PHOTOCURABLE ACRYLIC COATED POLYCARBONATE ARTICLES

Abstract: A polycarbonate article having an adherent mar, abrasion and chemical resistant ultraviolet light cured coating on the surface thereof comprised of the photoreaction products of an acrylate modified polymer and at least one polyfunctional acrylic acid ester monomer represented by the general formula (FORMULA) wherein n is an integer having a value of from 2 to 4, and R is a n functional aliphatic hydrocarbon residue, n functional substituted aliphatic hydrocarbon residue, n functional aliphatic hydrocarbon residue containing at least one ether linkage, and n functional substituted aliphatic hydrocarbon residue containing at least one ether linkage.

Description: - l - Description Photocurable Acrylic Coated Polycarbonate Articles This invention relates to polycarbonate articles coated with • a. photocured- coating comprised of the reaction product of certain multifunctional acrylate ester monomers and certain acrylate modi¬ fied polymers. More particularly, this invention relates to a polycarbonate article having a photocured coating thereon which coating is clear, mar, abrasion, and solvent resistant, has good adhesion to the polycarbonate substrate, and is compatible with the polycarbonate; i.e., does not adversely affect the polycarbonate substrate by stress cracking and crazing it, by causing crack propagation into the polycarbonate as a result of brittleness of the coating itself and/or by adversely affecting the properties of the polycarbonate generally such as, for example, impact resistance, elongation, and tensile strength. BACKGROUND OF THE INVENTION Polycarbonates are commercially important materials possess¬ ing excellent physical and chemical properties which are useful in a wide range application from non-opaque impact resistant sheets to shaped articles. Generally, however, polycarbonates have rather low scratch resistance and are somewhat susceptible to attack by many common solvents and chemicals. Previous efforts to overcome this low scratch resistance and susceptability to attack by solvents have included lamination procedures and application onto the polycarbonate of a surface coating. Many of these prior art remedial efforts have been unsuc¬ cessful due to the incompatibility of the laminae and coating materials with the polycarbonate substrate. This incompatibility has resulted in stress cracking and crazing of the polycarbonate, crack propagation into the polycarbonate as a result of the brittleness of the coating, and a reduction of the advantageous OMPI WIPO properties of the polycarbonate such as, for example, impact resistance, tensile strength, non-opacity and elongation. The prior art coatings for polycarbonates have included organopolysiloxanes, U.S. 3,707,397; polyester-melamines or 5 acr lic-melamines, U.S. 3,843,390; and allyl resins, U.S. 2,332,461. These types of prior art coatings are generally applied from solutions of inert solvents and are cured to final properties by baking at elevated temperatures. The disadvantages of such systems are obvious. The heat curing requires a supply 10 of thermal energy thereby adding to the cost of the system. Further, the thermal curing step is somewhat limited by the heat distortion temperature of the polycarbonate which is to be coated Thus, in coating of polycarbonates, sheets of 30 mils and less # generally cannot be coated and cured economically because of 15 excessive warpage of the sheets during the thermal curing process It is also known in the art to impart abrasion resistance to the surface of a synthetic resin article by forming on the surfac of said article a cured film containing, inter alia, a mixture of a compound having a total of at least three acryloxy and/or meth- 20 acryloxy groups and a copolymerizable mono- or diethylenically un saturated compound. Thus, for example, U.S. 3,968,305 describes synthetic resin shaped article having a mar-resistant polymer surface layer consisting essentially of, in polymerized form, (a) 20 to 100 weight % of a compound having a total of at least 25 three acryloxy and/or methacryloxy groups linked with a straight chain aliphatic hydrocarbon residue having not more than 20 carbo atoms and (b) 0 to 80 weight % of at least one copolymerizable mono- or diethylenically unsaturated compound. U.S. 3,968,309 describes a molded article of plastic having on its surface a OM cured film of a coating material comprising at least 30% by weight of at least- one polyfunctional compound selected f om the group consisting of polymethacryloxy compounds having at least three methacryloyloxy groups in one molecule and a molecular weight of 250 to 800 and polyacryloxy compounds having at least three acr loyloxy groups in one molecule and a molecular weight of 250 to 800, and a fluorine-containing surfactant, in which the fluorine atom is bonded to a carbon atom. It has now been found that certain specific polyfunctional acrylic monomers in conjunction with certain acrylic modified polymers can be used to provide excellent UV cured coatings for polycarbonate. Thus, the present invention provides a certain acrylate estei monomer-acrylic modified polymer based UV-cured non-opaque coating for polycarbonates which has improved adhesion, especially after exposure to weathering, to the polycarbonate, is compatible with the polycarbonate, and is mar, abrasion and solvent resistant. DESCRIPTION OF THE INVENTION In accordance with the present invention, there is provided a non-opaque, more particularly a transparent, polycarbonate article having deposited on the surface thereof, mar, abrasion, and chemical resistant non-opaque coating having improved adhesion to the polycarbonate substrate, said coating comprising a UV-cured composition .containing the photoreaction products of certain UV curable polyfunctional acrylic monomers and certain UV-curable acrylic modified polymers. In the practice of this invention, any of the aromatic poly¬ carbonates can be employed herein. These are homopσlymers and copolymers and mixtures thereof that are prepared by reacting a dihydric phenol with a carbonate precursor. Typical of some of the dihydric phenols that may be employed in the practice of this invention are bisphenol-A (2,2-bis (4-hydroxyphenyl) propane), bis (4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl) propane, 3,3-bis(4-hydroxyphenyl}pentane, 2,2-bis(3,5-dichloro-4- hydroxyphenyl)propane, 2,2-bis (4-3,5-dibromo-4-hydroxyphenyl) propane, bis(3-chloro-4-hydroxyphenyl) methane, other dihydric phenols of the bisphenol type are also available and are disclosed, in U.S. Patents, 2,999,835, 3,028,365 and 3,334,154. It is, of course, possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol or with hydroxy or acid terminated polyester, or with a dibasic acid in the event a carbonate copolymer or interpolymer rather than a ho opolymer is desired for use in the preparation of the aromatic carbonate polymers of this invention. Also employed in the practice of this invention may be blends of any of the above materials to provide the aromatic carbonate polymer. The carbonate precursor may be either a carbonyl halide, a carbonate ester of a haloformate. The carbonyl halides which can be employed herein are carbonyl bromide, carbonyl chloride and mixtures thereof. Typical of the carbonate esters which may be employed herein are diphenyl carbonate, di-(halophenyl)carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc., di-(alk lphenyl) carbonate such as di(tolyl) carbonate, etc., di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, O fa WI ' ' phenyl- tol-y-1 -carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. The haloformates suitable for use herein include bis-halofor ates of dihydric phenols (bis ' chloro- formates of hydroquinone, etc.) or glycols (bishalofor ates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred. Also included are the polymeric derivatives of a dihydric phenol, a dicarboxylic acid and carbonic acid. These are dis- closed in U.S. Patent 3,169,121 which is incorporated herein by reference. The aromatic carbonate polymers of this invention may be pre¬ pared by employing a molecular weight regulator, an acid acceptor and a catalyst. The molecular weight regulators which can be employed in carrying out the process of this invention include monohydric phenols such as phenol, chroman-I, para-tertiary- butyl-phenol, para-bromophenol, primary and secondary amines, etc. Preferably, phenol is employed as the molecular weight regulator. A suitable acid acceptor may be either an organic or an inorganic acid acceptor. A suitable organic acid acceptor is a tertiary amine and includes such materials as pyridine, triethyl- a ine, dimethylaniline, tributylamine, etc. The inorganic acid acceptor may be one which can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal. The catalysts which are employed herein can be any of the suitable catalysts that aid the polymerization of bisphenol-A with phosgene. Suitable catalysts include tertiary amines such as, for example, triethylamine, tripropyl mine, N,N-dimethyl- aniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-hyptyl-ammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride, tetramethyl ammonium hydroxide, tetra-n-butyl-ammonium iodide, benzyltrimethylammonium chloride 5 and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phos¬ phonium bromide. Also included herein are branched polycarbonates wherein a polyfunctional aromatic compound is reacted with the dihydric 10 phenol and carbonate precursor to provide a thermoplastic randoml branched polycarbonate. These polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl or mixtures thereof. Examples of these polyfunctional 15 aromatic compounds which may be employed in the practice of this invention include: trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyro- mellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, 20 benzophenonetetracarboxylic anhydride and the. like. The preferred polyfunctional aromatic compounds are trimellitic anhydride or trimellitic acid, or their haloformyl derivatives. Also included herein are blends of a linear polycarbonate and a branched polycarbonate. 25 The first component of the UV curable coating compositions o the present invention is a polyfunctional acrylate ester monomer. The polyfunctional acrylate ester monomers of the present invention are represented by the general formula O wherein n is an integer from 2 to 8, preferably from 2 to 6, and more preferably from 2 to 4; and R is a n functional hydrocarbon residue, a n functional substituted hydrocarbon residue, a n functional hydrocarbon residue containing at least one ether linkage, and a n functional substituted hydrocarbon residue con¬ taining at least one ether linkage. Preferred n functional hydrocarbon residues are the n func¬ tional aliphatic, preferably saturated aliphatic, hydrocarbon residues containing from 1 to about 20 carbon atoms and the n functional aromatic hydrocarbon residues containing form 6 to about 10 carbon atoms. Preferred n functional hydrocarbon residues containing at least one ether linkage are the n functional aliphatic hydrocarbon residues, preferably saturated aliphatic hydrocarbon residues, containing from 1 to about 5 ether linkages and from 2 to about 20 carbon atoms. Preferred n functional substituted hydrocarbon residues are the n functional aliphatic hydrocarbon residues, preferably the saturated aliphatic hydrocarbon residues, containing from 1 to about 20 carbon atoms, and the n functional aromatic hydrocarbon residues containing from 6 to about 10 carbon atoms which contain substituent groups such as the halogens, i.e., fluorine, chlorine, bromine and iodine, hydroxyl, -COOH, and -COOR' groups wherein R 1 represents alkyl groups containing from 1 to about 6 carbon atoms. Preferred n functional substituted hydrocarbon residues con¬ taining at least one ether linkage are the n functional aliphatic, preferably saturated aliphatic, hydrocarbon residues containing from 2 to about 20 carbon atoms and from 1 to about 5 ether linkages which contain substituent groups such as the halogen hydroxyl, -COOH, and -COOR' groups wherein R' is as defined above. It is to be understood that where substituent groups are present, they should be such that they do not unduly hinder or interfere with the photocure of the polyfunctional acrylic monomers. The more preferred polyfunctional acrylic monomers are those represented by formula I wherein R is selected from the group consisting of an n functional saturated aliphatic hydrocarbon residue containing from 1 to about 20 carbon atoms, a hydroxyl substituted n functional saturated aliphatic hydrocarbon residue containing from 1 to about 20 carbon atoms, an n f nctional satur- ated aliphatic hydrocarbon residue containing from 2 to about 20 carbon atoms and from 1 to about 5 ether linkages, and a hydroxyl - substituted n functional saturated aliphatic hydrocarbon residue containing from 2 to about 20 carbon atoms and from 1 to about 5 ether linkages. The preferred polyfunctional acrylate ester monomers are those wherein R is an n functional saturated aliphatic hydrocarbon, ether, or polyether radical, with those monomers wherein R is an n valent saturated aliphatic hydrocarbon radical being more preferred. More particularly, the difunctional acrylic monomers, or di- acrylates, are represented by formula I wherein n is 2; the tri- functional acrylic monomers, or triacrylates, are represented by formula I wherein n is 3; and the tetra-functional acrylic mono¬ mers, or tetraacrylates, are represented by formula I wherein n is 4. More particularly, the difunctional acrylic monomers, or diacrylates, are represented by formula I wherein n is 2; the tri- functional acrylic monomers, or triacrylates, are represented by formula I wherein n is 3; and. the tetra-functional acrylic monomers, or tetraacrylates, are represented by formula I wherein n is 4. Illustrative of. suitable polyfunctional acrylate ester monomers of formula I are those listed below in TABLE I. TABLE I Diacrylates of Formula I 1. CH 2 =CHC00-CH 2 -00CCH=CH 2 2. CH 2 =CHCOO-CH 2 -CH 2 -OOCCH=CH 2 3. CH 2 =CHCOO-CH 2 -CHOHCH 2 -OOCCH=CH 2 4. CH 2 =CHCOO-{CH 2 )g-OOCCH=CH 2 5. CH 2 =CHC0O-CH 2 -CH 2 -CH-CH 3 OOCCH=CH 2 6. CH 2 =CHCOO-CH 2 CH 2 OCH 2 CH 2 -OOCCH=CH 2 7. CH 2 =CHCOO-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -OOCCH=CH 2 CH 3 8. CH 2 =CHCOO-CH 2 -C-OOCCH=CH 2 CH 3 CH 2 Br 9. CH 2 =CHCOO-CH 2 -C-OOCCH=CH 2 CH3 CU2OH 10. CH 2 =CHCOO-CH 2 -C-OOCCH=CH 2 CH 3 CH,OH - ' 11. CH 2 =CHCOO-CH 2 -C-OOCCH=CH 2 CH20H CH2OH 12. CH 2 =CHCOO-CH 2 -C-OOCCH=CH 2 CH2Br 13. CH 2 =CHCOO-CH 2 -CH«CH-CH 2 -CH 3 -OOCCH=CH 2 OMPI fs, ~~m? ~~ ' 14. CH 2* CHCOO-CH 2 -CH=CH-CH-OOCCH«CH 2 CH 2 OH CH 2 OH 15. CH 2 =CHC00-CH 2 -C-CH 2 00CCH=CH 2 CH 2 C1 OCH, 16. CH 2 =CHC00-CH 2 -C IH 2 - 3 CH 2 -00CCH=CH 2 Triacrylates of Formula I 00CCH=CH 2 22. CH 2 =CHCOO-CH 2 CH 2 C IH 2 CH 2 -OOCCH=CH 2 " - Tetraacrylates. of Formula I 27. CH 2 =CHCOO-CH 2 -CH-CH-CH 2 -OOCCH=CH 2 CH 2 =CHOO-CH 2 CH 2 -OOCCH=CH 2 These polyacrylate esters and their production are well known to those skilled in the art. One method of producing the di-, tri-, and tetraaσrylate esters involves reacting acrylic acid with a di-, tri-, or tetrahydroxyl compound to produce the daester, triester or tetraester. Thus, for example, acrylic acid can be reacted with ethylene glycol to produce ethylene glycol diacrylate (compound 2 in Table I) . The second component of the coating compositions of thepresent invention is an acrylate modified polymeric resin. The_ acrylate mod¬ ified polymeric resins are conventional polymer types whose struc- ture and preparation are known in the art. These acrylate modified polymers have UV reactive acrylate groups incorporated into the polymer. Generally, these acrylate modified polymers have the general . fa WIPO structure represented by the formula II. Polymer -|-Acrylate wherein x is an integer of fr ]om 1 to about 5 and Polymer is an n valent polymeric material. Thus, a difunctional polymer, wherein 5 x is 2, would have a structure represented by the formula III. Acrylate - Polymer - Acrylate, a trifunctional polymer, wherein x is 3, would have the structure represented by the formula Acrylate - Polymer - Acrylate, Acrylate 10 and so forth. Thus, a polymer having monof nctional acrylates attached thereto would be represented by the formula 0 IV. Polymer r- O - C I I - OH = CH 2 ι x wherein polymer and x are as defined above. A polymer having 15 polyfunctional acrylates attached thereto would be represented by the formula 0 V. Polymer -4— R - £4- 0 - C - CH = CH 2 wherein Polymer, R, n, and x are as defined above. Polymers having both monofunctional and polyfunctional acry- 20 late groups attached thereto are also useful in the practice of the present invention. These types of acrylate modified polymers are represented by the structural formula wherein Polymer, R, and n are as defined above, and y and z are 25 integers having a value of from 1 to 3, provided that the sum of y + z does not exceed 5. Exemplary typical acrylate modified polymers are acrylate polyesters"xepresented by the formula 0 0 o 0 CH 2 =CH- ICI-0(CH 2 ) 6 r-0 C II-(CH 2 ) 4 -C ιι-0-(CH ■ 2 )g- i 0-C ιι-CH=CH 2 acrylate epoxies represented by the formula CH =CH- and acrylate urethanes represented by the formula Acrylate modified polymers are the acrylate epoxies as described in U.S. 3,586,526, acrylate urethanes as described in U.S ,297,745, acrylate alkyd urethanes as described in U.S. 3,673,140, acrylate polycaprolactσnes as described in U.S. 3,700,643, acrylate unsat¬ urated acid modified drying oils as described in U.S. 3,712,871, acrylate polyesters, and acrylate polyethers as described in U.S. 3,380,831, said references being incorporated herein by reference. Preferred acrylate modified polymers are the acrylated urethanes and acrylated polycaprolactones. Generally, the coating compositions of the present invention contain a sufficient amount of monomer to give relatively free flowing solutions; however, a suitable organic solvent such as xylene, toluene, benzene and the like may optionally be incorpor¬ ated in the coating compositions to lower the viscosity thereof. The coating compositions generally contain, in % by weight, from . about 30% to about 90%, and preferably from about 40% to about 80% of said polyfunctional acrylate ester monomer, and from about 10% to about 70%, preferably from about 20% to about 60%, of the acrylate modified polymer. OMPI fa WIPO The photocurable coating compositions also contain a photo¬ sensitizing amount of photosensitizer, i.e. , an amount effective to effect the photocure of the coating composition. Generally, this amount is from about 0.01% to about 10% by weight, preferabl 5 from about 0.1% to about 5% by weight of the photocurable coating composition. These additives and the cure thereof are generally well known in the art. Some nonlimiting examples of these UV radiation photosensitizers include ketones, such as benzophenone, acetophenone, benzil, benzyl methyl ketone; benzoins and substi- 10 tuted benzoins such as benzoin methyl ether, θ(-hydroxymethyl benzoin isopropyl ether; halogen containing compounds such as C -broraoacetophenone, p-bromoacetophenone, -chloromethyl- naphthalene, and the like. The coating compositions of the instant invention may also 15 optionally contain various flatting agents, surface active agents, thixotropic agents, UV light absorbers and dyes. All of these additives and the use thereof are well known in the art and do not require extensive discussions. Therefore, only a limited number will be referred to, it being understood that any compounds 20 possessing the ability to function in such a manner, i.e., as a flatting agent, surface active agent, UV light absorber, and the like, can be used so long as they do not deleteriously affect the photocuring of the coating compositions and do not adversely affect the non-opaque character'of the coating. The various surface-active agents, including anionic, cationic and nonionic surface-active agents are described in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 19, Interscience Publishers, New York, 1969, pp. 507-593, and Encyclopedia of Polymer Science and Technology, Vol. 13, Inter¬ science Publishers, New York, 1970, pp. 477-486, both of which are references and incorporated herein. The ultraviolet light absorbing compounds which can option¬ ally be present in an amount effective to protect the polycarbon- ate substrate from the degradative effects of ultraviolet light, provided that they do not unduly interfere with or hinder the photocuring of the coating compositions. Some non-limiting examples of suitable ultraviolet light absorbing compounds are benzophenone derivatives such as 2,2'-dihydroxybenzophenone, 2,2'-dihydrgxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4*- diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'- dihydroxy-4-methoxy-4'-ethoxybenzophenone, 2,2 < -dihydroxy-4- methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'- butoxybenzophenone ? and the like;- and benzotriazole derivatives such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'- hydroxy-5'-tert-butylphenyl) benzotriazole, 2-(2'-hydroxy-3 '- methyl-5'-tert-butylphenyl) benzotriazole, 2-(2'-hydroxyp-5'- cyclohexylphenyl)-benzotriazole, 2-(2'-hydroxy-3* ,5'-di ethyl- phenyl) benzotriazole, and the like. In the practice of the present invention, the photocurable coating compositions are first compounded by adding together the. -5tJRE OMPI /4 WIPO polyfunctional acrylic monomer, the polymerizable acrylate modifi polymer, the UV photosensitizer, and, optionally, any of the othe aforementioned additives. Additionally, if so desired to reduce the viscosity of the coating formulation, an organic solvent may 5 be incorporated into the formulation. Generally, the amount of solvent, if any, present should be such that evaporation of the solvent occurs before any deleterious effect on the substrate due to the aggressiveness (in the chemical etching sense) of the coating compositions develops. The various components are 10 thoroughly mixed so as to form a generally homogeneous coating composition. A thin, uniform film of the coating solution is then applied onto the polycarbonate surface by any of the known means such as dipping, spraying, roll-coating and the like. Generally, the coating composition is applied in an amount suffi- 15 cient to provide a cured coating of from about .1 mil to about .5 mil, preferably from about .2 mil to about .3 mil thick. The coating is then cured in an inert, e.g., nitrogen, atmosphere, by UV irradiation which can have a wavelength of from 1849A. to 4000A. The lamp systems used to generate such radiation can 20 consist of ultraviolet lamps which can consist of discharge lamps, as for example, xenon, metallic halide, metallic arc, such as low or high pressure mercury vapor discharge lamps, etc., having generating pressure of from as low as a few milli- torr up to about 10 atmospheres, can be employed. After UV curing, there is 25 present on the surface of the polycarbonate article a hard, non- tacky, non-opaque, mar, abrasion and chemical resistant coating which is tenaciously adhered to the polycarbonate. The coating is comprised of the photoreaction product of the polyfunctional acrylate ester monomer and the acrylate modified polymer. C ^ Upon the application of UV light, the composition is cured b " the polymerization- of the further polymerizable acrylate modi¬ fied polymer. These polymers further polymerize through the olefinic unsaturation of the acrylate groups. Besides further chain growth of the acrylate modified polymers, crosslinking of these polymers occurs through the olefinic unsaturation of the acrylate groups. The polyfunctional acrylate ester monomers, besides serving as crosslinking agents for the acrylate modified polymers, also form polymers with each other, which polymers can in turn crosslink with each other or with the acrylate modified polymers.- PREFERRED EMBODIMENT OF THE INVENTION In order to more fully and cle'arly illustrate the present invention, the following specific examples are presented. It is intended that the examples be considered as illustrative rather than limiting the invention disclosed and claimed herein. EXAMPLE 1 An aromatic polycarbonate is prepared by reacting 2,.2-bis(4- hydroxyphenyl) propane and phosgene in the presence of an acid acceptor and a molecular weight regulator and having an intrinsic viscosity of 0.57. The product is then fed to an extruder, which extruder is operated at about 265°C and the extrudate is comminuted into pellets. The pellets are then injection molded at about 315 C into test panels of about 4 in. by 4 in. by about 1/8 in. thick. The test panels are subjected to an abrasion test and an adhesion test. The abrasion test is one wherein test panels having a 1/4 inch diameter hole cut in the center are subjected to a Taber Abraser. The Taber Abraser is equipped with CS-10F wheels which are resurfaced every 200 cycles by abrading for 25 cycles on a S-ll refacing disc. The weights used in combination with the CS- 10F wheels are 500 gm. weights. Initial measurements of % Haze a made at four places around the future wear track of the sample 5 using a Gardner Hazemeter. The sample is abraded for 100 cycles, cleaned with isopropanol, and the % Haze is remeasured at the sam four places. The four differences in % Haze are calculated and averaged to give the iΔ Haze. The adhesion test consists of using a multiple blade tool to 10 cut parallel grooves through the coating into the substrate, the sample is then rotated 90° and the cutting process is repeated. This leaves a grid pattern of 1 mm squares cut into the coating. An adhesive tape is applied over the cross-hatched area and quickly pulled off. A sample fails the adhesion test if any of 15 the squares are pulled off. EXAMPLE 2 An acrylated urethane resin - acrylate monomer composition is made as follows. To a dry 1 liter flask equipped with a stirre reflux condenser and addition funnel 174.2 parts by weight of 20 tolμlene diisocyanate and 416.6 parts by weight of hexanediol diacrylate are added. The flask is heated to 50°C employing a nitrogen sparge. To a mixture of 33.6 parts by weight of penta¬ erythritol triacrylate and 208.8 parts by weight of 2-hydroxyethy acrylate is added 0.04 parts by weight of phenothiazine. The 25 pentaerythritol triacrylate/hydroxyethyl acrylate/phenothiazine mixture is added from the addition funnel to the stirred mixture of tolylene diisocyanate in hexanediol diacrylate over a two hour period. The mixture is then heated at 60 C with stirring for thre hours. After this time, the resulting reaction product is allowe to cool to room temperature and 4.2 parts by weight of the penta¬ erythritol triacrylate-hydroxyethyl acrylate-phenothiazine is added to the product to react with any unreacted isocyanate. EXAMPLE 3 A coating composition is prepared by blending 100 parts by weight of the acrylated urethane resin-acrylate monomer composition prepared in Example 2 with 2 parts by weight of 0 ,O^-diethoxy acetophenone, and 0.5 parts by weight of a surface active agent BYK-300 produced by Mallinckrodt Chemical Company. A film approxi- mately 0.3 mils thick of this coating composition is applied to a polycarbonate panel prepared in accordance with Example 1 using a wire wound drawdown bar. The film is cured bypassing the coated panel twice through a Linde UV Curing Apparatus at approximately 50 feet/ in. The UV Curing Apparatus consists essentially of a nitrogen blanketed conveyor containing germicidal and medium pressure mercury vapor lamps which emit light mainly at 2537A°, 3150A° and 3654A°. • The film is tack-free, cured, abrasion and solvent resistant after this treatment. The coated polycarbonate panel i- subjected to the Taber Abrasion Test and to the Adhesion Test and the results are set forth in Table II. EXAMPLE 4 An acrylated urethane resin-acrylate monomer composition is made as follows. To a dry liter flask equipped with a stirrer, reflux condenser and addition funnel are added 174.2 parts by weight of tolylene diisocyanate and 416.6 parts by weight of neopentalglycol diacrylate. The flask is heated to 50°C employing a nitrogen sparge. To a mixture of 33.6 parts by weight of penta¬ erythritol triacrylate and 208.8 parts by weight of 2-hydroxyethyl acrylate is added 0.04 parts by weight of phenathiazine. The pentaerythritol triacrylate-hydroxyethyl acrylate-phenothiazine mixture is added from the addition funnel to the stirred mixture of tolylene diisocyanate in neopentalglycol diacrylate over a two hour period. The resulting mixture is then heated at 60°C with 5 stirring for three hours. After this time, the resulting reactio product is allowed to cool to room temperature and .2 parts by weight of the pentaerythritol triacrylate-hydroxyethyl acrylate- phenothiazine is added to the product to react with any unreacted isocyanate. 10 EXAMPLE 5 A coating composition is prepared by blending 100 parts by weight of the acrylated urethane resin-acrylate monomer compositi prepared in Example 2 with 2 parts by weight of ,θ-diethoxy acetophenone and 0.5 parts by weight of BYK-300. A film approxi- 15 mately 0.3 mils thick of this coating composition is applied to a polycarbonate panel prepared in accordance with Example 1 using a wire wound drawdown bar. The film is cured by passing the coated panel twice through a Linde UV Curing Apparatus at approximately 50 feet/min. The film is tack free, cured, abrasion and solvent 20 resistant after this treatment. The coated polycarbonate panel i subjected to the Taber Abrasion Test and to the Adhesion Test and the results are set forth in Table II. EXAMPLE 6 An acrylated urethane resin-acrylate monomer composition is 25 made as follows. To a dry 1 liter flask equipped with a stirrer, reflux condenser and addition funnel 174.2 parts by weight of tolylene diisocyanate and 416.6 parts by weight of trimethylol¬ propane triacrylate are added. The flask is heated to 50°C employing a nitrogen sparge. To a mixture of 33.6 parts by weigh of pentaerythritol triacrylate and 208.8 parts by weight of 2-hydroxy ethyl acrylate is added 0.04 parts by weight of phenothiazine. The pentaerythritol triacrylate-hydroxy ethyl acrylate-phenothiazine mixture is added from the addition funnel to the stirred mixture of tolylene diisocyanate in trimethylol¬ propane triacrylate over a two hour period. The mixture is then heated at 60°C with stirring for three hours. After this time, the resulting reaction product is allowed to cool to room temper¬ ature and 4.2 parts by weight of the pentaerythritol-hydroxyethyl acrylate-phenothiazine is added to the product to react with any unreacted isocycnate. EXAMPLE 7 A coating compo ' sition is prepared by blending 100 parts by weight of the acrylated urethane resin-acrylate monomer composition prepared in Example 6 with 2 parts by weight of 0 ,C\-diethoxy acetophenone and 0.5 parts by weight of BY -300. A film approxi¬ mately 0.3 mils thick of this coating composition is applied to a polycarbonate panel prepared in accordance with Example 1 using a wire wound drawdown bar. The film is cured by passing the coated panel twice through a Linde UV Curing Apparatus at approximately 50 feet/min. The film is tack free, cured, abrasion and solvent resistant after this treatment. The coated polycarbonate panel is subjected to the Taber Abrasion Test and to the Adhesion Test and the results are set forth in Table II. EXAMPLE 8 An acrylated urethane resin is made by reacting 41.6 parts by weight of a polycaprolactone with 55.6 parts by weight of isophor-. one diisocyanate in 54 parts by weight of 1,6-hexanediol diacry¬ late for 8 hours at room temperature and then with 36.4 parts by OMPI /,.. WIPO weight of hydroxyethylacrylate for 11 hours at 70°C. A blend is made containing 40 parts by weight of the acrylated urethane resin, 43 parts by weight of neopentylglyool diacrylate, 17 parts by weight of 1,6-hexanediol diacrylate, 2 parts by weight of 0 ,0\- 5 diethoxyacetophenone, and 0.5 parts by weight of BYK-300. A film approximately 0.3 mil thick is applied to a polycarbonate panel made substantially in accordance with Example 1. The film is applied, cured and tested as set forth in Example 3 and the results are set forth in Table II. 10 EXAMPLE 9 A blend was made of 40 parts by weight of Actomer X-80 (an acrylated epoxidized linseed oil) produced by Union Carbide Corp. of New York, New York, 60 parts by weight neopentylglycol diacrylate, 2 parts by weight 0 ,0 \ -diethoxyacetophenone, and 0.5 15 parts by weight of BYK-300. A film of this blend is applied to a polycarbonate, cured and tested as in Example 3 and the results are set forth in Table II. EXAMPLE 10 A blend is made of 40 parts by weight of Dow XD 8008-04 (an 20 acrylated bisphenol-A diglycidyl ether) produced by Dow Chemical Co., of Midland, Michigan, 60 parts by weight of neopentyl glycol diacrylate, 2 parts by weight of ^ , -diethoxyacetophenone, and 0.05 parts by weight of BYK-300. A film of this blend is applied to a polycarbonate, cured and tested as in Example 3 and the 25 results are set forth in Table II. TABLE II Example No. Abrasion (Δ% Haze) Adhesion 1 (no coating) 34.0 — 3 3.5 Pass 5 4.3 Pass 7 3.6 Pass 8 8.5 Pass 9 17.2 Fail 10 15.9 Fail EXAMPLES 11 - 12 A number of blends are made which are generally similar to Example 2 except the acrylic monomers are varied. Films of these blends are made and applied to polycarbonate panels and cured substantially in accordance with Example 3. The results are set forth in Table III. TABLE III Example No. Monomer Results 11 Ethylene diacrylate Film wrinkled 12 Tetraethylene glycol Film wrinkled diacrylate The following are examples of combinations which-produce unsatisfactory coatings, i.e., coatings which are inoperative in the present invention. EXAMPLES 13-16 A number of blends are made which are generally similar to Example 2 except the acrylic monomers are varied. Films of these blends are made and applied to polycarbonate panels and cured substantially in accordance with Example 3. The results are set forth in Table IV. TABLE IV Example No. Monomer Results 13 Hydroxyethyl acrylate Unsatisfactory (too wrinkled) 14 Ethoxyethyl acrylate Unsatisfactory (too wrinkled) 15 Ethylene dimethacrylate Unsatisfactory (wrinkled and tacky 16 1,3-butylene dimethacrylate Unsatisfactory (wrinkled and tacky As can be seen from the foregoing Examples and Tables II-IV, only certain combinations of the acrylated resins of. this inventi and certain polyfunctional acrylate monomers give acceptable results. Thus, satisfactory results are obtained by using a com¬ bination of the acrylated urethane resin of this invention in com bination with neopentylglycol diacrylate, trimethylolpropane tri¬ acrylate, hexanediol diacrylate, or butyleneglycol diacrylate. Unsatisfactory results are obtained using an acrylated bisphenol- diglycidyl ether and a neopentyl glycol diacrylate; an acrylated epoxidized linseed oil and neopentyl glycol diacrylate; and an acrylated urethane in combination with ethylene diacrylate, or tetraethylene glycol diacrylate. As shown in Table IV, combina¬ tions of acrylated urethane resins with ethylene dimethacrylate o butylene dimethacrylate or with monofunctional acrylates are inoperative in the practice of the present invention. It is apparent from this that not all combinations of resins and monomers give films which cure readily on polycarbonates to give smooth films which have good abrasion resistance and adhesio to the polycarbonate. Certain combinations of acrylated resins with polyfunctional acrylate monomers give better results than others, while the methacrylate monomers and monofunctional acrylate " monomers" are unsuitable in forming the coatings of the present invention. In fact, there appears to be no way in which one may predict from the starting blend that this set of optimum properties will be obtained. From the foregoing Examples, it is clear that a combination of an acrylated urethane resin as described in Example 2 with a 1,3-butylene diacrylate monomer, 1,6-hexaήediol diacrylate monomer, neopentylglycol diacrylate, and trimethylolpropane triacrylate monomer results in a coating composition which upon curing gives a coating having excellent properties, i.e., a coating comprising the photoreaction product of an acrylated urethane and a polyfunc¬ tional acrylate monomer selected from the group consisting of neopentylglycol diacrylate, 1,3-butylene diacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate, gives excellent results.

Claims: . 1. A non-opaque shaped polycarbonate article having on the surface thereof a UV curable non-opaque coating composition com¬ prised of: (i) an acrylate modified polymer; and (ii) at least one polyfunctional acrylic acid ester monomer represented by the general formula wherein n is an integer having a value of from 2 to 4, and R is a n functional aliphatic hydrocarbon residue, n functional substi¬ tuted aliphatic hydrocarbon residue, n functional aliphatic 10 hydrocarbon residue containing at least one ether linkage, and n functional substituted aliphatic hydrocarbon residue containing at least one ether linkage. 2. The article of claim 1 wherein said acrylate modified polymer is selected from the group comprised of acrylated polyurethanes. 3. The article of claim 2 wherein said polyfunctional acry lic acid ester monomer is selected from the group consisting .of neopentylglycol diacrylate, trimethylol propane triacrylate, hexanediol diacrylate, and 1,3-butylene diacrylate. 4. The article of claim 3 wherein a photoinitiator is present in an amount effective to initiate the photocuring of said coating composition. 5. The article of claim 4 wherein said coating composition contains a UV light absorber. O W - 6-i —- -A non-opaque-shaped polycarbonate article having on the surface thereof a UV cured non-opaque coating comprised of the photoreaction product of an acrylate modified polymer and at least one polyfunctional acrylic acid ester monomer represented by the general formula 0 CH 2 = CH - C - 0 - R n wherein n is an integer having a value of from 2 to 4, and R is a n functional aliphatic hydrocarbon residue, n functional substitu¬ ted aliphatic hydrocarbon residue, n functional aliphatic hydro- carbon residue containing at least one ether linkage, and n functional substituted aliphatic hydrocarbon residue containing at least one ether linkage. 7. The article of claim 6 wherein said acrylate modified polymer is selected from the group comprised of acrylated polyurethanes. 8. The article of claim 7 wherein said polyfunctional acrylic acid ester monomer is selected from the group consisting of neopentylglycol diacrylate, trimethylol propane triacrylate , hexanediol diacrylate, and 1,3-butylene diacrylate. 9. A method of forming an adherent, mar, abrasion and chemical resistant coating on a polycarbonate substrate comprising: a. forming a coating composition containing: (i) an acrylate modified polymer; (ii) at least one polyfunc- tional acrylic acid ester monomer represented by the general formula CH 2 = CH - C - - 01- R 20 wherein n is an integer having a value of from 2 to 4, and R is a n functional aliphatic hydrocarbon residue, 10 n functional substituted aliphatic hydrocarbon residue, n functional aliphatic hydrocarbon residue containing at least one ether linkage, and n functional substituted aliphatic hydrocarbon residue containing at least one ether linkage; and (iii) a photoinitiator; 15 b. applying a thin, uniform coating of said coating composition to said polycarbonate substrate; and, c. UV curing said coating composition under an inert atmosphere until an adherent, mar, abrasion, and chemical resistant coating is formed. 10. The method of claim 9 wherein said acrylate modified polymer is selected from the group comprising acrylated polyurethanes. 11. -The method of claim 10 wherein said polyfunctional acrylic acid ester monomer is selected from the group consisting ' of neopentylglycol diacrylate, trimethylol propane triacrylate, hexanediol diacrylate, and 1,3-butylene diacrylate. 12. The method of claim 11 wherein the photoinitiator is present in an amount effective to initiate the photocuring of said coating composition. 13. The method of claim 12 wherein said coating composition contains a UV light absorber.

Inventors: MOORE J, ORKIN O, SCHROETER S
Applicants: GEN ELECTRIC, GENERAL ELECTRIC CO
Application year: 1979
Main classification: B32B27
IPC codes: B05D7, B32B27, C08F290, C08J7