CA1246292A - Blends of cyclic vinyl ether containing compounds and linear vinyl ethers - Google Patents

Abstract

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

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

24~
æLl~ttDS 0~ CYCLIC YINYL E'r~iER
CONTAINIt;lG COMPOUNDS AND
LINEAR VINYL E'rHERS
_ BACl~GRl:)UND C~F ~HE INVENTION
~ t ~ well known that coatlng6 play a ~eful rol~ ~n the Danuf~cture o~ ~ wide variety of useful ~rticles. ~ntil recently, ne~rly all ~onting~ ~ere formul~tea ~n~ appli~d by employment of an organic ~olvent, which often comprised a major portion of the t~tal formulated coating. After tbe ~o~t~ng is applie~ to the ~rticle to be coatedp the organic ~olvenk ~ ~vapor~ted le~ving the dried coating sn the ~rtic~e to ~erve it decorative or functional purpose. Thi~ ~oating 0ystem has met with $ncreasing ~i~favor ~5 the cc~t of energy needed to evaporate the ~olvent at the ra~e required by ~ndustry ~ncrea~ed, as the price of the ~olvent increased, ~nd ~s the deleterious environmental effects of the evaporated 601vent became better understood. In addition, governmental regulation~
have placed ever increasing reEtric~ions on the ~mount~ and type~ of ~olv~nt~ or organic volatiles permitted to escape into the at~o~phere from eoatings c~mp~itions. ~ystems aimed at ~olvent recovery to reduce pollution and conserve 601vent have generally proven to ~e energy intensive ~nd expensive.
Considerable ef~ort6 have been expended by those skilled ~n the art to develop coating composition6 having n minimal amount of volatile or~anic components and thi3 has led to development of powder ooatings, radiation-curable coatings, water borne coatin~s and hig~ 6~1ids coatings. In D-13,B~5 i. ~.;

the~e rec~nt ~eve~opment~, the amounts of organic ~olvents present are mini~l and con6equently there i6 lit~le or n~ atmospheric pol1utiDn.
AmQng t~e new ooating 6y6tem~, radi~tion-curable co~t~ngs, usually cured with ultravi~let liqht or electron beam radi~tion, ~ffer a variety of advantages. ~hey regu~re only minlmal ~nergy to effect cure -- change ~rom liquid to 601id ~tate -~ they ~o not contain solvent~, and thus do not c~use deleteriou~ effect~ to the environment, and they are cost effective, since e~fectively all of the applied liqul~ i~ converted to a ~olid coating.
An important di advantage of photocurable 6ystems i~ the freguent requirement that the curing process be conducted in an ~nert atmosphere because of the inhibiting effect of oxygen.
Responding to ~uch problems, thcse skilled in the art have devised photocurable coatings which cure through a mechanism termed cation~c polymerization. In these systems, the starting materials ~re mixed with catalysts which form acids when exposed to ultraviolet light; the ~tarting ~aterials are therefore polymerized via cationic cataly~i6.
Epoxy resins, linear vinyl ethers, and cyclic vinyl ether~ have been ~hown to be 6uitable starting materials fGr photocure via cationic polymerizat~on, ~6 disclosed in, ~or example, U.S.
Patent 3,794,576; the public~tion ~New Monomers for Cationic UV-Curing~, Conference Proceedings, Radiation Curing VI, pages q-28, September 20-23, 1982; and ~ritish publication G~ 2,073,760A.

~_~3,855 _ 3_ ~Z~62~'~

~ owever~ a photo~urable coatinq COmpOBitiOn that c~n be cured by cationiC p~lymerizatîon ~nd ~aving increased toughness over compositions a~ ~re currently known ~ould be ~ighly desirable.
THE INVENTION
It h~ nc~ been found that photocurable ~oatin~ ~an be prepare~ from blends of oyclic vinyl ether ~ontaining comp~unds ~nd ~ linear vinyl ether.
~hese photocurable ~oating~ can be cured by ~a~ionic polymeri2ation. These ~ovel photocurable eompositions cure to glve coati~gs ~ith ~arkedly i~proved flexibil-ity and ~mpact re~fitAnt prop~rtie~. The blend can optionally contain an epoxide and/or polyol~
The cy~lic vinyl eth~rs suitable ~or use in th;s inventiGn ~nclude dihydropyranyl ~nd/or di-(dihydr~pyranyl) compounds.
The ~ dihydropyranyl) compound~ employed in the pre~ent invention comprise tw~ 3,4-dihydro-2H-pyranyl rings which are interconnected by a linking chain bonded ~t either end to the 2-position of the respective pyranyl rings. ~n simplified form, the preferred compounds for u~e in the present invention have the following general For~ula A:
~2 l'2 / \C Z Z'2__C/ \C--Z' 11 i I 11 Z - C C - X Q - X' - C /C - Z' O Z Z' C) wherein:
Z and Z' ~when Z and Z' are defined herein the definition includes Z2 and Z'2) each represents hydrogen or an alkyl group having from 1 to 10, and uBually no more than 6, carbon atoms;

D-13,~55 4 ~4~29 X an~ X' are ~e~ber~ of the ~lass con6isting of a bivalent 6aturated hydrocarbon group.~ R, ~hving the ~tructure, ~~n~2n , wher i6 an integer having a value ~f from 1 to 10; an oxy radical, -0-; ~nd a carbonyl group, -C~O)-: an~, ~n additlon X' may be a csrbonyloxy group, -~tO)C-, the ~arbo~ atom of ~hich ~ bon~ed to the 2-p~sition of the ~ihydropyranyl ring; X and X' may be the ~ame or ~ifferent provided that taken together they contain ~ither ~ero or 2 oxygen atomg;
a bas a value of $rom zero to 1, a being ~ero only when X' ~ the sforeeaid carbonyloxy group;
Q is a ~ember of the cla~s consi6ting of the aforesaid R gr~up: a dioxylakylene group, -ORO-, wherein R is a6 defined above; a dicarboxylate group, -OC-~O)-R'-C(O)O,- wherein R' i~ the nucleus of a dicarboxylic acid; and a polycarbamate group ~uch as the dicarbamate group, -OC(O)NH-R~-N~-C(~)O-, wherein R n ~ as illustrated, is the nucleus of a dii60cyanate; and X, X' and Q taken together is such that the linking chain, -X-Q-X'-, contains ~n even number of oxygen atoms from two to ~our, provided that when X
~nd X' are both oxy radical~, the linking chain contains no other oxygen atoms (that is, Q or ~), and when X and X' are both carbonyl groups, the linking chain contains four oxygen atDms (that i6, Q
i6 -ORO-).
Among the ~uitable di-(dihydropyranyl) c~mpounds which are u~eful in accordance with the teachings of this invention are the following classes of compounds design~ted by For~ulas A-l through A-6 below.

D-13,B55 1. 3,~ hy~ro-2R~pyran-2-methyl(3,~-dihydro-2H-pyran-2-carboxylates) h~ving the formula:
~ ~2 ~, ~ e ~ (A-l) I`b CH2 - O - C ~
o wherein Z ~nd Z' ~re ~s above-defined. Preferably a total of from 5 to 7 of the re~pect~ve æ ~nd Z~
groups ~re hydrogen ~nd correspondingly, from 3 to rero are alkyl groups. When Z ~nd ~' ~re ~lkyl ~roups, they are u~ually bonde~ ~o the 2- and/or S-po~it~on of the re~pect~ve ring~. Typical example~ of thi~ cl~ss of reactants are:
3,4-d~hydro-2-~-pyran-2-methyl~3,~-dihydro-2H-pyran-2-carboxyl~te) and ~orresponding ~lkyl-substituted compounds ~uch as 3,4-dihydro-2,5-dimethyl-2H-pyran-2-methyl~3,~-dihydro-2,5-dimethyl-2H-pyran-2-car~oxyl~te); 3,4-dihydro-2,5-dii60butyl-2H-pyran-

2-methyl~3,4 aihydro-2,5-diisobutyl 2~-pyran-2-carboxylate); 3,4-dihydro-2,5-dihexyl-2H-pyran-2-methyl ~3,~-~ihydro-2,5-dihexyl-2H-pyran-2-carboxylate~; and 3,~-dihydro-2,5-didecyl-2~-pyran~
2-~ethyl(3~4- dihydro-2,5-~idecyl-2H-pyran-2-carboxylate). The 3,4-dihydro-2H-pyran-2-methyl-~3,~-dihydr~-2B-pyran-2-carboxylate) which is commonly referred to as acrolein tetramer iE
preferred ~nd ha~ the etructure:

~-CH2 - - ~ ~ o~

Alkanedioxy-bi~ ( 3 ', 4 ' -dihydro-2 ' ~-pyran-2 ' -carbonyl ) compounds havirlg the 6tructure:

D-13,855 ~2 ~ ~2~

(A-2) 0~ - C ~ (Cn~2n) ~ C~

~herein ~ ana Z' are as above-dl~cus~ed, and n ~ an ~nteger from 1 to 10, preferably from 1 to ~.
Typical examples o ~ueh compound6 whi~h Bre ~ultable ~n the pra~tice ~f thi~ invention are:
1,2-ethanedioxybi~-t3',~'-dihydro 2'~-pyran-2'-~arb~nyl)~ 1,2 ethanedioxybi~-(3',~ ihydro-S'-~ethyl-2'~-pyran-2'~carbonyl), and corresponding 1,2-isopropanedioxy and 1p4-butanedioxy ~ompounds.
~uch compounds can be prepared by the reactiQn of an alkylene dihal~de, X~ ~(Cn~2n)~XR, whereln ~ ~ a-~
aforesaid, and xw $~ halogen, particularly iodine, chlorine or brominep ~ith the ilver ~alt of a

3,~-dihydro-2H-pyran-2-carboxylic ~cid. The latter 6alt5 are in turn prepared by the oxidation of 3, ~-dihydro-2H pyran-2-carboxaldehyde in the presence of a 6ilver ~alt ~uch as ~ilver oxide, preferably in an anhydrous medium containing an organic solvent ~uch as benzene, as described in .5. Pat. No. 2,514,172.
3. 8i~(3',4'-dihyro-2'~-pyran-2'-oxy~alkanes having the fGrmula:

~0--(CnH;!n)--o~J

wherein Z, Z' ~nd n have the significAnce discus~ed ~bove. ~llustrntive co~pounas of this group of di-~dihydropyranyl) compounds are: 1,2-bis-(3',4'-~-13,855 dihydro-2'B-pyran-2'~xy~ethane; 1,2-b~3',4'-dihydro-5'-methyl-2lH-pyran-2'-oxy)ethane; 1,3-bis ~3',~'-dihydro-5'-~ethyl~2'~-pyran~2'-oxy)propane;
~nd 1,4-bi~3~,4'-aihydro-2'~-pyran-2'~xy)butane.
~uch ~omp~una~ are prepare~ ~y Diel~-~lder ad~tion reactions of divinyl bi~ether~ ~uch as the ~ivinyl ether6 of alkylene glycols, wi~h ~lpha, ~eta-un6aturate~ aldehyde~ ~uch ~6 acrolein, methacrolein, and crotonaldehyde unaer conditions deecribed, ~or exa~ple, by Curti~ W~ Smo~h et al., Journal of the ~eric~n Chemical Society, Vol. 73, 5267 (1951)o ~r exa~ple, the reaction between ~ ~ole of ethylene glycol diYinyl ether and 2 moles of acrolein provide6 1,2-bis(3'',4'-dihydro-2'~-pyran-2'=~xy) ethane.

4. Bis-(3',4'-dihydro-2'~-pyran-2'-alkoxy) alkanes having the ormula:

(CnH2n)-o-(cnH2n3 (CnH2n) ~2 (A-4) wherein Z, Z' and n ~re as defined hereinabove.
Typical examples of this type of reactant are:
1,1-bis(3',4'-dihydro-2'H-pyran-2'-methoxy)ethane;
1,1-bi~(3',4'-dihydro-5'-methyl-2'~-pyran-2'-~ethoxy)ethane; and 1,2-bi~3',~'-dihydro-2'H-pyran-2'-methoxy~ethane. Such compounds are prepared by the addition of alphn, beta-un6aturated aldehydes (~uch as, for example, acrolein ~nd methacrolein) to the corresponding bis-unsaturated ether~.

5. Bi6-(3',~'-dihydro-2'H-pyran-2'-~lkyl) carboxylates having the ~eneral formula:

D-13,355 ~2 J~ nH 2 n tA-5) ~her~in Z, ~' ~nd n ~re ~s above-defined; and R' the nucleu~ ~f a ~icarboxylic acid and ~ay ~e a b~v~l~nt ~liph~t~c, cycloaliph~t1c or hr~matic ~ucleus including correfiponding halogen-subs~ituted ~uclei. Thu~, R' ~y be: ~ ba~lent ~lkylene group, -(Cn H2n") , wherein n~ i~ an integer of from 1 to 10 as ~n the ~atura~ed acyclic diba~ic ~cid 6eries, ~OC-(CB2)n~-COOH, an alkenylene group hav~ng from 2 to 10 carbon atoms ~s in ~aleic ~cid ~nd itaconic acid; dimer or trimer acids, or ~ixtures thereof; ~n Arylene group as in phthalic, isophthalic ~nd terephthalic ~cids: an aralkylene nucleus as in bomophthalic Acid; cycloaliphatic nuclei as in the hydrophth~lic acids including di-; tetra-, and hexa-hydrophthalic acids, ~nd bicyclo[2~ hept-5-ene-2,3-dicarboxy.lic acid; and corre~ponding halogena~ed nucli as in chloromaleic acid, tetrachloro- and tetrabromophthalic acids and chlcrobicyclol2.2.13-hept-5-ene-2~3~dicarboxylic acids ~uch as chlorenclic acid. Specific examples of this class of compounds are: bi6-(3,4-dihydro-2H-pyran-2-methyll-succinate, -~dipate, -azel~te, -sebacate, -tetrachlorophtha- late, -tetrabromophthalate and -chlorendate. Thi6 type of reactant is prepared by the conden~at~on of 3,4-dihydro-2H-pyranyl-2-alkanols ~ith the diba~ic acid or acid halide of the dibasic acid.

6. Poly-(3',4'-dihydro-2'H-pyran-2'-alkyl) carbamates which comprise the reaction product~

D-13,855 ~ormed by conden~tion of 3,4~dihydro-2H~pyranyl-2-csrbip~ls and ~n organic polyisocysnate ~uch a~
t~ose ~escribed below. Among the ~uatable polyi~ocyanates ~hieh ~ay be u~ed in the prep~ration of ~uch ~ono~er~ for u~e ~n the presen~ invent~n are tho~e hav~g the for~ul~ (NCO)i, wherei~ i i6 ~n integer ~ tw~ or ~ore and R~ is an organic radical hnving the ~alence of ~. ~w can be ?n aliphatic, cycloaliphatic or aromatic radical which m~y be unsubsti~uted hydroc~rbyl qroups or hydrocarbyl gr~ups ~ub~titute~, for example, wi~h halogen or alkoxy groups. ~hu~, w~en i is two, for example, R~ ifi a bivalent ~ubstituted or unsubstituted ~ydrocarbon group 6uch ~ alkylene, cycloalkyl~ne, aryle~e, alkyl-~ub~tituted cycloalkylene, alkarylene, ~ralkylene and like groups. ~ypical ex~mples of 6uch polyiso~yanates are: 1,6-hexam~thylene dii~ocy2nate;
1,4-tetramethy:lene dii60cyanate;
l-methyl-2,4-diisocyanatocyclohex~ne;
bis~4-isocyanatophenyl)methane; phenylene diisocyanates ~uch as ~-methoxy-1,3-phenylene-diisocyanate, 5,6-dimet~yl-1,3-phenylenediiso-cy~nate, 2,4-and 2,~-tolylene diisocyanates~
tolylene ~ ocyanate, ~ opropyl-1,3-phenylene-dii~ocyanate, durylene dii~ocyanate, triphenyl-methane-~,~',4~-triisocyannte, 3-isocy~natomethyl-3,5,5-trimethylcyclohexyl-i~ocy~n~te, or ~'-dicyclohexyl-methylene diisocyanate and many other orangic polyisocyanates that are known in the ~rt ~uch as those disclosed $n an article by Siefkin, Ann. 565,75 (1949). Also included 35 u~eful in the preparation of the carbamate monomers employed in this invention ~re the polyisocy~nates of the ~niline-formaldehyde poly-~romatic type which are produced by phosgenation of the polyarnine D-13,855 obtained by a~oid~a~alyzed ~ond2nsa~c~ on of ~ni line wi th f orm~ ldehyde . P~lsrphenylme~chylene pc~lyi~ocy2lnat~ of thi~ ~ype ~re av~i lable commer~ially under $u~:h ~r~de names ~s PAP~ ~?PI, ~c~ndu~ n~e~90Pt NC0-120 an~ NC0-~0. ~he product~ ~re low vi~osity t 50-500 ~entipoi~es alt 25C. ) l~ uids h~Y.ring aYerage is~cyan~tcs ~unctionalitie~ ~n the rAn~e of ~bc~ut 2v 25 to about 3.2 c~r hi~her, dependin~ upon the ~pecifi~
~niline-to~form~ldehyde ~olar ra~io u ed in the polyamine prepar~tion. Other useul polyisocyanates are! c~mbin~tionc of dii~c~cy~n~tes with pol~eric isocyanates containing mc~re than two ieocyanate groups per mole~ule. Illu6trative of ~uch combinations are: a ~ixtur~ ~f 2,~-tolylene diisocy~nate, 2,6-tolylene diiso~yanate and the ~foresaid polyphenylmethylene polyi~ocyanates; and a ~ixture of is~meric t~lylene diisocyanates with poly~eric tolylene diin~cyanate6 ~btained ~s residues frcm l:he manufacture of the diisocyanates.
When the i~ocyanate which i5 reacted with the 3~4-dihydro-2H-pyran-2-carbinol contains two isocyanat~ funl:tions, bi~-(3',~'-dihydro-2'H-pyr~n-2-alkyl)dicarbamates are fQrmed having the generai formula:

~-t CH nH 2n ~ C-NH --R~ -NH -~ -O ~ Cn~ 2n ~A-6) wherein Z, Z' ~nd n are ~s defined hereinabove; ~nd R~ corresponds to the R~ nucleus of the isocyanate reactant, R~(NC~)i when i is two. It i6 to be ~trad~ rnar~<

D-13,855 understo~& that ~hen the ~ocyanate ~ n i~ooyanato function greater ~han two, the pyranyl monome~ will h~ve a oorresponding ~ver~ge number of c~rbamate groups and the gener~l formula:

Cs~Z)~ ~C~H2") OC(O) NH R~ [-NHC~O) O
~n~2n~ ~5~2')2~

wherein C~tZ~20 ~nd C~')20 are the respective 3,~dihydro-2~-pyranyl ring6. Typical examples of this cl~ss o di-~dihydropyranyl) ~omp~unds are toluene-2,~-~ or 2 ~ 6 ) ~ bi ~- 3 ~ di hydro- 2 ' ~-pyran-2'-methyl) carba~ate, and the reaction produ~t6 of 3~-dihydro-2'~ pyranyl-2~carbinol with the aforesaid polymerio liquids h~ving an average iso~yanato func~ion of about 2.25 to about 3.2.
It is, of course~ underxtood by those skilled in the art that when such nitrogen e~ntaining compounds are used with photoinitiator~, only minor amounts of basic organic nitro~en cont~lning compounds may be used 60 ~S not to interfere with the polymerization reaction.
Additional ~yclic vinyl ether compounds include the following:

~ H20H ~ ~ CH

2CIX ; ~ ORl ' ' ' ;
Rl wherein Rl is hydrogen or methyl, Rl'i' is alkyl of 1 to 10 carbon atoms, ~Ind X is selected fro~

~-13,~55 ~13 -~C~-C~-O)n ~ 1' or ~[-~-tC)~
~1 ~3 ~herein n has a value of fr~m 1 to 50 ~na where~n R~ he residue of A carboxylic acid and c~n be (1) hydrogen~ l2~ alkyl which ~s ~ubstitute~ with ~ny ~ubstltuent ~h ~DeS ~0~ unduly i~terfere with the polymerizati~n, or unsubst~tuted, linear or br~n~he~, ~ontaining up to 20 carbon ~t~ms, such es ~et~yl~ ethyl, i80propyl, decyl, eicosyl and ~he l~ke~ and ~3) ~ryl whi~h ~ æu~stituted with any ~ubcti~uent which does not unduly interfere with the polymeri~ation or, which i~ un6ubstituted, having 6 to 10 ring carbon atoms, ~uch ~s phenyl, naphthyl, benzyl, pene~hyl, and the like.
Another 9FOUp Gf compounds which are useful in the compositions of this invention are the ~lkylene oxide ~dducts of 3/4-dihydropyran-2-methanol of the general formula:

~ CH2~(C~~cBO)n wherein Rl a~ n are ~s hereinbefore defined.
This cla~s of compounds is prepared by the ethoxylation or propoxylation of 3,4-dihydropyran-2-methanol with ~ base c~talyst 6uch as potassium or sodium ~etals. The catalyst concentration can be from 0.1 weight percent to 0.4 weight percent, preferably from 0.2 weigh~ percent to 0.3 ~eight percent based on the weight of the final product. ~he reaction can be carried out a~ a temperature of from about 75~C to about 150C, prefer~bly from about 100C to about 120C.

~_~3,85~

~ 13 Another group of compounds which can be used in the composition6 of this invention are ~he lactone ~dduct~ of 3,~-dihyaropyran-2-methanol of the general for~ula:

CH~0~ e -(Ct~D]~B
~3 wherein R3 i6 a hydrogen, alkyl, alkoxy, aryl, cycloalkyl, ~lkaryl, or ~ralkyl ~roup having up to 12 carb~n ~toms and ~t leas~ ~2X-3) of the R3 groups are hydr~gen ~toms, x ba6 ~ value of 2 to 12, and R
and n are as hereinbefore described. This class of ~ompounds i prepared by reacting a lac~one with 3,~-dihydropyran-2-~ethanol ~t a ~emperature of 100C ~o 200G. ~ catalyst ~uch as stannous octanoate ~n dibutyl tin dilurate and the like can be used to facilitate the polymerization~ The lactones that can be used are epsilon-caprolactone, epsilon-methyl-epsilon-~aprolactone, gamma-methyl-epsilon capro:L~ctone, bet~-propiola~tone, deta-valerolac~Qnell zeta-enanthGlactone, gamma-ethyl-epsilon-~ethyl-epsilon-caprolactone, ~nd the like.
These lactone adducts of 3,4-dihydropyr~n-2-methanol ~ay be reacted with alkylene oxides such 5S ethylene oxide or propylene oxide to from ~lkyleneoxide adducts of the lactone adduct6 of the general formula:

~CH2Cl~--tC)~Oln tCH2-CHO)~

wherein Rl, R3,~ n, and ~ are as hereinbefore described.

D-13 t ~55 o~
~ ~4 ~

Ineluaed ~n thi6 cla~6 of compounas w~uld be the lactone adduc~ of ~he alkylene ~xide adducts ~f 3,i-dihydropyran~2-me~hanol of the general for~ula:
~ 7 ,, ~2(~Z-~ O)~-IC~ o;~

wherein Rl, R3, n, ~nd x are hS hereinbefore ~escribedO
~ till ~nother gro~p of ~ompounds which can be used in the composi~ion6 of this invention are the ester~ of a~ least one organie carboxylic acid ~nd 3, ~-dihydropyrarl-2-methanol corresponding t~ the f ormu la .

~ ~RCH2~ 1 wherein Rl and Rl' re as hereinbefore defined.
These compounds are prepared by conventional esterification ~r transesterification procedures with a ~uitable cataly6t and can c~ntain substituents in the molecule provided they do not unduly interf2re with the reaction. These procedures and catalyst~ are well known to those ~killed in ~he art ~nd reguire no further elaboration. In the tran&esterification, the lower alkyl esters ~f organic acids are preferred sources of the acid moiety.
~ nother ~roup of ~ompoùnds which can be used are reaction product6 of the following:

~H

wherein Rl ~8 ~S previously ~efined with ~ompounds ruch ~,s pentaerythritol, formaldehyde, other aldehydes ~u~h ~s i~obutyraldehyde t~ yield cyelic vinyl ether pr~duct6 Eu~h h~:
~CE~C C

[o~

~ 2 ~-CH
~H3 The linear vinyl ethers are well known in the art and many are commerci~lly available. The vinyl ethers include the alkyl vinyl ethers, aryl vinyl ether~, divinyl ~therfi, ~- and B-substituted vinyl ether~ and functionally ~ubstituted vinyl ethers. ~he alkyl vinyl ether mon~mers include:
methyl e~hyl ~opropyl n-butyl irobutyl ~-butyl t-butyl n-~myl isoamyl 1,2-dimethylpropyl n-hexyl ~-13,855 ~ ' - ~

1,2 d 2 tri~ethylpropyl 2-ethylbutyl 1,3-di~ethylbutyl 2j2-di~ethylbutyl ~ opropylmet~yl n-octyl 2 ethyl~exyl l~ethylheptyl 2,2-~imetbylhexyl n-decyl 2,2-dimethyloctyl 2~2-di~ethyldecyl n-tetradecyl 2,2-di~ethyldodecyl n-hexadecyl 2,2-dimethyltetra~e~yl o~tad~cyl oleyl The aryl vinyl ether ~onomer~ include:
pheny:l o cre~syl p-cresyl p-chlorophenyl 2,~-dichlorophenyl 2,~,6~trichlorophenyl ~-naphthyl B-naphthyl The divinyl ether~ include the ~ollowing:
C~2 C~ (CH2)2 CH CH2 CH2~CH-O- (CH2 ) 3-0~ R~CH2 C~ C~2 0 CH2-CH2-~l~-0-CH-CH2 CHl CH2~CH-o-tc~2)6-4-~ ~H2 CH2 CH ~-C~2-c~:l2)2-O-C~=CH2 CH2 CH (~-CH2-~2)3-o-cH=cH2 D-13,~55 ~ 17 C13 2~ H 2 ) J ~ ~cEil 2 C8~H~ cH2)~ c~2~ H2)~ 2 CB2-~B O~CH ~ C~2 V~CH~C~2 (ci~ and trans) ter~iol ~iv~nyl eth~r~
The ~- And ~- æubstituted vinyl et~er~
include the ~ollow~ng:
~ethyl ~-~ethyl~inyl ~ther ~ethyl ~-chlorovinyl ether ~ethyl ~-~ethylvinyl ether ~ ~rPr~G ) ~ethyl B-ehlorovinyl et~er ethyl ~-ethylvinyl ether ethyl ~-methylvinyl e~her ~i6) (trans3 ethyl ~-phenylvinyl ether i60propyl ~-~et~ylvinyl ether ( c i s ) (trans) n-butyl-~-mekhylvinyl ether (tsans~
i ~butyl-~-methylvinyl ether (Ci6) Stran~) t-butyl-~-methylvinyl ether (ci~, tran~) Fun~tionally sub~tituted vinyl ethers are of the formula:

D-13,855 - lB ;

wherein ~ ~s selec~ed ~rom:
, CH2C~20H
CH2S~H2~ H2C~2 C~2~ 2~1 ~3 C~(CF332 C~CF3)(C~2Cl) CFtCF2C1~2 CY2~H20C~2C~2 CH2C~2C~013CH3 ~CH20cH2~20c~3 CH2C~20C~2CH20c2B5 C~2C~CB2 The cyclic vinyl ether containing compound i~ used in amount~ of from 1 to about 99, preferably from about 5 to about 95, and the li~ear vinyl ether is used in amounts of from 1 to about 99, preferably from about 95 to about 5 part6.
~ he composition of this invention may include a poly(active hydr~gen) organic compound.
These poly(active hydrogen organic compounds include ~ny compatible organic compounds contnining two or more active hydrogen atoms per ~olecule. The poly(acti~e hydro~en) ~rgani~ compounds are well known to ~ho~e skilled ~n the Art ~nd include, for example, ~rganic polyols and the like.
Sub~tant$ally ~ny of the organic polyols previou61y used ln the hrt to ~ake coating compositions c~n be used and are preferred as the poly(active hydrogen) organic compounds in thi~
invention. Illu~trative of the polyols useful in pro~ucing coating compositions in accordance with this invention are the polyether polyols 6uch as polyhydroxyalkanes and polyoxyalkylene polyols, the ~-13,855 19 ~ ;3L,f6~

~ryli~ and vihyl polyol~ the polye~ter polyol6, the polycaprolactone polyol~ ! ~nd ~ther lactone polyols ~uoh as polyv~lerolactone polyols, poly-~ethyl-caprol~ctone polyol6 ~ ~nd the like~ the polymer/polyol~ t ~na the llke. Among the po~yetheY
polyols ~hi~h can be employed ~re those ~elected from one or ~vre of the followins cla~es of ~mp~itlons, ~lone or ~n admixtur~, known t~ tho~e ~killed ~n the art:
~ ) Al~ylene ~xide adduct~ of polyhydroxyalkane~;
(b) Alkylene oxide ~dduct6 of non-reducing 6ugars and ~ugar ~eriv~tives;
(c) Alkylene oxide adducts ~f phosphorus and polyph~fiphorus a~ids;
(d~ Alkylene oxide adduct6 of polyphen~ls;
~ e) The polyols ~rom natural ~ æuch ~s eastor oil, and ~he like.
Illu~trative ~lkylene oxide addu~t~ of polyhydroxyalkanes include, ~mDn9 others, the ~lkylene oxide ~dducts of ethylene glycol, propylene glycol, 1,3-~ihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,~-, 1,5-, and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6-, and 1,8-dihydroxyoctane, l,10-dihydroxydecane, glycerol, 1,2,~-trihydroa~y~ut~ne, 1,2,6-trihydroxyhexane, l,l,l-trimethyloleth~ne, 1,1 t l-trimethylolprop~ne, pentaerythritol, polycaprol~ctone, xylitol, ~rabitol, ~orbitol, ~annitol, And the like. A
preferred clas~ of alkylene oxide adduct6 of polyhydroxyalkanes are the ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, ~dducts of trihydroxyalkanes.

D-13,8ss further ~1a~B t7f polyelther pe~lyol~ whi~h ~an be employed are the alkylene oxide add-~c~ of the nbf~reduclrlg sug~r~, w~lerein the ~lkylene oxides have f rom 2 tc~ 4 c:arbon at~ms . Among the n~n-reduc~ng ~ugar~ ~and ~ugar deriv2ltiv~
eontemplated Are ~ucro~e, alkyl glycoside~ ~uch ~s ~Det~yl glucos~e, ethyl gluco~Se, an~ ~he like, glyccl g lycos ide~ xuch 115 ethylene 9 :Lycol g lu~ os i de, propylene gly~ol gluco~de, glycerol glucoside, 1,2,6-hexanetr~s:l glucosi~e, ~nd the like, as well as the alkylene oxide adduc~cs of the alkyl ~lyco~ide~ ~s ~et fortll ~n U.~;. 3,073, ï~8.
The ~l)cylene ~xide a~l~uct~ of phosph~rus and polyphosphoru~ acids are another u~eful class of polyether polyol~. ~Sthylene oxide~
1,2-epoxypropane, the epoxybutanes, 3,-chloro-1,2-epoxypropane, and the like are preferred alkylene oxides. Phosphori~ acid, ph~sphoru~ acid, the polyphosphoric acids 6uch as tripolyphosphoric acid, the polymetaphosphoric acids, and the :like are desirable for use in this conne~tion.
A ~till fur~her ~sQful class of polyether polyols ~ the polyphenols, and preferably the alkylene oxide adducts thereof wherein the alkylene oxides have ~rom 2 to 4 carbon atoms. Among the polyphenols ~hich ~re contemplatea are, for ex~mple, bisphenol Ag b~6phenol F, ~ondensati~n products of p~enol and ormaldehyde, the novol~c resins, condensAtion products of vDrious phenolic compounds ~nd ~crolein; the simplest member of this class being the 1,1,3-tri~hydroxyphenyl) propanes, condensation producte of various phenolic compounds and glyoxal, glutaraldehyde, and ~ther dialdehydes, the ~implest member~ of this cl~ss being the 1,1j2,2,-tetra ki~thydroxyphenol) ethanes, and the llke.

q`he polyether polyol~ ~e~crlbe~ hereir;hbove can have hydroxyl number~ which v~lry oveY a widP
range.~ In general, the hydroxyl number~ of ~he above àecribed polyols employed in thi~ inventi~r can range fro~ about 15~ and lower, to ~bout 90a, and higher . ~Irhe hydroxyl number i~ def ined ~ the number of miil~grams of pota ~ium hydroxide required for ttle coi~plcte neutral~ation of the ully phth~lated derival'c~ve prepared from 1 S;ram of polyol. The ~lydroxyl number can also be def ined by the egu at i on:
56.1 x 10~ x ~ .w.
where OH ~ hydroxyl number of the polyol;
functic)nal$ty~ th~t i6, average number of hydrc~xyl groups per ~nolecule sf polyol;
~nd m.w - molecular weight of the polyol.
The polyether polyols describPd hereinabove ~an be prepared by conventional me'chods and are cc:mmercially avail~ble from 21 number of manuf ~cturers .
~ he p~lyeaprola~tone polyols, alone or in admixture, that c2n be used to prep~re the coating compositions of this invention include any of the known polycaprolactone poly~ls that are commercially available ~nd that are fully described, for example, in U.S. Pat. No. , 169,945. As described in this patent the polyc~prol~ctone p~lyols ~re produced by the catalytic polymerization of an excess of a caprolactone and an organic polyfunctional initiator having as least two reactive hydrogen atoms. The organic functional ini~i~tors can be any polyhydroxyl compound ~s is Rhown in U.S. Pat. No.
3,169,945. Illustrative thereof are the diol~ ~uch as ethylene glycol, diethylene glycol, triethylene glycol, 1,2~pr~pylene glycol, dipropylene glycol, D-13,~55 - ~2 1,3-propyl~ne glycolO pol~ethylene ~lyeol ?
polyprspylene gly~ol, poly(oxyethylene-oxypropylene) glyco~s~ and ~i~ilar polyalkylene glycols~ either blocked, c~pped or ~eteric, con~aining up to ~bou~
~0 or ~ore alkyleneoxy unit~ in ~he ~olecule~
3-~ethyl~1-5-pentanediol, ~yelohe~nediol, ~,4'-methyle~e-bis-cyclohexanol, ~,4'-isopropylidene bis-~yclohex~nol, xylenediol, 2-54-hydroxymet~ylphenyl) ethanol, 1,4-butanediol, 1,6-~exanedi~l and the like; triols such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanslaminel triisopr~panolamine, and lche like;
tetr~ls ~uch ~s erythritol, pentaery'chritol, N,N ,N ' ,N ' -tetraki6 ( 2-hydroxyethyl ) ethylene diamirae, and the like.
When the organic function~l initi~tor is reacted ~i~h the caprolactone ~ reaction occurs that can be represented in its ~implest form by the equation:

R4~H~X ~ ~=C~f ~fHR'. ~ [OCtC)4 CHR~-mOH)X

t ~1 In this equati~n the organic functional initiator is the R4-tOH)X compound ~nd the caprolactone is the o=~c ) 4CHR5 O R5 ¦

compound; this cnn be csprolactone itself or a substituted caprolactone wherein R5 is ~n alkyl, a;ko~y, aryl~ cycloalkyl, ~lkaryl or aralkyl group h3ving up to twelve carbon atoms and wherein at D-13,855 lel!l5~ ~lx of ~he R~ groups are hydr :sgen e~Q5~15, as 8hOWII ~n U~S. Pet. No~ 3~169,945. The polycaprQlaotone polyol6 ~hat are used are shown by the formula on the ris3ht hand li;ide of the equation;
they ~an have Jln ~verage ~ole~uïar ~eight of from 200 tc~ a~out 6, 000 . The pref erred p~ly~aprolactc)ne polyol compound~ are those hav~ng an aYer~ge ~oleeular ~eight of from abc~ut 290 ~o about 6, 000, ;nost preferably from about 290 to 3,000. The most pref erred nre the polycaprolaotone diol e~umpounds having ~n ~verage mQlecular wei~ht Qf from about 290 tt) abc)ut 1, 500 and the polyc~prolac~one triol ~nd tetrol compounds having an aver~ye mole~ular weigh~c of from about 290 to about 3,000; these ~re most preferred because ~f their l~w Vi~ 06ity properties.
In the formula ~ i8 an integer repre~entin~ the average num~er of repeating unit~ needed to prc~duce the compound haviny 6aid mole~ular weight6. ~he hydroxyl number of the polycaprolactone polyol can be from ubout 15 to 600, preferably from 200 to 500; and the polycaprolactone can have an average of from 2 to B, preferably 2 to ~, hydroxyl groups.
Illu~trative of polycaprolactone polyols that can be used in the coating compositions of this in~en~ion, one c~n mention the reaction product~ of a polyhydroxyl ~ompound having an average from 2 to 6 hydroxyl groups wi~h ~prolactone. The manner in whiGh these type polycaprolactone polyols is pr~duced is 6hown in ~.S. Pat. No. 3,169,945 and many 6uch compositions ~Ire commerciully available. ~n the following table there are 11sted illustrative polycaprGlactone pc~lyols. The first column lists the organic functional initiator that is reacted with ~he caprol~ctone and the aveY~ge molecular weight of the polycaprolactone polyol .is shown in the second column.

D-13,8S5 - 2~ ~

~n~wing the ~olecul~r weights of the initiator and of the p~lycaprolactone polyol one can readily determine the ~veraqe number of ~ole~ule~ of caprolaetone (CPL
~nit63 that reaeted to pro~u~e the ~omp~un~, tbi~
figure ~8 ~own ~n t~e third ~olumn.
P~LYCAPR~LACTONE POLYOLS
Average A~erage No.
MW of of CPL units Initiator pol~l in_mole~ules 1 Ethylene glycol 290 2 2 Ethylene glycol ~03 6.5 3 Et~ylene glyeol 2,11~ 18 4 Propylene glycol ~74 5 Q~tylene glycol 602 4 6 Decalene glycol ~01 5.5

7 Diethylene glycol 527 3.7

8 Diethylene glyeol 8~7 6.5

9 Die~hyler,e glycol 1,246 10

10 Diethylene glycol 1,998 16~6

11 Diethylene ~ly~ol 3,526 30

12 ~riethylene ~lycol 754 5.3 1~ Polyethylene qly~ol(MW 200)~ 713 4.5 14 Polyethylene gly~ol~MW 600)~ 1,398 7 15 Polyethylene glycol~MW 1500)~ 2,868 12 16 1,2~Propylene gly~ol 646 5 17 1, Propylene glycol 988 8 18 ~ipropylene glycol 476 3 19 Polypropylene glycol(MW ~25)~ 835 3.6 20 Polypropylene glycol(MW 1Q00)*1,6B4 6 21 Polypropylehe glycol~MW2000)~ 2,456 4 22 Hexylene glycol 916 7 23 2-Ethyl-1~3 hexanediol 602 4 24 1,5 Pentanediol 446 3 25 l,~-Cycl~hexanediol 629 4.5 26 1,3-Bi~(hydroxyethyl)-benzene 736 5 27 Glycerol 54B 4 ~B 1,2,6-~exanetr~ol 476 3 29 Trimet~ylolpropane 590 4 30 Trimethylolpropane 750 5.4 31 Trimethylolpropane 1,103 ~.5 32 Triethanol~mine 890 6.5 33 Erythritol 920 7 34 Pentaerythritol 1,219 9.5 35 1,4-Butnnediol 546 ~.0 36 Neopentyl glycol 674 5.0 ~Average ~olecular weight of glycol.

D 13,855 2~ ~

The ~tructures of ~he ~ompounds in ~he above ta~ulation are ~bvious to one ~killed in the ~rt ~ased on the infor~ti~n given. ~he stru~ture of oompound O
8~SC~2)5~ lrC~2C~2~C~2C~21~ 2 5 r ~herein the ~riable r ~ ~n int~ger, the E~um e~f r r has ~n ~verage Y~lue of 3. ? and the aYerage ~oleoular weight i~ 527. The l3~cructure of e~mpound No. 20 is:
O O
! 11 ~ 2)5CO1r(C3B~)n~3~6[C(C~2)5~ ~
wherein the ~u~ of r ~ r has an avera~e value of 6 and the nverage ~olecul~r weight is 1,684. This explanation m~kes cxpli~it the ~tru~tural formulas of oompounds 1 to 34 6et forth above.
Polycaprolactone hexols ~uitable for use in the present invention can ~e prepared ~y the catalytic polymerization of ~n excess of polycaprolactone pc\lyols and ~ ~ycloaliphatic epoxide. Illu~trat.ive polycaprolacto~e polyols useful in the prepalration of polycaprolactone hexols ~nclude polycapr~l2~ctone diols, polycaprolactone triols and the like including mixtures thereof.
~any of these polycaprolactone polyols are commercially ~vail~ble from Union Carbide Corporation. CycloaliphRtic epoxides suitable for use in preparing t~e polyc~prolactone hexols include 3,~-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl~te, bis (3,~-epoxycyclohexylmethyl) adipate, vinyl cyclohexane ~ioxide and the like.
~any of these cycloaliph~tic epoxides ~re ~_~3~55 ~,'?~'DC,j~

~ ~6 ~

commercially ~vAil~ble rom Union Carbide Corpor~tion. A ~uitable polymerizAtion ~atalyst i6 ~iethylam~nium triflate ~hi~h i6 co~mercially ~ail~ble fr~m t~e 3M Gompany a6 ~C-52Q.
A preferr~d ~ethod fQr preparation of the polyc~prolactone ~ex~16 compr~se~ adding one or ~ore p~lycarpolactone triol~ to a rea~tor~ heating the polycaprolactone tri~l~ to a te~perature o~ about lOO~C and addi~g the ~atalyst using a nitr~gen sparge as ~Qn ns the polyc~prola~tone tri ls Rre molten. The polycapr~laetone tri~ls and catalyst ~ixture ~B then he~ted to a temperature of from about 150C to about 2Q0C and a cycloaliphatic epoxide is added to the ~i~ture. ~he re3ction is carried out for about one hour to About three hours or until the oxir~ne cQntent has been redu~ed to a nil or almost ~ nil v~lue. A ~difi~ation of thi~
pr~cess can involve initially adding all of the ingredients into the reactor. A further modification of this method can involve a v~cuum treatment of from 10 to 30 ~inutes af~er the catalyst addition and/c~r the use of ~ va~uum during the heatin~ of the polycaprolatone triols to a mol~en ~ta~e. Preferred polyc~prolactone hexols ~Lit~ble as ingredientEi in the oonting compositions of thi~ invention have an average molecular weight of from about 600 ~o about 1500.
~ he polymer/p~ly~ls th~t cnn be used to prepare the ~oating compositions of th.is invention nre known materials. Such polymer/polyols can be produced by polymerizing one or ~ore ethylenically unsatur~ted monomers dissolved or dispersed in a base polyol in the preBenCe of a free radical o~talyst. ~he production of polymer/polyols is more fully described in U.S. Patent Rei~sue 28,715, U.S.

D-~3,~5~

~ 27 ~

Patent Re~u~ 29,118, ~.~. Pa~ent ~,652,639, V~S.
Patent Rei~ue 29,014, U~S. ~ent 3,950,317~ U.S.
Patent'4,20~D314~ U~S. Patent ~,104,236, U.S. Patent ~,172,82~ and ~.S~ P~tent 4,198,~B8.
~ hile poly~oxypropylene) polyol6 are preferred, ~ubstantially any of the polyol~
prev;ou~ly u~e~ ln the art to ~ake polymeripolyols can be u~ed ~ the ba~e polyol. Illu6trative ~f the base po~yols use~ul in producing poly~er/polyol compositions hre the polyether polyols ~uch as polyhydroxyalkanes ~nd polyQxyalkyl.ene polyols, or t~e like. A~ong the base polyols whi~h c~n be employed are thQse Bel ec~ed from ~ne or m~r~ of the following cla~es of compositionsl alone or in ~dmix~ure, known to those ~killed in the nrt and descri~ed ~ore fully hereinabove:
(a) Alkylene oxide adducts of polyhydroxyalkaneQ;
(b) Alkylene oxide adducts of non-reducing ~ugar-~ and sugar derivatives;
~ c) Al~ylene oxide adducts of phosphorus and polyphosphorus ~cids;
td) Alkylene oxide adducts thereof of polyphenol~;
(e) The polyol from natural oils such as castor oil, and he like.
The most preferred base polyol6 employed in the polymer~polyols which are useful as ingredients in the coating composition~ of this invention include the poly~oxypropylene) polyols. It fihould be appreci~ted that a blend or ~xture of more than one base polyol c~n be utilized, if desired, to form the polymer/polyol.
Conceptually, the monomers used in preparing the polymeripolyols can comprise ~ny ~13,8S~

~ 2~ --ethylen~calls~ un~turate~ ~Qnomer or monomerfi. A
variety of monomer~ are ~iisGlo~ed in the patents relating to polymer/polyol6 previously reiEerred t~.
The ~eleotion of the mQnomer or ~onomers u3ed ~ill ~epend on con2l~erat1c~ns such 8E~ the relDt~e CoBt of the ~onomer~ a~sd l~he product chara~teri~tics required for the ~ntended appli~ati~
The preferred monomer and ~onomer ~ixture used to make the polymer por~ion of the polymer/polyol~ $c acrylc>ni~crile as)d a ~ixture of ~crylonitrile ~nd ~tyrene respectively. The relative wei~ht proportion~ of ~crylon;trile to styrene ~an range from about 80:2Q to about 20:80.
It may be de irable in ~ome applications to utilize, with scryl~ crile~ a cc~m4nc~mer other than ~tyrene.
Re2resentative examples of ~uitable COmQn~merS
include methyl ~eth~crylate, vinyl chlc~ride and vinylidene ~hloride.
The polymer and polyol content of the polymer/polyols can vary within wide limits, depending upon the reguirement6 of the anticipated end use ~pplic~ion. In general, the polymer content will vary from about 10 to ab~ut 50 percent, based upon t~e weight of the polymer/polyol. The polyol content of the polymer/polyols varies from about 50 to about 90 percent, based upon t~e weight of ~he p~lymer/polyol.
~ he polymer~polyol~ ~ay, if desired, be blended wlth other convent$onal polyols described hereinabove to reduce the polymer content to the level desirnble for the partieular end use ~pplication. Blends in which the resulting polymer content i~ ~s low as 4 percent of the total weight of the blend cr even less may be useful in the coating compo~itions cf thi6 invention.

D-13,855 2 ~

~ he ~t pref~rre~ e~ o~ polyol~
empl~yed in the coating co~poiSion6 o~ thi~
~nven~ion ~re the polycaprolAc~one polyol~ ~uch ~s ~ONE-0200 ~n~ ~oNE~030~ commercially available ~om Vnion ~rb~e ~rporaeion, th~ ~ihydroxyl fun~tion~l polytetramethylene oxide polyolx ~u~h a~ Polym~g 65~, 1000 ~nd 2000 eommer~ally a~a~lable ~rom Qua~e*r O~t~ Co~p~ay~ tbe poly~er/polyol6 ~uch ~5 NIAX Polymer Polyol 31-23 and 3~-28 co~mereially ~va~lable fro~ UnioA C~rbide Corporation9 and of course the ~thyl~ne oxi~e an~ propylene oxide ~flduct3 ~ncluding ethylen~ ~lycol, diethylene glycol, the p~ly(oxyethylene) glyco~6, the poly~oxypropylen~) glycol~, triol~ and higher funct~on~l~ty polyol~ uch ~8 L~T-67~ L~S-112, and LG-56 commercially available from Union Carbide Corporation. A preferred al~ylene oxide derived polyol ~uitable for u~e ~n the co~ting co~posi~ions of thi~ invention has the foll~wing for~ul~:
~6 ~ O --tCH2 _ ~H - o ~ ~ ~ 3 wherein ~6 ~ alkane ~f 3 to 10 carbon atom~, prefer~bly 3 carbon atoms, ~nd n i8 an integer of from about 10 to ab~ut 25. ~heEe polyols ~lso include poly (oxypropyl~ne-oxyethylene~ polyols;
~owe~er, desirably, the oxyethylene content 6hould ~mpr~e les~ than ~0 p~r~nt of the totel and prefer3bly l~x~ than 60 percent. The ethylene oxide ~hen u ed ~n be incorporated in any fashion ~long the poly~er ch~in. Stat~a Another way, the ethylene oxide can be incorp~r~ted either in internal blocks, ~s terminal block~, ~uch a5 the propylene oxide polyols capped ~ith ethyl~ne oxide, i.e., NI~X
Polyol 11-27 ~nd 11-34 and E-~74, commercially * T~ade ma~k 3 t ~S5 3 ~ ~L~

~vailable from Union C~rbide Corporation, o~ may be randomly di~trib~ted ~long ~he polymer ch~in~ A~ i~
~ell ~nown ln the art, the polyol~ that are ~o~t preferrea ber~n ~onta~n Yarying ~m~ m3unts of unsaturati~n. ~nsaturation in ~self does not affect ~n ~ny a~er~e ~ay t~e f~rmation of the coating compositions ~n ~cc~rdance with the present ~nventi~n.
Other preferred repre~entative examples of organic polyol~ t~xt may be employed in the coating ~ompo~itions of thi~ inYention include ~opslymers of hydroxypropyl and hydroxyethyl ~crylate~ and meth~crylAtes with other free radical-polymerizable monomers ~uch ~s acrylnte e6ter~, vinyl halides, vinyl ac~at~ or ~tyrene; copoly~ers containing pendent hydroxy ~roups formed by hydrolysis or parti~l hydrolysis of vinyl acet~te copolymers, polyvinylacetal resins containing pendent hydroxyl groups; modified cellulose pol~mers such as hy~roxyethylated ~nd hydroxypropylated cellulose;
hydroxy terminal:ed polyesters and hydroxy terminated polyalkadiene6. The polye6ter polyols are the reaction product~ of polyfunctional organic carboxylic acids ~nd polyhydric alcohols and include, for example, poly(hex~methylene ~d ipAte ) ~
poly~ethylene adip~te), poly(b~tylene adipate) and the like. Many of these organic polyols can be prepared by ~onventional ~ethods and are commercially ~v~ilable from A number of manufactuxer6 ~uch a6 polyvinylacetal resins commercinlly ~vailabl~ from Monsanto Chemical ~fh~de rn~ r~) J~ Company as ~u~varAB-7~A, B-73, B-76, B-90 ~nd B-98 `~ ~f~&d~ ~c~
and ss ~or~varA7/70, 12/85, 7/955, 7~95E, 15/9SS and lS/95E; an aliphatic polyester diol~m~merc~a~ly avail~ble from Rohm and Haas as Pa plex~

D-13,~55 - 31 ~

~atur~ted polyester polyols commero al~ly ava~lable from ~ob~y Chemic~l Cvmpany ~5 Mul~ron~R-2, -12A, R-l~, R-18, ~-38, R-6~f and R-74; a hydroxypropyl~te~ cellulo~e havin~ ~n equival~nt ~eiyht of approxi~ately 100 commercially available n ~ fro~ ~ercule~ In~. a~ ~lu~e ~ nd a ~ellulo6e ~cetate butyrate e~ter hnving a hydroxyl equi~alent weight of hpproxi~ately 4DO commercially avaîlab1e from Eastm~n ~od~k a~ Alcohol Soluble ~utyrat~.
Tbe poly(~ctive hydrogen) organic oompounds utili~ed in the ~oatin~ co~po~itions of this inventiDn ~an be mixtures or blends of organi~
polyols. ~or example~ when utili~ing a polycaprolactone polyol, it ~ay be desirable to mix or blend one or more of a propylene oxide poly~l~ a propylene oxide p~lyol capped ~i~h e~hylene oxide, a polytetramethylene oxide polyol or a polymer/polyol therewith. Other mixtures or blend~ may similarly be used ~f des;r~d.
The composition of this invention may include an epoxide. The epoxide~ which may be used herein ~ontain at least one epoxy group having the formul~:
O
-- C C--The epoxy groups ~an be termlnal epoxy groups or ~nternal epoxy gr~up~. ~he epoxides are primarily cycloaliph~tic epoxides. ~hese cyclo~liphatic epoxide resinfi ~ay be blended with minor ~mounts of glycidyl type epoxides, aliphDtic epoxides, epoxy cresol novolac resins, epoxy phenol novolac resins, polynuclear phenol-glycidyl ether-derived resins, ar~m~tic and heterocyclic glycidyl amine re~in~, hydantoin epoxy resins, Ind the like, and mixtures thereof. The cycloDliphatic epoxide resins may ~lso ~tr~ ~

~-13,~55 - 32 ~

be blended with minor amc~un'c~ of ~ycle~aliphatic epoxides ~laving a vi~co~ity of le5s th~n 200 cent~pc~i~e ~uch ~:

or ~ urther ~ ~ut:h cycloalipha~ic epoxides may be blended with other epoxides described ab4we.
~hese epc~xid*s are well kn~ n the art and m2rly are c:omrnercially avai lable .
Suitable cycloaliphatic epoxide resins for purpose6 of this invention ~re tho~e having ~n average of two or mc~re epoxy groups per mole~ule.
Illustrative of 6uitable cycl~aliphatic epoxides are the following:
_.
Diepoxides of cycloaliphatic esters of dicarboxylic acids having the fosmula:

R7 ~ Rlo ~ 16 ~--C~l;i!O R _OCH _ ~ ~

R15 \ R12 R21 /\ R24 R14 Ri3 R22 R23 wherein R7 through R24 cnn be the 6ame or different, are hydrogen or alkyl radicals generally containing one to nine carbon ~toms inclusive, ~nd preferably cont~ining one to three carbon atoms, inclusive, as ~or example methyl, ethyl, n-propyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl and the li~e; R i6 el valence bond or ~ divalent hydro c~rbon D~13, 855 ` ' ? ~ ~
~ ~3 ~

r~d~cal gener~lly ~ontanin~ one ~o ~enty ~rbvn ~t~ms, inclu~iYe, ~nd prefer~bly, containing f~ur to six c~rbon atoms; inclusive, ~s for example, alkylene radicals, ~uch as trimethylene, tetra~ethylene~ pentamethyl~ne, hexamethylene~
2-ethylhexamethyle~e, octAme~hylene, n4name~hylene, ~exadecamethylene ~nd the 11ke; ~ycl~aliphatic radi~al~, ~uch a~ 1,4-cyclohexane, 1,3-cycl~hexane, 1,2-cyclohexane, and the l~ke~
P~rti~ularly desirable epoxides~ falling within the ~cope of For~ula I, are those wherein ~1 thr~ug~ R18 are hydrogen ~nd R ~ ~lkylene cont&ining fuur to ~ix carbon atoms.
~ mong specific diepoxides of cycloaliphatic e~ter6 of dicarboxylic ~cids are the following:
bi~(3,4-epoxycyclc~hexylmethyl)oxalateO
bi~(3,4-epoxycyclohexylmethyl)adipate/
bi~(3,~-epoxy-6-methylcyclohexylmethyl) adipate, bisl3,q-epoxycyclohexylmethyl)pimelate, and the l.ike.
Other ~uitable compounds are descri~ed in 7 for example, U~S. ~atent No~ 2,750,3 FORM'JLA II
A 3,4-epoxycycl~hexylmethyl-3,4-epoxycyclo-hexane carboxylate h~ving the f~rmul~:

~ ~~O

9~ R15 ~8 R~ R16 R17

13,~55 3~ ~

~here~n Rl through R18 which can be ~he ~ame or different ~re a~ defined for R7 to R~ in ~rmula I. Partcularly de~ir~ble ~ompounds are ~ho~e ~ere~n Rl throu~h R 8 ~r~ hydrogen.
~ mong ~pecific compounds falling with~n the ~ope of For~ul~ re the ~ollowi~g: 3,4-epoxy-cyclohexyl~ethyl~3,~-epoxyeyclohexane carboxylate;
epo~y-l~methyloyolohexylmet~yl-3,~-epoxy-1 ~ethyl~y~lo~exane ~arb~xylate; 6-me~hyl-3,4-ep~xy-~yclohexylmethyl-6-met~yl-3,~-ep~xycy~lohexane ~arboxylate; 3,4-~pvxy-3 methyl~yclohexylmethyl-3,4-epoxy-3-~ethylcyclohexane ~arboxylate; 3,~-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl-cyclohexæne carboxylate. Other suitable ~ompounds ~re des~rabed in; for example, ~.S. ~ate~t No.
~,890,~9~
~ORMULA III
~ iepoxides having the formula:
R3' R~' Rll R12 C

Rlo 7 Rl Rlge Rg' R8~ R16' R15' wherein the R'~, which can be the ~ame ~r different, are monovalent ~ubstituent6 ~uch as hydrogen, hal~gen, l.e. chlorine, bromine, iodine or fluorine, or ~onovalent hydroc~rbon r~dicals, or r~dicals ~s further defined in U.S. Patent No. 3,318,822.
Particularly, desirable compounds are those wherein all the R'ç are hydrogen.

D 13,B55 ~RMULA I I I
" ~
Diepoxides havlng the formula:

R ~ Rq ' k ' 2 ~ R ' ~ C~2 \/ Rl 3 R~>~ 6 17 /~ ~ 4 ~ 9 ~B Rlt, ' R15 ' wherein tl~e R'~, which can be the same or dlfferent, are monovalent ~ubstituents such as hydrogen, halogen, i.e~ chlorine, bromine, iodine ~r fluorine, or monovalent hyc~rocarbon raulcals, or radicals as further defined in U.S. Patent No. 3,318,822.
Rartlcularly, desirable compounds are those wherein all the R'~ are hydrogen.
Otner ~ultable ~ycloallE,h~tic epoxides are the followint30 ~ 2----0---~H2--~\ / CH2 ~=D

~nd the 1 i k e .
The preferred cycloaliphatic epoxlaes are the fol lowin~:
3,4-Epoxycyclohexylmethyl-3,4-Epoxy-cyclohexane carboxylate ~ o~CN2 ~C

13, 855 ~ 35b~

Other sui~ab~e eycloaliphatic epoxides are the foll~wing:

~ H~ H ~ 2 a~

~nd the lik~.
~ he preferred ~ycloaliphatic epoYides ~r~
the following:
3 t 4-Epoxyc~clohexylmethyl-3~-E
cyclohexane car~xylate o - C~2~p Bis(3,4-Epoxycyc~ohexylmgthyl)adipate --CH 2----~--C ~ B -C - O- CH ;~
2-~3,~Epoxy~yclohexyl-5,5-~piro-3,4-epoxy)cyclohexane-meta-dioxane ~r ~ixture~ there~f.
Epoxides with ~ix membered ring 6tructures ~ay also be used, ~uch as diglycidyl ester6 of phthalic acid, partially hydrogenated phthalic acid or fully hydr~genated phthalic ~cid.
representative diglycidyl ~Dster of phthalic aeid is the foll~wing:

D-13,855 -~ 36 ~
.~

a )D\
C H 2C~ 2 ~~ 2~ ~ 2 O
D~lyol~yl e~ter~ ~f hexahydrop~thalic ~cid~ being preferred.
The glyci~yl-type ~poxides are preferably diglycidyl ether~ o bisphenol R which are derived from bisp~en~l A and epichlorohydrin and have the following ~r~ulas ~H3 OH
CHz CHCH2 O ~ C ~ OC~2CHCH2_ CH3 n _ ~
CH ~ ~CH~C ~ C~2 The cresol~ovolac epoxy resins are ~ultifunctional., ~olid polymers characterized by low ionic and hydrolyzable chlorine impurities, high chemical resi~tance, and thermal performance~
The epoxy phenol novolac resins ~re generally of the f~llowing f~rmula:

~H P

D-13,855 ~ 3 - 37 ~

The polynuclenr phenol-glyoidyl ether-derive~ resin ~se generally of the formula:

( ~ ~ \ ( J 3 Among the ar~mat~c and heterocyclic glycidyl amine resin~ which ~ay be in~luded herein are the following: tetra~lycidylmethylenedianiline derived resins of the following formula:

~2----CHC~ 2~ N ~;C8 2 Triglycidyl-p-aminophenol derived resins, triazine based resins and hydantoin epoxy resins of the formula:
i ~' "0 , ~

~' = C~3 D-13,855 3 i~

~ t ~ c~:E cour~e under~tot~dl by tho~e ~kîlled ~n the art t~t wherl ~ phvtoiniti~or is used only minor ~mc~unt6 Qf t>asic ~rganic ni~:rc~gen cc~ntainin~
epoxide compounds may be used 60 æs not to ~nterf ere ~ith tl~e phc~tc~copc~lymeri~tic)n reDct~ n.
~ he photoiniti~tor~ w23i~h may be u~ed herean ~nclu~e one e~r more o a ~etal ~lu~rohorate ~Ind c~mplex of boron trif luoride, as dles~ribed in 1~.5. Patent 3~379,653; a bis(perfluor~alkylsulf~nyl~
methane metal ~alt, as described in U.S. Pel~ent 3,5B6,616, an ~ryldiazonium c~mpourld, ~s desor1bed ~n li.S. P~terlt 3,7û8,2g6; a~n sromatic onium ~alt of Group ~ elements, as des~ribed in U.S. Pa'cent ~1,058,~00; an aromatic onium ~alt t)f :;roup Va element~, as de~cribed in U.5. Patent 4,069,0~5; a dicar~onyl cheleate ~f a Group IIIa-Va element, ~s described in U.SO Patent ~,086,091; a thiopyrylium ~alt, as described in ~.S. P~tent ~,139,655; a Group VIa element having ~n MF6 anion where M i~ ~elected from P, As and Sb, ~s described in U.S. Patent 4,161~47B; a triarylsulfonium complex ~alt, as described ih U.S. Patent ~,231,951: and an aromatic iodonium complex 6alt and an ar~matic sulfsnium complex ~alt, a5 described in U.S. Patent 4,256,~2B. Preferred photoinitiators include triarylsulfonium complex 6al~s, aromatic ~ulfonium or i~donium 6aits of h~logen-containing complex ions, and arom~tic ~nium salts of Group IIIa, Ya and r.~ VIn elementE. Some ~f s~lch ~lts ~re comme~cially ~vailable, auch ~s ~ ~ ~(an~)FC- ~9~aval1~ble from Minnesota Minin~ ~nd Manufacturing Company), and /f ~a'e rn~ r fC ~
UVE-~014~(a~ail~ble from General Electric Company).
~ he photoinitiators are used in conventional amounts in the composition~ ~f this invention such as in amount~ from ~bout 0~1 to 30 parts by weight per 100 parts by weight ~f the epoxides.

~_~3,~55 .

~ 3~ --The ~omposi~ions herein ~ay ~nclude additives such ~s oiis, particularly ~ilieone oil, ~ura~c~tants ~uch as ~ilicone-alkylene c~xide c~pol3r~er~ and ~ylic polymer~, ~u~h a~ the Z~ 'e ~ r ) Modaflows~ tobtair~e~ from Mon6an~0 Che~mi~ oc, ~, ~ilicone oil ~:ontAis~iDg aliphatic cpoxlde groups, fluor~carb~n ~urfactants; low rn~lecular weight a~ h~ ; s:~llo~ ves ~ ~uch a8 butyl ~:ello~olve;
carbit~ls, such as butyl o~rbitol and diethylene-~1YCQ1, and the like.
If desLred, c~ne ~ay in~lude in the ~:o~positis~ns o~ thi~ ~nvention ~arious conventional non-basic ~iller~ le.q., ~ilica, talc, glass beads or bubble~, elays, powdered ~et~l ~uch a5 aluminum, er, ~inc oxide~ ete.~ ~nd other additives ~uch as ~ cosity modifiers, rubber, t~okifying ~gents, piS~men'cs, and the lilce.
The photocopolymeriz~ble compositions are particularly ~uit~ble ~n ~ variety of applications in the fields of protective coatings and graphic arts due to their flexibility, impact resistance, ~br~si~n-resictance, hardness ~nd adhesion to rigid, resilient and flexible ~Ubfitr~tes BUCh hS metnl, plastic, rubber, qlass, paper, woQd, ~nd ceramics.
~ he c~mposition ~ay ~nclude ~ reactive diluent which :i~ an unsubstituted or ~n unsubstituted cy~loalip~atic monoepoxide. The unsubsti~uted cycloaliphatic monoepoxides include cyclohexene monoepoxide, ~nd the like. The substituted ~ycloaliphatic monoepoxide i~
~ubstituted with alkyl of 1 to 9 c~rbon atoms, halogen, oxygen, ether, ester, hydroxyl or vinyl rndical~. Preferably, the ~ubstituted cycloaliphatic monoepoxide is vinyl substituted cycloaliphatic ~onoepoxide and i6 preferdbly D-13,~55 ~elec~e~ ~rom one or ~ore ~f the followiny:
~ vinyl cyclohexane monoepoxide h~ving the f~r~ula ~ 2~

(2) norbornene monoepoxide ha~ing the formula:

C~2~ or ~ 3) ll~onene ~ono~po~ide having the formula~

C ~ C~2 c~3 Another preferred 6ubstituted cycloaliphatie m~noepoxide i& hydroxyl substituted cycloaliphatic ~onoepoxide of the following for~ula:

~0 The photopolymerization of the compositions of the invention ~ccurs upon exposure of the composit~onr to any source of radiation emittin~
~ctinic radi~t~on ~t ~ wavelength within the ultraviolet and visible ~pectr~l regions. Suitable ~our~es of radiation include ~ercury, xenon, carbon arc lamps, sunlight, etc~ Exposures may be from less than ~bout 1 6econd to 10 minutes or more dependinq upon the ~mounts of particular polymeriz~ble ~teri~16 and photoinitiator being utilized and depending upon the r~diation ~ource ~nd ~istance from the ~ource ~nd the th;ckness of the D-13,855 cca~ing to be cured. The composition5 ~ay al~o be photo~olymerl~ed by exposure ~o electron beam ~rrAdiation. Generally ~peakin~ ~he do~age neces~ry ~ ~rom less than 1 ~egarad eo 100 ~egarads ~r mvre.
~ he i:o~p~ition6 of thiR invention ~nay be prepared ~imply by ~ixing the formulati~n ~gredi~nt6 t~qether~ preferably under ~6~fe light~
conditions when the photoini~iator is incorporateda E _ ~ he ~ollowing Examples 8erve o ~ive specific illustration of the practice of this invention but they are nst intended in any way to ACt to li~it th~ ~cope o thiB i~Ye~tiOIl.
The following design~tions used in the Examples have the following ~eaning:
Tetramer:

¢~LCB2OC _~
O O

Dimer ~lCXO
~ E~X: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane c~rboxylate.
Polyol 1: A trihydroxyfunctional polycaprolactone polyol with sn ~verage hydroxyl number ~f 3,10 and ~n average molecular weight of 540 f~e fn~z~
i`~ tT~NE-0305~obtaine~ from Union Carbide Corporation).
` Polyol ?: A dihydroxyfunctional polycaprolactone polyol with an average hydroxyl nun~er of 2L2 ~nd an ~verage molecul~r weight of 530 ~ra~
~ONE-020 ~ obtained ~ om Union Carbide Corporati~n)v D-13,~55 Polyol 3: A propylene o%ide polyol th~t has be~n c~pped with 15 percent ethylene oxide. It Ihas ~ hydrc,xyl n-umber s:~f 28 which ~orre ponas to ~n ~quivalent ~ig~t ~f 200~11.
~ : ~ivinylether of butan~aiol V~nyl ~ther II: divinylether of diethylene ~Y~
Surf~t~nt: A ~ilicofle surfactant with the _ _ ~tructure ~f~3~ 3 3 3 S i O _ ~; i O -- - ~ i ~ CH ~ ) 3 3 1 ~ ( C~ 2 ~ t:~C 2H 4 )~H 5 . S
~,, Photoinit aa or ~: UVE-1014, a solution of triarylsulfonium hexafluoro~ntimony 6alt with A
6pecif ic gravity of 1. 39 and a Brookf ield viscosity of 74 centipoi~e (obtained from General Electric Co. ).
Photoiniti~tor II: FC-508, a ~olution of a triarylsulfonium hexafluorophosphate with a specific gr~vity of 1. 33 and a Brookfield viscosity of about ~,000 cent~poi6e (~t 25~C) lobtain~d from Minnesota Hining and ~anufacturing Company).
The procedures used to test coatings cured with the compositions of this invention were as follows:
501vent Resistance (Double Acetone Rubs):
measure of the resi~tance of the cured film to ~ttack by acetone in which a film coating surface was rubbed with sn ~cetone soaked cheese cloth back and forth with hand pressure. A rub back and orth with hand pressure over the film coating surface with the acetone soaked cheesecloth was designated ~6 one Udouble ~cetc~ne rub" ~ The ef f eck that h D-13, 855 ~3 -~ertain number of double acetone rubs had on the film ~o~ting ~urf~ce was reported by a number in parenthe~s ~ollowing the number of ~ouble acetone rub~. The rating ~y~te~ or ev~lu~tinq ~ceto~e re6i~t~nce ~or ~ given number of double ~cetone rubs 8 ~ollo~:
~umber ~n Parenthesis After ~umber of Rubs Sl) No chAnge in ~ating app~r~n~e.
(2) ~cratched ~urface.
13) ~ulled~ ~arred, ~ome coating removed.
(4) ~reaks in coating ~ppe~ranee.
(5~ About ~ne-half of the coating removed.
Penci 1 Hardne s - ASTMD-3363-74 The ratlng ~ystem ~or pencil hardness was as follows:
6B-5B-4B-3B-2B-B~B~F-B-2H-3H-~-5H-6H
Ssfter Harder Crosshatch adhes~on - refers to a test uxing 10 __ parallel, 6ingle-edge, ra~or blades to scribe test films with 2 ~e~s of perpendicular lines in a crosshatch pattern. Ratings ~re bas~d on the mount of film removed Rfter applying and ~ubsequently pulling ~ ~ontact ~dhe~ive t~pe (Scotch Br~nd 606) away from the ~urf~ce of a ~cribed coating ~t a 90 degree angle i~ ~ fast, rapid movement. It is important to carefully ~pply ~nd press the tape to the scribed coatinq to eliminate air bubbles and provide ~ qQOd bond becau~e adhesion i5 reported as the percent of film rem~ining on the 6ubstrate with a l~0 percent r~ting indicating complete adhesion of the film in the ~ubstr~te.
Reverse or face impact resistance - measures the ~bility of a give~ film to resist rupture from a falling weight. A Gardner Imp~ct Tester u~ing Gn eight-pound dart i6 used to test the films cast nnd D-13,855 eured on tl e ~teel panel. The dart is rai6eà to a given ~leight in inc2~es ~nd dr~pped onto the reverse or face ~idle o~ a ~oated ~etal panel. The inches times pound~, design~ted ~nch-p;:~und , ~bs~rbe~ by the ilm with~ut ruptur~ng la recorded a~ the ever~e or ~ace i~np~ct re~i~tance of ~he f ilm.
le~ i t~ ~
The ~ngr~ien'c~ ~n Table I were pla~d in amber bottles ~nd mixed while working under a yellow light sour~e. ,~
The ~ys'cems were coated onto Bonderite 37 cteel plates with ~ ~30. 20 wire-wound rl~d and cured with one pass under ~ 190 watt per inch medium pre~sure mercury vapor W ~ource At 30 fee'c per mi nut e .
The propertie~ ~re 6hown in Table II.
TPiBLE I
Ingredients xamples _~rams ) ~ 1 2_ 3 Tetramer 3. 9 3 . 9 2 . 5 Dimer - ~ 1. 0 m-diis~propyl benz~ne - - 1. 0 Vinyl ether I 3. 9 1. 0 1. 0 P~lyol I 2 . 0 2 . 0 2 . O
Epoxy - 2. 9 2. 3 Surf actarlt I - O ~ 4 0 . 4 Photoinitiator 0. 2 0. 2 0. 2 All co~tings were tack f ree w~en warm immediately after ultr~violet light exposure.
TABLE II
ProPerties___ Examples Double Acetone Rubs100 ( 1 )100 ( 1 ) 100 ( 1 ) Penci 1 Hardness 3H 2H F
Crosshatch Adhesion ~) 0 98 100 Gardner Imp~ct ~in.lbs. ) Face 5D 25 25 Rever~e 15 <5 C5 ~ t~e rna~k ~-13, ~S, f-~
~ ~5 ~

Cc~trol~ A ~nd 13; Examples 4 tv ?
J The foll~wing examplE!!s describe coatings obtained f rom ~lend6 of c~fcli~ ~rinyl e~hers ~na l~near vinyl cther~ ~nd these ~n ~mbinaton ~ith cycl~aliph~'cic e~poscide~.
The lngreaient~ ted ln Table III ~fere ~lended, ~oa~ed, ~nd ~ured ~5 deseribed in Examples 1 to 3~
~ he properties are listed in Table IV.

., O~ ~ S~ 6 I~ U~
~1 ~ t~ I

6~
~DC~ ~ O

_~ _l ~ O O
~ O iD 1~
111 Ll o ~ ~ c ~ JJ I~ ~ I~ O
_ O
0 t.) ~ ~U~ ~ U
E
~1 ~. .
1-4 i~ 1` ~:)I N I C~
~1 11~ ~ ~D
l?J
~S ~ ~
P~

¢C
_I I~ O ~
O ~ o ~r h ~
I 1~ I r~ I o ~:
o U

~ O
V ~ V
C .C: V V C
_ ~ ~ C C
E ~
_~ 0 j~ ~ ~ 0 L~
C
3J ~ .c .c:
~-4 ~ E~ ~ P. ~ U~

~7 ~ Z

o ~
r' Q ~ ~ v ,_, _ o-- r o ~n _~ o o U~
~, U~ ~ C:7 ._ c O
a'l Q ~ ~ o c~ u~
~11 ~ c~ ~ rt 1 7 ~)~
C~ 1 r~ V
~ A ~
a ~:

O C~
~ O _IO _~ V

o ~) -n c _, o~
C ~^ ~1 O Cd~
ao a) ~ ~u c ~d) _ e: ~~ O u~
07 CJ CU ~
o ~1~ e o ~ ~ ~, æ
) 1 ~ a~11 h ~ ~ ,J
~ C~

~B ~

Control~ ~, D ~nd E; Exan~ples 8 11 The ~oll~wing e3c~mples describe ~he co~tin'g~ obtained frolD lblend~ of s~yclic vinyl ether~
~nd linear ~irinyl ether6 ~n ~ombin~tion with ~ycloaliph~t~ ep~xides or ~ni%tures l~f po~yDl~ ~nd cy~ al~pha~ic epoxides an~ al~o, photoini~ats:~r and ~urf ~ctant .
The ~ngre~ierlt~ lirted in ~able V were blended, coated as~d ~ured as des~ribed in Examples 1 to 3.
The prQperties are liæted in Table VI~

D~ 13 ~ 8S5 o o ~ Q c~ o e~
_~ ~sr ~ i 0 1 1 o ~
O ~ u~ o o e ~ ~ O ~ .
1:: i ~ ~ 1 t`J ~ 3 5, o oC~ o o C~
6, . . .
_l c~r ~~DI I i E
C
_ _l C~ o 1~ o ~ o4~
_I ~ Isc r oI I o E O ~", ~, r~ I I
~1 8 t.
C~ ~ ~ ~~ C
~D c~ v-lCD n~ ~ _1 ~o E~ o~ c~

a~ a~
~D
~ ~ I I ~
o o o C:~ o c~ ~ c~ e, O l ~ ~ l l ~
c _I N
~J ~
O O
~ .IJ
V ,c ~ V C
~ ~ ~ c c ~
O O ~'D
K ~ ~ A v iY C ~ ~ ~ O
A ~ ~ O ~ O
tn ~6,'~

~1_~I NO t~ V
~_j~
1::~

_I ~ CC 6~
) ~ ~O N V
_ _i ~ C~
O ~

~4 o e~ v e~

_~
_I O ~ V
3 ~ _ _~
E ~Je~
C
K ~_I
~ V

>O~ ~ V
~ C
~D
E~
CD ~ ~ ~ V
o _~ ~- tDO U- U~
O
_ _i O f`
O

_.
tl7 C
D o c a~ Q) U~ .c a~

.d~1 2J~
~J ~.1 ~.1 OJ
~U--I ~0 CV ~
O9 VC ~~ oe ~e~

p~
~ 51 ~

Thu~, the l~nebr vinyl ether And divinyl ether of âiethylene glycol cures well with these iEor~ul~tion~. ~he results ~ho~d ~chat vari~us prc:perti~ ~an ~e altered is~ ~ ~y~em when the linear vinyl ether~ ~re com~ne~ with the cycl~
~r~nyl ~ther~., Th~t ~, their ~e in llny ~ive~n ~y~t~m ~ill vary properties and nllow ~ greater ~egree l~ ~:ontrol to be obtai~ed. It ~i6 necessary to optimi2e a system for its end u~e ~y varying the amount of the cc~mponent~ ~n the l3y~tem. The above re~ult6 aO rlot represerlt optimi æ~d cc~ating sy~tems--they are ~eant to l!lemc~nstrate c~nly that properties ~an be ~ltered w}~en linear vinyl ethers are ~ocured with ~y~tems of the~e 'cyp~s.
.

D-13, 855

Claims (56)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition suitable for photocopoly-merization comprising from abouth 1 to about 99 percent of a cyclic vinyl ether containing compound and from about 99 to about 1 percent of a linear vinyl ether.

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 dioxyalkylene group, -ORO-, wherein R is as defined above; a dicarboxylate group, -OC-(O)-R'-C(O)O,- wherein R' is the nucleus of a dicarboxylic acid; and a polycarbamate group much as the dicarbamate group, -OC(O)NH-R"-NH-C(O)O-, wherein 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:

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, cycloaliphatic or aromatic radical which may be substituted hydrocarbyl groups or hydrocarbyl groups substituted with halogen 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:

-56(a)-wherein 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 an alkyl, an alkoxy, an aryl, a cycloalkyl, an alkaryl, an aralkyl group having up to 12 carbon atoms, a halogen, or a hydroxyl group or unsubstituted, linear or branched, containing up to 20 carbon atoms, and (3) aryl which is substituted with an alkyl, an alkoxy, an aryl, a cycloalkyl, an alkaryl, an aralkyl group having up to 12 carbon atoms, a halogen, or a hydroxyl group 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.

-56(b)-

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 viny 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 the cyclic viny 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 the cyclic vinyl ether containing compound is the reaction product of the following:
wherein R1, is as defined in claim 9, and pentasrythritol 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 linear vinyl ether is an alkyl vinyl ether.

19. A composition as defined in claim 1 wherein the linear ether is an aryl vinyl ether.

20. A composition as defined in claim 1 wherein the linear vinyl ether is a divinyl ether.

21. A composition as defined in claim 1 which contains a poly(active hydrogen) organic compound.

22. A composition as defined in claim 21 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.

23. A composition as defined in claim 22 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.

24. A composition as defined as claim 21 wherein the poly (active hydrogen) organic compound is a polymer polyol.

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

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

27. A composition as defined in claim 21 wherein the poly (active hydrogen) organic compound is an acrylic polyol.

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

29. A composition as defined in claim 21 wherein the poly (active hydrogen) organic compound is a mixture of a polyether polyol and a polycaprolactone polyol.

30. A composition as defined in claim 21 wherein the poly (active hydrogen) organic compound is a mixture of at least two poly (active hydrogen) organic compounds.

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

32. A composition as defined in claim 31 wherein the epoxide is a cycloaliphatic epoxide.

33. A composition as in claim 32 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.

34. A composition as in claim 32 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.

35. A composition as in claim 32 wherein the cycloaliphatic epoxide has the formula:
wherein the R's are the same or different and are monovalent substituents of hydrogen or halogen or monovalent hydrocarbon radicals.

36. A composition as in claim 32 wherein the cycloaliphatic epoxide is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

37. A composition as in claim 32 wherein the cycloaliphatic epoxide is bis(3,4-epoxycyclohexylmethyl) adipate.

38. A composition as in claim 32 wherein the cycloaliphatic epoxide is 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane.

39. A composition as defined in claim 32 wherein the cycloaliphatic epoxide is vinylcyclohexene diepoxide.

40. A composition as in claim 32 wherein the cycloaliphatic epoxide is a mixture of bis(3,4-epoxy-cyclohexylmethyl) adipate and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-meta-dioxane.

41. A composition as in claim 32 wherein the cycloaliphatic epoxide is a mixture of 3,4-epoxycyclo-hexylmethyl-3,4-epoxycyclohexane carboxylate and bis(3,4-epoxycyclohexylmethyl) adipate.

42. A composition as in claim 41 which includes 2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane.

43. A composition is defined in claim 32 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.

44. A composition as defined in claim 1 wherein the epoxide is a glycidyl type epoxide.

45. A composition as defined in claim 44 which contains a cycloaliphatic epoxide.

46. A composition as defined in claims 1 or 20 which contains a photoinitiator.

47. A composition as defined in claim 43 wherein the photoinitiator is selected from diazonium salts or onium salts, or mixtures thereof.

48. A composition as defined in claim 1 which contains a substituted or unsubstituted cycloaliphatic monoepoxide, said substituted cycloaliphatic monoepoxide contains substituents selected from 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 fiubstituted cycloaliphatic monoepoxide.

50. A composltion 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 48 wherein the substituted cycloaliphatlc monoepoxide is hydroxyl substituted cycloaliphatic epoxide.

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 47 wherein the unsubstituted cycloaliphatic monoepoxide is cyclohexene monoepoxide.

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