NZ207376A - Radiation curable coating for photographic laminate - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £07376 7 Priority Date(s): Complete Specification Filed: Class: !(h}CQ$m$.lQQ..

C&WtVfo &Q3C. 7JM}G03CJ1QD 2 9 MAY 1987, Publication Date: P.O. Journal, No: ,/£36. «»••••••» r -* i t (« « | i § MAR 1984 No.: Date: NO HAVINGS NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION "RADIATION CURABLE COATING FOR PHOTOGRAPHIC LAMINATE" v> Aw 4 f/Wc, THIOKOL CORPORATION, a corporation ""fia the State of Delaware, 110 North^Drive, Chicago, Illinois 60606, United States of America, hereby declare the invention for which £/ we pray that a patent may be granted to i^g/ue, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 - (followed by page la) 2073 76 i Q 1085-31-00 TITLE: RADIATION CURABLE COATING FOR PHOTOGRAPHIC LAMINATE BACKGROUND OF THE INVENTION A. Field of the Invention .This invention relates to ultraviolet radiation curable compositions suitable for use as optical coatings 5 for use in photographic films.

Manufacturers of photographic films have been attempting to perfect three-dimensional-effect color films for some time. One approach currently under investigation is to deposit a clear, lenticulated optical coating onto 10 conventional photographic print material. The optical . coating is responsible for the three dimensional effect and is usually composed of a cross-linked, ultraviolet-radiation-cured acrylic polymer supported by a clear plastic base such as cellulose triacetate, polypropylene, or 15 polyester. The optical coating is typically 8-11 mils (0.008-0.011 inch) thick. Lenticulated optical coatings are described in J. Nims e_t al, "Three Dimensional Pictures And Method Of Composing Them," U.S. Patent No. 3,852,787 (December 3, 1974).

An optical coating should possess several char acteristics; foremost among them is optical clarity. The optical coating must not be susceptible to yellowing or 207376 other discoloration prior to, during, and after exposure and developing of the color print material underlying the optical coating.

In addition to optical clarity, the optical coating v 5 must be sufficiently flexible so as not to crack when the film is bent in half.

The physical characteristics of the optical coating are highly dependent upon the choice of acrylate-terminated oligomers employed in the manufacture of the optical > 10 coating. In addition to providing a cured acrylic optical coating which satisfies the requirements discussed above, the uncured optical coating composition should possess a rapid cure rate, thereby allowing processing speeds of at least 15 feet per minute and preferably 30-60 feet per 15 minute.

Typically# acrylate-terminated oligomers which possess polyester or polyether backbones have been employed in the manufacture of optical coatings. Polyester-based acrylic coatings display poor hydrolytic stability. 20 Conventional water-based photographic developers can easily penetrate polyester-based acrylic optical coatings, thereby causing severe yellowing of the optical coating. Poly-ether-based acrylic coatings suffer from poor oxidative stability, and are also permeable to photographic 25 developers.

Optical coating compositions which employ polyurethane-based acrylate-terminated oligomers have been disclosed elsewhere.

B. Description of the Prior Art H. Hisamatsu et al, "Photopolymerizable Iso-cyanate-Containing Prepolymers," U.S. Patent No. 3,891,523 (June 24, 1975) discloses UV curable, acrylate-terminated polyurethane prepolymers which have a free isocyanate 35 content of from 0.3 to 15 percent based on the total weight 0 • U i IL) of the prepolymer and a cure initiator. The excess isocyanate groups are stated to impart superior adhesion to a substrate.

N. Miyata et^ al, "Photopolymerizable Vinylurethane Monomer," U.S. Patent No. 3,907,865 (September 23, 1975) discloses acrylate-terminated polyurethane oligomers which are highly UV curable and which, upon curing, form a non-yellowing acrylic film. The reference requires the use of xylylene diisocyanate in the preparation of its 3 10 acrylate-terminated polyurethane oligomer.

D. Lorenz e_t al, "Radiation Curable Coating Composition Comprising An Acryl Urethane Oligomer And An Ultra-violet Absorber," U.S. Patent No. 4,129,667 (December 12, 1978) discloses an acrylate-terminated, polyether or 15 polyester-based polyurethane oligomer which is employed in combination with an acrylic ultraviolet radiation absorber.

D. Lorenz et al^, "Radiation Curable Coating Composition Comprising An Acryl Urethane Oligomer And An Ultra-violet Absorber," U.S. Patent No. 4,135,007 (January 20 17, 1979) discloses'a radiation curable coating composition comprising an acrylate-terminated, polyether or polyester-based polyurethane oligomer and a benzylidene acid ester.

H. Suzuki et al^ "Thermosetting Resins," U.S. Patent 25 No. 4,020,125 (April 26, 1977) discloses an acrylate- terminated hydrogenated polybutadiene polymer which may be cured by exposure to electron beam radiation. The thermoset resin so produced has utility in electrical components.

SUMMARY OF THE INVENTION 30 The applicants' invention is a composition of matter comprising: i) from 45 to 7.9,5percent, based upon the total weight of the composition, of an oligomer of the formula OH HO OH M—Q_ III , 1 II . II I , 1 11 x-0-c-n-r2-n-c-0-rl-0-c-n-r2-n-c-( ■ 207376 wherein R^ is a linear or branched hydrocarbon of from 1,000 to 4/000 molecular weight, r2 is a linear, branched or cyclic alkyl of from six to twenty carbon atoms, X and Q are independently either a) a radical of the formula r R3 -i OR5 (C)m-0' L R4 J II 1 -c-c=ch2 p wherein r4 an<g r5 are independently selected from the group consisting of hydrogen, methyl, ethyl or propyl,m is an integer from 1 to 10, and p is either 15 zero or one, or b) a saturated alkyl of from nine to twenty carbon atoms with the proviso that said oligomer must possess at least one acrylate or methacrylate 20 terminal group; ii) from 20 to 50 percent, based on total weight of the composition, of an acrylate or methacrylate terminated reactive diluent of from 3 to 20 carbon atoms; iii) from 0.5 to 5 percent, based on total weight of the composition, of a photoinitiator selected from the group comprising 2-hydroxycyclohexylphenone, diethoxyacetophenone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-l-one, 2-hydroxy-2-methyl-30 . 1-phenyl-propan-l-one and mixtures thereof.

When cured, the composition described above solidifies into a dry, water-impermeable film which is resistant to yellowing and suitable for use in a lenticulated optical coating. /' * 2073 7 DETAILED DESCRIPTION OF THE INVENTION The applicants have discovered that a composition comprising an acrylate-terminated oligomer conforming to formula I above, at least one reactive diluent, and a 5 specific photoinitiator satisfies the rigorous criteria required of optical coatings.

A. THE ACRYLATE-TERMINATED OLIGOMER The acrylate-terminated oligomer is composed of an organic polymeric backbone which has been end-capped with a 10 diisocyanate which is itself then further reacted with an acrylation agent. 1. The Organic Polymeric Backbone The organic polymeric backbone which is employed in the applicants' invention is formed from a linear or 15 branched hydrocarbon of from 1,000 to 4,000 molecular weight. By "hydrocarbon" it is meant a non-aromatic compound containing a majority of methylene groups (-CH2-) and which may contain both internal unsaturation (-CH=CH-) and pendant unsaturation (-CH-CH-). Fully saturated hydrocarbons are hc=ch2 preferred because the long-term flexibility of the cured optical coating increases as the degree of unsaturation decreases. Suitable hydrocarbons include hydroxyl-terminated, fully hydrogenated 1,2-polybutadiene or 25 polyisobutylene. Hydrogenated 1,2-polybutadiene is preferred due to its superior resistance to yellowing when cured. It is commercially available from Nippon Soda, Ltd. under the trademark GI-1000. 2. The Diisocyanate ' The choice of diisocyanate has an effect upon the flexibility and optical clarity of the cured optical coating. Non-aromatic diisocyanates of from six to twenty carbon atoms may be employed in the preparation of the isocyanate-terminated precursor. Aromatic diisocyanates are 35 unacceptable due to their tendency to cause yellowing of the cured optical coating. Suitable saturated, aliphatic 207376 \ diisocyanates include dicyclohexylmethane-4,41-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Isphorone diisocyanate is preferred because it provides superior surface hardness 5 in the cured acrylic film.

The reaction between the hydroxyl-terminated hydrocarbon and the diisocyanate generally requires a small amount of catalyst, typically from 100 to 200 ppm. Suitable catalysts include dibutyltin oxide, dibutyltin dilaurate, 10 stannous oleate, stannous octoate, and lead octoate.

Tertiary amines such as triethylamine, diethylmethylamine, triethylene diamine, dimethylethylamine, morpholine, N-ethyl morpholine, and piperazine may also be employed. Dibutyltin dilaurate is preferred because of its high reactivity. 3. The Acrylation Agent The acrylation agent is a hydroxyl-terminated aliphatic acrylate or methacrylate or acrylic acid or"an~alkyl"acrylic acid. The acrylation agent must conform to the formula r R3 ~1 OR5 HO- I! 1 -c-c=ch2 — (y) m~0-- r4 J p wherein R3, R^, and r5 are independently selected from the group consisting of hydrogen, methyl, ethyl, or propyl, m is an integer from 1 to 10, and p is zero or one.

The choice of acrylation agent affects the degree of 25 crosslinking of the cured optical coating. The choice of acrylation agent also affects the cure rate of the acrylate-terminated oligomer. Suitable hydroxyl-terminated monoacrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl 30 methacrylate. Hydroxyethyl acrylate is preferred because it imparts a faster cure rate to the polyurethane oligomer.

The acrylation agent should be added to the polyurethane precursor in the absence of light. To further minimize the possibility of premature gellation, one or more 35 of the following precautions may be taken: 207376 1. Maintaining the reaction temperature at or below 65°C. 2. Adding 30 to 100 ppm of an acrylate stabiliser such as phenothiazine, hydroquinone or methyl ether of ) hydroquinone. 3. Adding 15 to 20 weight percent of a reactive diluent to lower the reaction mixture viscosity, thereby permitting more efficient heat transfer. Suitable ) reactive diluents include lauryl acrylate and 2-ethylhexyl acrylate. 4. Running the reaction under dried air.

B. THE REACTIVE DILUENT 15 The oligomer formed by the acrylation of the isocyanate-terminated precursor is a typically high viscosity liquid. A low molecular weight acrylic monomer is added as a reactive diluent to lower the viscosity of the oligomer. Important considerations governing the selection 20 of the reactive diluent include toxicity, volatility, effect on the optical clarity of the cured optical coating, and cost. Acceptable reactive diluents include lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, 25 neopentyl glycol diacrylate,' isodecylacryl ate and ethyl hexyl acryl ate. Lauryl acrylate is preferred because it imparts superior flexibility to the cured optical coating. Ethylhexylacrylate is preferred due to its low cost.

Diacrylates or triacrylates may be employed as the 30 reactive diluent to impart enhanced surface hardness and adhesion to the cured optical coating composition. The cure speed of the optical coating composition is usually more rapid, and the cured film harder, when diacrylates or triacrylates are employed as the reactive diluent '-*1? w .i.J 8 A mixture of acrylic monomers is preferred as the reactive diluent to achieve the optimum balance of flexibility and mar resistance in the cured optical coating while achieving the desired viscosity in the uncured optical 5 coating composition at the lowest cost and toxicity. A reactive diluent comprising a mixture of ethylhexylacrylate and hexanediol diacrylate, illustrated in Example III, is preferred.

C. THE PHOTOINITIATOR 10 The selection of photoinitiator is critical. It must provide reasonable curing speed without causing premature gellation of the optical coating composition. It must not affect the optical clarity of the cured optical coating.

Only four photoinitiators - 2-hydroxycyclohexylphenone, 15 diethoxyacetophenone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-l-one, and 2-hydroxy-2-methyl-l-phenyl-propan-l-one - are acceptable for use as the photoinitiator. 2-hydroxycyclohexylphenone is commercially available from Ciba-Geigy Corp., Dyestuffs and Chemicals Division, 20 Greensboro, North Carolina 27409 under the tradename CGI-184. 2-hydroxy-2-methyl-l-phenyl-propan-l-one is commercially available from EM Chemicals Corporation, 500 Executive Blvd., Elmsford, New York 10523, under the tradename DAROCUR 1173. 1-(4-dodecylphenyl)-2-hydroxy~ 25 2-methylpropan-l-one is commercially available from EM Chemicals Corporation under the tradename DAROCUR 953. Diethoxyacetophenone is commercially available from the UpJohn Company, Fine Chemicals Division, North Haven, Connecticut 06473.

-Cure of the optical coating composition is achieved by depositing the coating composition onto a clear plastic support and passing the supported coating composition under an ultraviolet or ionizing (electron beam) radiation source.

The coated side of the support is exposed to the radiation 35 for a time sufficient to initiate addition polymerization of the acrylate or methacrylate groups of the coating composition. The polymerization process is preferably 2073 76 performed under an inert atmosphere such as nitrogen. The resulting clear acrylic film bonded onto a clear plastic support is termed a "cured optical coating." By "ultraviolet radiation" it is meant any radiation 5 source which will emit ultraviolet radiation in wavelengths of from 2000 to 4000 angstroms in sufficient intensity to produce free radicals in the optical coating composition and thereby induce addition polymerization of olefinic bonds, typically from 0.0004 to 6.0 watts/cm2. Suitable radiation 10 sources include Type RS sunlamps, carbon arc lamps, xenon arc lamps, mercury vapor lamps, tungsten halide lamps, fluorescent lamps with ultraviolet light emitting phosphors, and lasers.

D. HOW TO USE The cured acrylic film of the optical coating may be lenticulated by conventional processes. The clear plastic support of the lenticulated optical coating is then bonded to a conventional photoemulsion supported by backing material. The resulting laminate, consisting of the 20 following layers -lenticulated acrylic film which is resistant to yellowing, clear plastic support, photoemulsion and backing material - is termed an "unexposed color print material." Unexposed color print material may be developed by 25 conventional photographic development processes, which typically comprise: 1. Projecting the image of a color print negative upon the surface of the color print material surface, thereby "exposing" the color print material; 30 2. Immersing the exposed color print material in a "developer" solution for a time sufficient to react the dyes and pigments in the color print photoemulsion, typically 4 minutes; . 3. Immersing the exposed color print material in a "fixer" solution which stops further reaction of the color print material photoemulsion; 4. Immersing the exposed color print material in a water rinse for a time sufficient to remove all traces of the "developer" and "fixer" solutions, typically 4 minutes at 9l°F; and . Drying the developed color print material.

E. DESCRIPTION OF A PREFERRED EMBODIMENT The applicants have achieved optimum results from an optical coating composition comprising i) approximately 59 percent, based upon total composition weight, of an oligomer prepared by reacting hydrogenated NISSO GI-1000 hydroxyl-terminated polybutadiene with isophorone diisocyanate, followed by endcapping with 2-hydroxyethyl acrylate, ii) approximately 29 percent, based upon total composition weight, of 1,6-hexane-diol diacrylate, employed as a reactive diluent, iii) approximately 10 percent, based upon total composition weight, of 2-ethyl-hexylacrylate, also employed as a reactive diluent, iv) approximately 2 percent, based upon total composition weight, of 2-hydroxycyclohexylphenone, employed as a photoinitiator.

The preparation of this composition is illustrated by Example III below. 2073 76 li EXAMPLES: The Examples which follow are intended to illustrate the practice and advantages of the applicants' invention, and are not intended to limit the scope of their invention in any way. All concentration percentages are measured by total weight of the composition unless otherwise stated. ?07.3 ?6 12 EXAMPLE I 50 grams (.45 equivalents) of isophorone diisocyanate were added to a reactor vessel equipped with an agitator, a thermometer, an inert gas inlet and a charging port. The reaction vessel was continuously purged with dry air throughout the oligomer preparation. The isophorone diisocyanate was heated to 65°C and agitated. 0.04 grams of dibutyltin dilaurate were added. 178 grams (0.225 equivalents based on an equivalent weight of 791) of Exxon hydroxyl-terminated, hydrogenated polyisobutylene (molecular weight of 1582) were added.

When the theoretical isocyanate content (0.225 equivalents) was reached, the temperature was raised to 75°C. Over the course of 40 minutes, 26.43 grams (0.225 equivalents) of 2-hydroxyethyl acrylate were added to the reaction mixture. The reaction required approximately three hours to proceed to completion (final isocyanate concentration less than 0.2%) at a final temperature maintained about 75-80°C. 54.5 grains of 2-ethylhexylacrylate and 3.6 grams of 2-hydroxycyclohexylphenone were added to 127.2 grains of the oligomer, which was then mixed thoroughly to produce a clear, viscous, optical coating composition, which was labelled IA. 54.5 grams of lauryl acrylate and 3.6 grams of 2-hydroxycyclohexylphenone were added to the remaining 127.2 grams of oligomer, and mixed thoroughly. The clear, viscous optical coating composition so prepared was labelled IB. 2073 7 6 13 EXAMPLE II Using the procedure of Example I, 111.7 grams (0.14 equivalents, based upon an equivalent of 782 grams/equivalent) of hydrogenated NISSO GI-1000 hydroxyl-terminated polybutadiene (approximately 1564 molecular weight) were added to 30 grams (0.28 equivalents) of trimethylhexa-methylene diisocyanate, in the presence of 0.03 grams of dibutyltin dilaurate to form the isocyanate-terminated precursor. 16.6 grams (0.14 equivalents) of 2-hydroxyethyl acrylate were added to form the acrylate terminated oligomer. 71.95 grams of the oligomer were mixed with 71.95 grams of 1,6-hexanediol diacrylate and 2.9 grams of 2-hydroxycyclohexylphenone to form a clear optical coating composition, which was labelled IIA.

The remaining 86.4 grams of the oligomer were mixed with 28.8 grains of 1,6-hexanediol diacrylate, 28.8 grams of ethylhexylacrylate, and 2.9 grams of 2-hydroxycyclohexylphenone to form a clear optical coating composition which was labelled IIB. -u/3 / EXAMPLE III Using the procedure of Example I, 106 grams (0.135 equivalents, based upon an equivalent weight of 782 grams/equivalent) of hydrogenated NISSO GI-1000 hydroxyl-terminated polybutadiene were added to 30 grams (0.27 equivalents) of isophorone diisocyanate in the presence of small amount of dibutyltin dilaurate to form the isocyanate terminated precursor. .7 grams (0.135 equivalents) of 2-hydroxyethyl acrylate were added to form the acrylate-terminated oligomer. 75.9 grams of 1,6-hexanediol diacrylate, 25.3 grams of ethylhexyl acrylate, and 5.1 grams of 2-hydroxycyclohexylphenone were added to the oligomer, which was then mixed thoroughly to produce a clear optical coating composition labelled III. ^ ' w# / Q EXAMPLE IV Using the procedure of Example I, 167.5 grams (0.225 equivalents, based upon a 744 equivalent weight) of unsaturated NISSO G-1000 hydroxyl-terminated polybutadiene were added to 50 grams (0.45 equivalents) of isophorone diisocyanate in the presence of a small amount of dibutyltin dilaurate to form the isocyanate-terminated precursor. 26.1 grams (0.225 equivalents) of 2-hydroxyethyl acrylate were added to form the acrylate-terminated oligomer. 40.6 grams of 1,6-hexanediol diacrylate, 121.8 grams of ethylhexyl acrylate, and 8.12 grams of 2-hydroxycyclohexylphenone were added to the oligomer, which was then mixed thoroughly to produce a clear optical coating composition which was labelled IV. 16 EXAMPLE V Using the procedure of Example I, 154 grams (0.135 equivalents, based upon an equivalent weight of 1141 grams/equivalent) of hydrogenated NISSO GI-2000 hydroxyl-terminated polybutadiene (approximate molecular weight of 2282) were added to 30 grams (0.27 equivalents) of isophorone diisocyanate in the presence of 0.04 grams of dibutyltin dilaurate to form the isocyanate-terminated precursor. .7 grains (0.135 equivalents) of 2-hydroxyethyl acrylate were added to form the acrylate-terminated oligomer. 93.19 grams of the oligomer were mixed with 26.63 grams of 1,6-hexanediol diacrylate, 13.31 grams of ethylhexyl acrylate, and 2.66 grams of 2-hydroxycyclohexylphenone to produce a clear optical coating composition labelled VA.

The remaining 106.5 grams of oligomer were mixed with 13.31 grams of trimethylolpropane triacrylate, 13.31 grams of ethylhexyl acrylate, and 2.66 grams of 2-hydroxycyclohexylphenone to produce a clear optical coating composition labelled VB. 2073 7 17 EXAMPLE VI Using the procedure of Example I, 150.5 grams (0.19 equivalents, based upon an equivalent weight of 777 grams/equivalent) of hydrogenated NISSO GI-1000 hydroxyl-terminated polybutadiene were added to 50 grams (0.38 equivalents) of dicyclohexylmethane-4,41-diisocyanate in the presence of 0.04 grams of dibutyltin dilaurate to form the isocyanate-terminated precursor. 22.5 grams (0.19 equivalents) of 2-hydroxyethyl acrylate were added to form the acrylate-terminated oligomer. 31.86 grams of trimethylolpropane triacrylate, 63.71 grams of ethylhexyl acrylate, and 6.37 grams of 2-hydroxycyclohexylphenone were added to the oligomer, which was then thoroughly mixed to produce a clear optical coating composition labelled VI. 18 EXAMPLE VII Portions of the optical coating composition of Example III were evaluated for various physico-chemical pr-operties. Results of these tests are listed in TABLE I below: TABLE I Viscosity @ 25@C 1200-1400 cps Refractive Index 1.470-1.475 Specific Gravity 1.01 Unsaturation 0.36 Isocyanate Content (0.2 Base No. <10.0 Acid No. <0.5 Portions of the optical coating composition of Example III were cast as films and cured by exposure to ultraviolet radiation. These films were then evaluated for tensile strength and elongation. Results of these tests are listed in TABLE II below: TABLE II Tensile Strength 1000-1200 psi Elongation 15-20% Tear Strength 20-30 lb/inch "Mar Resistance" is a measure of the surface hardness and surface lubricity ("slip") of the cured optical coating. A cured optical coating passes this test if a fingernail drawn across its surface does not leave any scratches.

"Flexibility" is determined by manually bending a sheet of cured optical coating in half (180°) and observing whether any cracks appear in the cured optical coating. A "Good" rating means no cracks appeared. An "Acceptable" 2073 19 rating means no cracks appeared, but the optical coating was harder to bend than optical coatings which were rated "good".

The "Sun Light" exposure test consists of exposing a cured optical coating to sun light for a minimum of four hours.

The "Sun Lamp" exposure test consists of exposing a cured optical coating to a 275 watt Sylvania sun lamp for a minimum of twelve hours at a distance of one foot.

The "Fluorescent Lamp" exposure test consists of exposing a cured optical coating to fluorescent light for a minimum of twelve hours at a distance of one foot.

The "Incandescent Lamp" exposure test consists of exposing the surface of a cured optical coating to a 100 watt incandescent lamp for a minimum of twelve hours at a distance of one foot.

The "140°F Oven" exposure test consists of placing the samples in an oven maintained at 140°F for a minimum of eighteen hours.

EXAMPLE VIII The compositions of Examples I through VI were deposited as films upon clear plastic supports (approximately six inches square), and cured by exposure to ultraviolet radiation. The cured optical coatings so prepared were immersed in a photographic "developer" solution for approximately four minutes, immersed in a "fixer" solution for 1.5 minutes, immersed in a water rinse for approximately three minutes, and dried.

Some of the samples were then tested for mar resistance and flexibility while others were subjected to various accelerated aging exposure tests to determine resistance of the cured optical coatings to yellowing. Results of these tests are set out in TABLE III below: TABLE III Physical Testing Degree of Yellowing After Accelerated Aging Optical Coatinq Processing Rinse Mar Resistance Flexibility 140°F Oven Sun Light Sun Lamp Fluorescent Lamp Incandescent Lamp I (A) Water Acceptable Good None None None None None I {B) Water Acceptable Good None None None None None II (A) Water Good Acceptable None None None None None II (B) Water Acceptable Good None None None None None III Water Excellent SIightly Brittle None None None None None IV Water Good Acceptable* None None None None None V (A) Water Good Good None None None None None V (B) Water Good Good None None None None None VI Water Good Good None None None None None *Upon accelerated aging under sunlamp, this formulation becomes brittle. The substantially hydrogenated compositions do not display this brittleness. 2073 7f 22 EXAMPLE IX The oligomer and reactive diluent of Example III were mixed with the four permissible photoinitiators to produce the four optical coating compositions set out in TABLE IV below: TABLE IV Component Composition Percentage A B C D oligomer 58.7 58.7 58.7 58.7 reactive diluent hexanediol diacrylate 29.5 29.5 29.5 29.5 ethylhexyl acrylate 9.8 9.8 9.8 9.8 photoinitiator 2-hydroxycyclohexylphenone 2.0 diethoxyacetophenone 2.0 2-hydroxy-2-methyl-l-phenyl- propan-l-one 2.0 1-(4-dodecylphenyl)-2-hydroxy- 2-methylpropan-l-one 2.0 100% 100% 100% 100% The four compositions described above were deposited as films upon clear plastic supports (approximately six inches square) and cured by exposure to ultraviolet radiation. The cured optical coatings so prepared were immersed in a photographic developer solution for approximately four minutes, immersed in a fixer solution for approximately three minutes, immersed in a water rinse for approximately three minutes, and dried. The samples were then tested for yellowing resistance by exposure to various accelerated aging exposure tests. Results of these tests are set out in TABLE V below:

Claims (14)

TABLE V Physical Testing Degree of Yellowing After Accelerating Aging Optical Coating Mar Resistance Flexibility 140°F Oven Sun Lamp Sun Lamp Fluorescent Lamp Incandescent Lamp IXA Excellent Slightly brittle None None None None None IXB Excellent Slightly brittle None None None None None IXC Excellent Slightly brittle None None None None None IXD Excellent Slightly brittle None None None None None to u> 24 2073*76 : R/VHAT /WE CLAIM IS:

1. A composition of matter that is essentially non-yellowing when cured comprising i) from 45 to 79.5 percent, based upon total weight of the composition, of an oligomer of the formula OH HO OH HO ii i ~ 1 o , ii i . i ii X-O-C—N-R2-N-C—0—R1—0—C-N—R2—N—C—0—Q wherein Rl is a linear or branched divalent hydrocarbon radical of from 1,000 to 4,000 molecular weinht, R2 is a 1 inear, branched or cyclic alkylene radical —> of from six to twenty carbon atoms and X and Q are independently either a) a radical of the formula p R3 -r O R5 I II I (C)m-0-—C-C=CH2 luf J7 wherein R3, R4, and R5 are independently hydrogen or methyl, m is an integer from 1 to 10, and p is either zero or one, or b) a saturated alkyl radical of from nine to twenty carbon atoms, with the proviso that said oligomer must possess at least one acrylate or methacrylate terminal group; _ ii) from 20 to 50 percent, based on total weight of the composition, of an acrylate or methacrylate terminated reactive diluent of from 3 to 20 carbon atoms;and iii) from 0.5 to 5 percent, based upon the total weight of the composition, of a photoinitiator selected from the group comprising 2-hydroxycyclohexylphenone, diethoxyacetophenone. 207376 25 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-l-phenyl-propan-l-one and mixtures thereof.

2- The composition of claim 1 wherein said reactive diluent comprises a mixture of at least two acrylate-terminated compounds of from 11 to 22 carbon atoms.

3. The composition of claim 1 wherein said reactive diluent - is selected from the group comprising lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, 2-ethylhexylacrylate, isodecyl acrylate, hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and mixtures thereof. ' . _

4. The composition of claim 3 wherein said reactive diluent is a mixture of^ethylhexylacrylate and hexanediol diacrylate.

5. The composition of claim 1 wherein r! is polybutadiene.

6. The composition of claim 1 wherein Rl is polyisobutylene

7. An essentially non-yellowing article of manufacture comprising a substrate coated on at least one surface with a coating comprising the addition polymerization reaction product of i) from 45 to79.5 percent, based upon total weight of f-7 APR 1937 207376 26 the composition, of an oligomer of the formula OH HO OH HO 11,11 ,11,1) X-0-C-N-R2-N-C-0-R1-0-C-N-R2-N-C-0-Q wherein Rl is a linear or branched divalent hydrocarbon radical of from 1,000 to 4,000 moleculariweight, R2 is a linear, branched or cyclic "alkyl ene radical of from six to twenty carbon atoms and X and Q are independently either a) a radical of the formula r R3 —1 OR5 II ] -c-c=ch2 I (C)m-O; l .! ft — R4 J p wherein r3, r4f and R5 are independently hydrogen or methyl, m is an integer from 1 to 10, and p is either zero or one, or b) a saturated alkyl radical of from nine to twenty carbon atoms, with the proviso that said oligomer must possess at least one acrylate or methacrylate terminal group; ii) from 20 to 50 percent, based on total weight of the composition, of an acrylate or methacrylate terminated reactive diluent of from 3 to 20 carbon atoms;and iii) from 0.5 to 5 percent, based upon the total weight of the composition, of a photoinitiator selected from the group comprising 2-hydroxycyclohexylphenone, diethoxyacetophenone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-l-one, 2-hydroxy-2-methyl-l-phenyl-propan-l-one and mixtures thereof.

8. The article of manufacture of claim 7 wherein said substrate is transparent. ii* Si17FEDl9S7 207376 27

9. The article of manufacture of claim 7 wherein said reactive diluent comprises a mixture of at least two acrylate-terminated compounds of from H to 22* carbon atoms.

10. The article of manufacture of claim 7 wherein said reactive diluent is selected from the group comprising lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, 2-ethylhexyl acrylate, isodecyl acrylate, hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and mixtures thereof.

11. The article of manufacture of claim 10 wherein said reactive diluent is a mixture of 2-ethylhexylacrylate and hexanediol diacrylate.

12. The article of manufacture of claim 7 wherein r! is polybutadiene.

13. A composition as claimed in any one of claims 1 to 6 substantially as hereinbefore described with reference to any example thereof.

14. An article of manufacture as claimed in any one of claims 7 to 12 substantially as hereinbefore described with reference to any example thereof. AGENTS FOR THE APPLICANTS ^ 4 *7 r- f- - -