 100(1) Pencil ~ardnes~ ~B H ~B
Crosshatch Adhc~ion ~) 100 100 100 Gardn r ImPact (in.lb~.) 15 25 Rever~e 25 <5 <5 ExamPles 6 to 8 These examples de~cribe blending of Tetramer, polyol, epoxides, photoinitiators and urfactant.
The inqredients listcd in Table V were blended, coated and cured as described in Control A, and Example 1 and 2.
The properties are listed in Table VI.

TABL~ V
Inqredients Examples ~parts bY Weiaht) : 6 Tetramer 75.6 65.6 34.0 Polyol 1 20.0 30.0 26.0 Epoxy 1 _ _ 33.6 Photoinitiator 1 - 2.0 2.0 Photoinitiator 2 ~.0 8urfactant 1 0.~ 0.~ 0.~

The cured compositions were tack free when warm immeaiately after ~V exposure.

D-13,833 i - ~8 - lZ4~785 TABLE VT

Examples ~aged at room temp., about 25C, ProPert~eff 6 for 18 hour-l 8 Acetone Double Rub~ ~OOll) 100~ OO(l) Pencil 8arane~ 8 H
Cro~hatch Aahe-ion l~) 0 0 0 Gardn r I~Pact (in. lbs.) 50 250 150 Rever-e 2S >320 175 Examples ~Post cured 10 minutes at 150C 8 Acetone Double Rubs 100~1) 100~1) 100(1) Pencil 8ardness ~8 4H 4H
Cros~hatch Adhesion ~) 100 100 100 Gardn r ImPact ~n. lb~.) 25 150 200 Rever~e <S 50 320 ExamPles 9 to 14 The~e examples describe blending of Tetramer, with different polyols, an epoxide, photoinitiator and ~urfactant.
The ingreaient~ l-ated 1n Table V~ were blended, coated, ana cured as described in Control A, and Examples 1 ana 2.
The properties are li~ted in Table VIII.
TABLE VII
Ingredient~ xa pleg 11 rt51bY l3 14 Tetramer 11.9 16.~ 18.9 18.9 18.9 18.9 Polyol 1 ~.0 ~
Polyol 2 - 7.5 Polyol ~ _ - S. O

Photoinitiator 2 1 0 1.0 1.0 1.0 1.0 1 0 Surfactant 1 0.1 0.1 0.1 0.1 0.1 0.1 D-13,833 .
.
: , 124~785 _ ~9 The co~tin~s wer- tack free ~t room temperature (about 25'C) after exposure to the UV
light ource.

D-13,~33 ~z~785 ~rl o_o_ o ~u~ o -'I ~ -~ o ~ v o o ~ o ~ ~ ~ U~ o~
.I o~o~ o~ ~V
,., ,, _ ~ o ~q ~1 o _ o _ o u~
~: _, o~o~ o ~V
I ,,~ ,, o ,,1 o ~ o _ o c~ o o~
~ -~1 ~ ~ 1 ~U~ o ~ o 1~ g _I g ~ U~ a~

~I g--g ~ oO m ~ _ ~ o ~ I
~C 0 ~, O O 1~1 ~ O ~ ¦ ~ ~\ ~ E

c ~ ~~ ~ _ ~1 ~ n c ~' ~ Uc o.c~ ~X
~e I u~

.

- 51 - ~ 2 4 ~ q 8 5 Control B and Example 15 This Example describes the curing of a blend of Tetramer and Dimer.
The ingredients listed in Table IX were blended, coated, and cured as described in Control A, and Examples 1 and 2.
$he properties are listed in Table X.
TABLE IX
Ingredients EXAMPLES ~grams) Control B 15 Tetramer 9.8 5.0 Dimer - 4.8 Photoinitiator 1 0.2 0.2 TABLE X
Properties EXAMPLES
Control B 15 Double Acetone Rubs 6 hours 100(1) 100(1) Pencil Hardnes~ 4H 3H
Crosshatch Adhesion.(%) 50 75 Gardner ImDact (in.lbs.) Face 5 5 Rever~e <5 <5 ExamDles 16 and 17 These examples describe blending of Tetramer, with different polyols, photoinitiator and surfactant.
The ingredients listed in Table XI were blended, coated, and cured as described in Control A, and Examples 1 and 2.
The properties are listed in Tables XII and XIII.

D-13,833 12~i785 TABLE XI
In~redients ~xamples (gr ms) Tetramer 16.4 18.9 Polyol 7 ~.5 __ Polyol 8 -- 5.0 Photoinitiator 1 0.5 0.5 Surfactant 2 0.1 0.1 After exposure to UV light, the coatings were tack free.
TABLE XII
ProPerties (No Post Cure) Examples (grams) Double Acetone Rubs16 17

5 hours 100(1) lO0(1) Pencil Hardness F F
Crosshatch Adhesion (%) 0 0 Gardner ImPact (in.lbs.) 50 Reverse 300 25 TABLE XIII
Properties (Post Cure ExamPles (grams) 10 Minutes at 150C)16 17 Double Acetone Rubs100(1) 100~1) Pencil Hardness 3H 3H
Crosshatch Adhesion(~) 50 75 Gardness Impact (in.lbs) 2S
Face Reverse <5 25 Examples 18 to 23 These examples describe blending of Dimer with different polyols, and epoxides, photoinitiator and surfactant.
:;

D-13,833 - S3 - 124~785 The lngredients li~ted in Table XIV were blended, coated, and cured as described in Control A
and Example~ 1 and 2. The viscosity of tSe blend was measured at 24.~-C.
The properties are listed in Table XV.
TAB~E XIV
Examples ~grams) Ingredients 18 19 20 21 22 23 Dimer 13.813.B15.6 9.6 9.6 2.0 Polyol 1 5.85.8 - 6.0 Polyol 9 - - ~.0 - 4.0 Polyol 10 - _ ~ 0 6.0 126 0o Photoinitiator 1 0.4 - 0.~ 0.4 0.4 Photoinitiator 2 - 0.4 - - - 0.8 Surfactant 1 0.08 0.08 0.08 0.08 0.08 0.0B
Viscosity 120 150 ~0 170 50 300 (Centipoise) All coatings were tack free when warm immediately after UV exposure.

D-13,833 12~Ç~785 N ¦ ~9 S~: _I N V N

~1 p~, o ~ U m ~1 ~ o ~ v ~ ~I
1~3 j I r~l ~ O N V u~
~1 -4 E~l~1 o u~

1,~1 o o u~
I .
I
C
I
O
~0 ~p ~C
l S ~ ~ ~ ~' S
c ¦ n ~ u`~ O ~ ~ ~

Claims (84)

WHAT IS CLAIMED IS:

1. A composition suitable for photocopolymerization comprising a cyclic vinyl ether containing compound and a poly(active hydrogen) organic compound.

2. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is selected from the following:

The Z's each represents hydrogen or an alkyl group having from 1 to 10 carbon atoms;
X and X' are members of the class consisting of a bivalent saturated hydrocarbon group, R, having the structure, -CnH2n-, wherein n is an integer having a value of from 1 to 10; an oxy radical, -O-; and a carbonyl group, -C(O)-; and, in addition X' may be a carbonyloxy group, -O(O)C-, the carbon atom of which is bonded to the 2-position of the dihydropyranyl ring; X and X' may be the same or different provided that taken together they contain either zero or 2 oxygen atoms;
a has a value of from zero to 1, a being zero only when X' is the aforesaid carbonyloxy group;
Q is a member of the class consisting of the aforesaid R group; a dioxylakylene group, -ORO-, wherein R is as defined above; a dicarboxylate group, -OC-(O)-R'-C(O)),- wherein R' is the nucleus of a dicarboxylic acid; and a polycarbamate group such as the dicarbamate group, -OC(O)NH-R"-NH-C(O)-, wherin R", as illustrated, is the nucleus of a diisocyanate; and X, X' and Q taken together is such that the linking chain, -X-Q-X'-, contains an even number of oxygen atoms from two to four, provided that when X
and X' are both oxy radicals, the linking chain contains no other oxygen atoms (that is, Q or R), and when X and X' are both carbonyl groups, the linking chain contains four oxygen atoms (that is, Q
is -ORO-).

3. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is 3,4-dihydro-2H-pyran-2-methyl(3,4-dihydro-2H-pyran-2-carboxylates) having the formula:

wherein Z and Z' are as above-defined. Preferably a total of from 5 to 7 of the respective Z and Z' groups are hydrogen and correspondingly, from 3 to zero are alkyl groups.

4. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is alkanedioxy-bis(3',4'-dihydro-2'H-pyran-2'-carbonyl) compounds having the structure:

wherein Z and Z' are as defined in claim 2, and n is an integer from 1 to 10

5. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is bis-(3',4'-dihyro-2'H-pyran-2'-oxy)alkanes having the formula:

wherein Z, Z' are as defined in claim 2 and n is as defined in claim 4.

6. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is bis-(3',4'-dihydro-2'H-pyran-2'alkoxy) alkanes having the formula:

wherein Z, Z' are as defined in claim 2 and n is as defined in claim 4.

7. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is bis-(3',4'-dihydro-2'H-pyran-2'alkyl) carboxylates having the general formula:

wherein Z, Z' are as defined in claim 2, n is as defined in claim 4 and R' is the nucleus of a dicarboxylic acid and may be a bivalent aliphatic, cycloaliphatic or aromatic nucleus including corresponding halogen-substituted nuclei.

8. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound has the general formula:

wherein Z, Z' are as defined in claim 2, n is as defined in claim 4, R" is an aliphatic, cyloaliphatic or aromatic radical which may be unsubstituted hydrocarbyl groups or hydrocarbyl groups substituted with haolgen or alkoxy groups.

9. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is selected from one or more of the following:

wherin R1 is hydrogen or methyl, R1 ''' is alkyl of 1 to 10 carbon atoms, and X is selected from wherein n has a value of from 1 to 50 and wherein R1' is the residue of a carboxylic acid and can be (1) hydrogen, (2) alkyl which is substituted with any substituent which does not unduly interfere with the polymerization, or unsubstituted, linear or branched, containing up to 20 carbon atoms, and (3) aryl which is substituted with any substituent which does not unduly interfere with the polymerization or, which is unsubstituted, having 6 to 10 ring carbon atoms; R3 is hydrogen, alkyl, alkoxy, aryl, cycloalkyl, alkaryl or an aralkyl group having up to 12 carbon atoms and at least (2x-3) of the R3 groups are hydrogen atoms, and x has a value of 2 to 12.

10. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is an alkylene oxide adduct of 3,4-dihydropyran-2-methanol of the general formula:

wherein R1 and n are as defined in claim 9.

11. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is of the formula:

wherein R1, n, R3 and x are as defined in claim 9.

12. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is of the formula:

wherein R1 and R1' are as defined in claim 9.

13. A composition as defined in claim 1 wherein thc cyclic vinyl ether containing compound is of the general formula:

wherein R3 is as defined in claim 9 and R1 and n are as defined in claim 10.

14. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is of the formula:

wherein R1, R3, n, and x are as defined in claim 9.

15. A composition as defined in claim 1 wherein tho cyclic vinyl ether containing compound is the reaction product of thc following:

wherein R1, is as defined in claim 9, and pentaerythritol or an aldehyde.

16. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is of the formula:

17. A composition as defined in claim 1 wherein the cyclic vinyl ether containing compound is of the formula:

18. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is selected from the group consisting of a polyether polyol, a polycaprolactone polyol, a polyester polyol, an acrylic polyol, a vinyl polyol, and a polymer/polyol

19. A composition as defined in claim 18 wherein the polyether polyol is selected from the group consisting of a propylene oxide polyol, an ethylene oxide polyol, a propylene oxide polyol capped with ethylene oxide, a tetramethylene oxide polyol and a polymer/polyol.

20. A composition as defined as claim 1 wherein the poly (active hydrogen) organic compound is a polymer polyol.

21. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is a polycaprolactone polyol.

22. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is a polyester polyol.

23. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is an acrylic polyol.

24. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is a vinyl polyol.

25. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is a mixture of a polyether polyol and a polycaprolactone polyol.

26. A composition as defined in claim 1 wherein the poly (active hydrogen) organic compound is a mixture of at least two poly (active hydrogen) organic compounds.

27. A composition as defined in claim 1 which contains an epoxide containing at least one epoxy group.

28. A composition as defined in claim 27 wherein the epoxide is a cycloaliphatic epoxide.

29. A composition as in claim 28 wherein the cycloaliphatic epoxide has the formula:

wherein R7 through R24, which can be the same or different, are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive; R is a valence bond or a divalent hydrocarbon radical generally containing one to ten carbon atoms inclusive.

30. A composition as in claim 28 wherein the cycloaliphatic epoxide has the formula:

wherein R1 through R18, which can be the same or different are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive.

31. A composition as in claim 28 wherein the cycloaliphatic epoxide has the formula:

wherein the R's are the same or different and are monovalent substituents or monovalent hydrocarbon radicals.

32. A composition as in claim 28 wherein the cycloaliphatic epoxide is 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate.

33. A composition as in claim 28 wherein the cycloaliphatic epoxide is bis(3,4-epoxycyclo-hexylmethyl)-adipate.

34. A composition as in claim 28 wherein the cycloaliphatic epoxide is 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane.

35. A composition as defined in claim 28 wherin the cycloaliphatic epoxide is vinylcylohexene diepoxide.

36. A composition as in claim 28 wherein the cycloaliphatic epoxide is a mixture of bis(3,4-epoxycyclohexylmethyl)adipate and 2-(3,4-epoxycyclo-hexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane.

37. A composition as in claim 28 wherein the cycloaliphatic epoxide is a mixture of 3,4-epoxy-cyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bis(3,4-epoxycyclohexylmethyl) adipate.

38. A composition as in claim 37 which includes 2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane.

39. A composition as defined in claim 28 which contains minor amounts of one or more glycidyl type epoxides, aliphatic epoxides, epoxy cresol novolac resins, epoxy phenol novolac resins, poly-nuclear phenol-glycidyl ether-derived resins aromatic and heterocyclic glycidyl amine resins or hydantoin epoxy resins.

40. A composition as in claim 1 which contains a glycidyl type epoxide.

41. a composition as in claim 40 which contains a cycloaliphatic epoxide.

42. A composition as in claim 1 which contains a linear vinyl ether.

43. A composition as defined in claim 42 wherein the linear vinyl ether is an alkyl vinyl ether.

44. A composition as defined in claim 42 wherein the linear ether is an aryl vinyl ether.

45. A composition as defined in claim 42 wherein the linear vinyl ether is a divinyl ether.

46. A composition as defined in claim 1 which contains a photoinitiator.

47. A composition as defined in claim 46 wherein the photoinitiator is selected from diazonium salts or onium salts, or mixtures thereof.

48. A Composition as defined in claims 1 which contains an unsubstituted cycloaliphatic monoepoxide or a substituted cycloaliphatic monoepoxide, said substituted cycloaliphatic monoepoxide contains substituents selected from an alkyl of 1 to 9 carbon atoms, halogen, oxygen, ether, ester, hydroxyl or a vinyl radical.

49. A composition as defined in claim 48 wherein the substituted cycloaliphatic monoepoxide is vinyl substituted cycloaliphatic monoepoxide.

50. A composition as defined in claim 49 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

51. A composition as defined in claim 49 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

52. A composition as defined in claim 49 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

53. A composition as defined in claim 49 wherein the substituted cycloaliphatic monoepoxide is hydroxyl substituted cycloaliphatic monoepoxide.

54. A composition as defined in claim 53 wherein the hydroxyl substituted cycloaliphatic monoepoxide is of the following formula:

55. A composition as defined in claim 48 wherein the unsubstituted cycloaliphatic monoepoxide is cyclohexene monoeposide.

56. A radiation cured coating derived from the composition of claim 1.

57. A composition as defined in claim 27 which contains a linear vinyl ether.

58. A composition as defined in claim 57 which comprises a linear vinyl ether that is an alkyl vinyl ether.

59. A composition as defined in claim 57 wherein the linear ether is an aryl vinyl ether.

60. A composition as defined in claim 57 wherein the linear vinyl ether is a divinyl ether.

61. A composition as defined in claim 40 which contains a linear vinyl ether.

62. A composition as defined in claim 61 which comprises a linear vinyl ether that is an alkyl vinyl ether.

63. A composition as defined in claim 61 wherein the linear ether is an aryl vinyl ether.

64. A composition as defined in claim 61 wherein the linear vinyl ether is a divinyl ether.

65. A composition as defined in claim 27 which contains a photoinitiator.

66. A composition as defined in claim 65 wherein the photoinitiator is selected from diazonium salts or onium salts, or mixtures thereof.

67. A composition as defined in claim 40 which contains a photoinitiator.

68. A composition as defined in claim 67 wherein the photoinitiator is selected from diazonium salts or onium salts, or mixtures thereof.

69. A composition as defined in claim 27 which contains a substitute or unsubstituted cycloaliphatic monoepoxide.

70. A composition as defined in claim 69 which comprises a substituted cycloaliphatic monoepoxide containing substituents selected from alkyl of 1 to 9 carbon atoms, halogen, oxygen, ether, ester, hydroxyl or a vinyl radical.

71. A composition as defined in claim 70 wherein the substituted cycloaliphatic monoepoxide is vinyl substituted cycloaliphatic monoepoxide.

72. A composition as defined in claim 70 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

73. A composition as defined in claim 70 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

74. A composition as defined in claim 70 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

75. A composition as defined in claim 74 wherein the unsubstituted cycloaliphatic monoepoxide is cyclohexene monoepoxide.

76. A composition as defined in claim 69 wherein the hydroxyl substituted cycloaliphatic monoepoxide is of the following formula:

77. A composition as defined in claim 40 which contains a substituted or unsubstituted cycloaliphatic monoepoxide.

78. A composition as defined in claim 77 which comprises a substituted cycloaliphatic monoepoxide containing substituents selected from alkyl of 1 to 9 carbon atoms, halogen, oxygen, ether, ester, hydroxyl or a vinyl radical.

79. A composition as defined in claim 78 wherein the substituted cycloaliphatic monoepoxide is vinyl substituted cycloaliphatic monoepoxide.

80. A composition as defined in claim 78 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

81. A composition as defined in claim 78 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

82. A composition as defined in claim 78 wherein the vinyl cycloaliphatic monoepoxide is of the following formula:

83. A composition as defined in claim 82 wherein the unsubstituted cycloaliphatic monoepoxide is cyclohexene monoepoxide.

84. A composition as defined in claim 77 wherein the hydroxyl substituted cycloaliphatic monoepoxide is of the following formula: