U.V. STABILIZED ARTICLE AND PROCESS FOR MAKING SAME

Abstract: A surface modified resinous article, which is made by immersing the article in a liquid (2), contacting the surface through the liquid with a solution of a modifier ingredient in a solvent (3), and displacing residual solution, without exposing the modified surface to the atmosphere.

Description: TT.V. STABILIZED ARTICLE AND PROCESS FOR MAKING SA g This invention relates to U.V. stabilized articles, and, more particularly^ to a PVC resinous sheet having its surface modified with a U.V. stabilizer. Photodegradation of many types of solid polymeric articles by U.V. light has been a continual problem confronting the in¬ dustry. Such U.V. degradation causes discoloration, embrittle- ment and deterioration of the article. Accordingly, U.V. ab—- sorber compounds have been incorporated into such polymeric ar¬ ticles in an attempt to provide effective stabilization to U.V. light. However, since photodegradation is known to be a surface phenomenon, incorporation of U.V. stabilizers into the polymeric material prior to shaping into solid form has been largely uneconomical and inefficient because the stabilizer is present substantially in the interior of the shaped article, where it ca not function effectively to prevent surface photodegradation. Accordingly, surface treatments have been proposed to provide more effective U.V. protection for such resins. These treatments are based on the ability of various organic solvents to swell such resins as polyvinyl chloride.. This swelling property enables the ultraviolet light stabilizer material to be directed principally into the surface region of the resin body. Howevβr, none of these surface treatments has been very succes ful commercially. Another surface method comprises laminating the surface of the polymer with a layer of a film-forming material containing the U.V. stabilizer. This lamination ap¬ proach, unfortunately, suffers from the problems of incom- patibilities between polymer, U.V. stabilizer, and the film- forming material and its carrier components. Furthermore, the laminated layer and the surface of the polymer do.not adhere well, and delamination upon shock or impact is a serious proble The swelling method is described by Katz, et al. in an ar- tide in the "Proceedings of the A.C.S. Div. of Org. Coatings a Plastics* lϋ, (1) p. 202-205 (1976), entitled "Ultraviolet Protection of Transparent PVC by Diffusion Coatings". Katz use a dip method to impregnate a transparent PVC sheet to a given depth with a non-migrating ultraviolet light absorber. The dip technique comprises swelling the polymer with a carrier solvent, infusing the stabilizer from a solution thereof with the carrie and, thereafter heating the treated polymer in air at an elevat temperature to drive the stabilizer below the surface of the polymer and to remove residual solvent. Under these process co ditions, however, only a small amount of stabilizer is absorbed into the surface region. Furthermore, the dip method produces product in which both sides of the sheet are modified with ultraviolet absorber. Jochanan, in Israeli Patent No. 39037, published Nov. 10, 1975, entitled "U.V.- and Oxidation-Proof Products from Organic Plastics and their Manufactured, describes various methods of a plying a solution or suspension of an ultraviolet light absorbe to the surface of a plastic sheet. The methods disclosed by Jochanan include immersion, spraying, brushing, roller-printing and curtain-coating. However, with such methods, a large amoun of residual stabilizer and solvent is left on the surface of t article, whereupon the modified surface is observed to be streaky, hazy, and has runs or pock- marks thereon. Humphrey, in U.S. 4,146,658, describes a process for prod ing an ultraviolet light stabilized polycarbonate article by d ping the polycarbonate sheet into an impregnating solution con sisting of a selected combination of ultraviolet absorber and solvent. However, all the disadvantages of the conventional d method are present here, too. Ching, in U.S. 4,349,607, describes the incorporation of certain U.V. stabilizers into thermoplastic resins by dipping* spraying and brushing followed by heating at 70°C., which metho is unsatisfactory for providing surface modified PVC sheets having a high degree of surface perfection. A borski, in U.S. 3,043,709, discloses an organic polymer article having an ultraviolet light absorber compound incor¬ porated adjacent to the surface of the article. The article i treated by several methods, including dipping-coating a polyethylene terephthalate film in a stabilizer solution, or applying a dispersion or melt of the absorber, or applying the absorber as a powder, and, thereafter, the coated film is heat in air to 115°C. and above to drive the absorber below the sur¬ face of the film and to remove the solvent. These processes, however, are disadvantageous because they require heat-treatm to fully modify the surface of the film. Furthermore, these methods form an article in which considerable residual absorber is present on both sides of the film, which affects its surface perfection and appearance. Fanning, in U.S. 3,297,462, discloses a process for render ing polymeric films resistant to the deteriorating effects of sunlight by immersing them in a solution of a benzophenone stab lizer in a solvent mixture of diethylene glycol and glycerine, and then washing successively in diethylene glycol and water. The polymers suitable for such treatment, however, must have a zero strength temperature of at least 200°C., which excludes man useful polymers, including polyvinyl chloride. Solvay and Cie, in Belgium Patent No. 612,206, discloses a process for surface treating rigid polyvinyl chloride objects. The method comprises immersing the object in a swelling solvent containing a light stabilizer and then evaporizing the . solvent i air. This procedure, however, is ineffective because some stabi lizer remains on the treated surface of the object, which gives poor physical appearance, and, environmental hazards are created during removal of the solvent in air. Cohnen, in U.S. 3,892,889, describes a method of applying a solution of a U.V. stabilizer to polycarbonate resin sheets. Such treated polymers, however, also are marred by the presence of residual stabilizer on the surface of the article. Chilton, in U.S. 4,323,597 teaches a flow-coating process for polycarbonate articles. In this process, the surface of the polycarbonate is heated and a liquid stabilizer composition, which is non-aggressive towards but wets the polycarbonate sur- face, is flowed over the heated surface. There is no indication in this patent, however, that the method is applicable to polyvinyl chloride. Bristol, in U.S. 3,519,462, describes the treatment of polyvinyl chloride and other polymers with a solution of a U.V. stabilizer in a diol or triol. These solvents, however, are no efficient swelling agents for PVC. Furthermore, there is no recognition therein of the need for removing excess stabilizer solution present on the treated surface. Chauffoureaux, in U.S. 3,783,011, diffuses a vapor of a U.V stabilizer into the surface of polyvinyl chloride and other polymers. Unfortunately, the vapor treated surfaces have poor physical characteristics. Katz, M. , Shkolnik, S. and Ron, i. in Soc. Plast. Eng., έ Technical Papers (1976) 22., P- 511-512, describes experiments relating to the preparation and testing of PVC which was surface coated by the dipping method. Lempkowicz, A. et al., U.S. Patent 4,126,660 describes sur- face modification by applying a stabilizer solution in air, vaporizing the solvent, and condensing the evaporated solvent fo recycling, this air treatment is disadvantageous because such evaporation leaves solid material on the surface of the sheet. Baumgaertel, H. et al., FRG Patent Applications 28 08 005 and 28 08 036, both filed 2/24/78, laid-open 8/30/79 describes a process for regenerating installed, weathered PVC siding by spraying, brushing, or roller-coating the object with a solution of a U.V. absorber in an organic solvent or mixture of solvents. Baumgaertel's method of treatment merely coats stabilizer onto the regenerated surface. This process also changes the base thermoplastic material which has been degraded by sunlight. In this invention, on the other hand, the treated PVC is modified with stabilizer within the surface region and is unaffected by such modification. Thereby, the article herein has long-term stability and retains its original appearance. In summary, these and other processes have not provided us ful U.V. stabilized articles, particularly polyvinyl chloride resin articles, for example, for residential siding, which use requires particularly effective protection from the weathering effects of sunlight, and an appearance and degree of surface per fection which is acceptable in commercial use. Accordingly, there is a present need to effectively modify the exposed surface of a PVC sheet, such as residential siding, with a U.V. stabilizer. Such a surface modified, U.V. stabilize PVC siding article preferably should have only one side surface modified with the stabilizer material. Furthermore, the expose surface of the sheet should be substantially free of residual stabilizer and solvent material, and the appearance and degree o surface perfection of the modified side should be the same as that of the unmodified side of the sheet. - In addition, the sur¬ face modification should be effected in situ to lesson environ- mental hazards. Accordingly, it is an object of this invention to provide a surface modified, U.V. stabilized resin sheet article having bo sides exposed to the air, wherein the surface is substantially fully modified in situ with a stabilizing amount of a U.V. stabi lizer material, the exposed surfaces are substantially free of residual stabilizer and solvent material, and the appearance and degree of surface perfection of the modified side are substan¬ tially the same as that of the unmodified side. It is another object of this invention to provide a meth for incorporating various types of ingredients such as ultraviolet light stabilizers, antioxidants, anti-static ar¬ ticles^^especially those fabricated from thermoplastic polyme such as PVC. SUMMARY OF THE INVENTION What is described herein is a surface modified, U.V. stabilized article which includes a resinous sheet whose sides are both exposed to the air. The surface region of one side o the sheet is substantially fully modified in situ with a stabi lizing amount of an ultraviolet light stabilizer material, whi the exposed surfaces are substantially free of residual stabi lizer and solvent material, and the appearance and degree of s face perfection of the modified side are substantially the sam as that of the unmodified side of the sheet. The surface region of the sheet extends for a depth of up 200 microns from the surface. This region is fully modified i situ in this invention with a stabilizing amount of a ultravio light stabilizer comprising at least 0.3 g/m 2 of the surface o the sheet, preferably 0.5 g. to 6.0 g./m 2 . At least 70% of th stabilizing amount is present within the first 100 microns of surface region, and 0.1 to 0.6 g/m 2 is present in the first 20 microns from the surface. In accordance with the invention, the U.V. stabilized res article is made by " a continuous process comprising immersing a resin body in a suitable liquid media, and- contacting the surf of the immersed body through the liquid with a solution of a ultraviolet light stabilizer in a suitable organic solvent and displacing residual stabilizer and solvent from the modified sur face in situ, both step being carried out without exposing the mαd±fiect surface to the atmosphere. The method of this invention thus involves incorporating at least on ingredient in a polymer fabricated from a polymer by the steps of: (a) immersing the article in a liquid; and (b) contacting the immersed article with a solution of the ingredient in a solvent, the liquid being one which is non-aggressive towards the article and which is immis¬ cible with the solvent. The term " non-aggressive" is used herein to signify that the liquid will not dissolve, swell or otherwise react with the polymer and is to be considered inert towards the polymer. * In a preferred embodiment, the method comprises incorporat¬ ing at least one ultraviolet light stabilizer in the surface region of an article fabricated from PVC by the steps of: (a) transporting the article through an aqueous media; (b) contacting substantially only one surface of the ar¬ ticle with a solution of the stabilizer on an organic solvent while the article is being transported through the aqueous media, the aqueous media being one which i non-aggressive with the article which is immiscible with the solvent; and (c) displacing any residual solution remaining on the con¬ tacted surface. Most preferably, the process is practiced in a continuous mode and involves incorporating at least one ultraviolet light stabilizer in the surface region of a sheet fabricated from PVC. The surface region extends up to a depth of about 200 microns the amount of stabilizer incorporated in this region will be a least 0.3, preferably 0.5 to 6.0 g/m 2 of the surface of the PV sheet, with at least 70% of such amount concentrated in the up 100 miczfons of the surface region. This most preferred embodi ment involves: (a) transporting the sheet substantially horizontally through an upper water layer, there being a methylen chloride solution containing 1-60 wt.% of the stabi- lizer present as a layer beneath the water layer; (b) flowing the solution from the bottom layer through th upper water layer onto substantially only one surface of the sheet as the sheet is being transported throug the water layer such that the solution is in contact with the surface for a period of time ranging from 1 second to 2 minutes; and thereafter (c) directing a jet of water onto the contacted surface t displace any residual solution on the surface. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more clearly understood by referring to the following drawings, in which: Fig. 1 shows the U.V. stabilized article of the present invention. Fig. 2 is a scanning election micrograph of the modified surface of a stabilized PVC article in accordance with the present invention. Fig. 3 shows the untreated surface of the sheet of Fig. 2. Fig. 4 shows the -edified surface of Fig. 2 after weatheri for 15 mos. in sunl.^ht. Fig. 5 shows the untreated surface of Fig. 3 after weather¬ ing for 15 mos. in sunlight. Fig. 6 is a schematic representation of an apparatus for making the U.V. stabilized article of Fig. 1 by a continuous process. DETAILED DESCRIPTION OF THE INVENTION Referring now to the drawings, Fig. 1 shows the U.V. stabi¬ lized article of the present invention. The article includes a resin body, such as a sheet or other shaped structure thereof of polyvinyl chloride or another polymeric resin. The article has sides S and S', both of which are exposed to the air. Each ex¬ posed side has respective surfaces SUR and SUR*. Side S has a surface region SR extending from surface S to a depth of about 200 microns into said sheet. Surface region SR is modified with a stabilizing amount of a U.V. stabilizer material, which is an amount of least 0.3 g/m 2 , preferably 0.5 to 6.0 g/m 2 of the sur¬ face of the sheet, and most preferably about 1.8 g/m 2 thereof. 70% or more of the stabilizer is found within the first 100 microns of the surface region at least 0.1 preferably at least 0.3 to 0.6 g/m 2 is present in the first 20 microns. Stabilizer is substantially absent in the interior or bulk of the sheet, an surface SUR also is substantially free of residual stabilizer. The uniformity, appearance and degree of surface perfection of the modified surface SUR is substantially the same as that of the unmodified surface SUR'. Surface perfection is defined as a surface which is non-tacky and non-streaking, and which retains its original shape and hardness after being modified with stabi¬ lizer. Referring now to Figs. 2-5, there are shown scanning electron micrographs of the modified surface SUR of the U.V. sta bilised"Yesin sheet (Fig. 2), its corresponding unmodified sur¬ face SUR' (Fig. 3), the modified surface after weathering (Fig. 4) , and the unmodified surface after weathering (Fig. 5) . These micrographs illustrate that the surface of the treated resin ar¬ ticle herein (Fig. 2) has substantially the same degree of sur¬ face perfection as that of its untreated surface (Fig 3) . In ad¬ dition, the treated surface (Fig. 4) remains substantially unaf- fected by exposure to ultraviolet light for a protracted period of time, while the untreated surface (Fig. 5) , under similar con¬ ditions of exposure, has deteriorated perceptibly. The shaped resin body itself is obtained by general mechani¬ cal processing techniques known to those skilled in the art. II- lustrative of such mechanical operations are compression, injec¬ tion, jet, transfer molding, vacuum forming, extrusion and the like. Such bodies can range from flexible sheets to rigid struc¬ tural members. However, the invention is aimed particularly at articles which are plagued by U.V. degradation accompanying out- door weathering, and, particularly, PVC residential siding. Accordingly, polyvinyl chloride is the preferred resin for the article of the invention. However, other resins susceptible to impregnation with U.V. stabilizers also are suitable, includ¬ ing ABS(acrylonitriLe/butadiene/styrene) rubber, polypropylenes, polyacrylates, poiyr.ethacrylates and polyesters, e.g. polyethylene terephthlate and polybutylene terephthlate. The resin article itself may be transparent, translucent, opaque or pigmented. Referring now to Fig. 6, there is shown schematically an apparatus useful for making the U.V. stabilized resin article of the invention. In general, the method comprises immersing a resin sheet in a suitable liquid media, contacting the surface of the immersed sheet to be modified through the liquid with a solu¬ tion of an ultraviolet light stabilizer in a suitable organic solvent, and displacing residual stabilizer and solvent from the treated surface in situ. Suitable solvents are those which swell the resin effectively and are immiscible with the organic solvent and non-aggressive towards the resin. More particularly, the preferred in situ method of makiijg the U.V. article of the invention is a continuous process which comprises immersing the resin sheet in an aqueous liquid, e.g. water, flowing a solution of an ultraviolet light stabilizer in a resin-swellable organic solvent through the water into contact with the surface of the sheet to be modified while it is immersed in the water, thereupon causing the surface contacted to swell sufficiently to allow the stabilizer solution to fully penetrate into the surface region of the sheet, and then displacing residual stabilizer and solvent from the modified surface in situ, preferably with said aqueous liquid. After contacting the surface of the sheet, excess stabilizer solution falls or rises from the thus-treated surface. The par¬ ticular direction will depend on the respective densities of the liquid and organic solvent employed. It is preferred to use liq¬ uids such as ater cr aqueous solutions thereof, and organic sol¬ vents having a density greater than water or such solutions. Ac¬ cordingly, the preferred arrangement of liquid and solution is a two-layered system, where water is the upper layer, and the solu- tion of stabilizer in the organic solvent is the lower layer. The organic solvent is selected among solvents which do n mix with the liquid media; otherwise, the solvent would not re the-resin sheet but would simply dissolve therein. Another con sideration in choice of solvent is an empirical one, namely, th desire to impregnate the resin article with the U.V. stabilizer within a minimum contact time. This property depends on a numb of factors, particularly the ability of the solvent to effec¬ tively swell the resin surface. The system shown in Fig. 6 is a two-layered system in whic the liquid phase is the upper layer and the stabilizer solution is the lower layer, and the resin sheet is oriented in an im¬ mersed state in the upper layer. In operation of such a two- layered process in a continuous manner, the stabilizer solution is pumped from the lower layer and applied over the sheet from beneath the aqueous upper layer. Excess stabilizer solution th falls off the sheet by gravity to return to the lower layer. T organic solvent in the stabilizer solution is blocked from evaporating into the atmosphere by the blanket of liquid above it, which is advantageous for producing modified surfaces havin a high degree of surface perfection, and for ecological reasons The apparatus of Fig. 6 includes tank 1 about 3/4 full wit water 2 as the upper layer. Stabilizer solution 3 of a U.V. ab sorber in an organic solvent, e.g. methylene chloride, is prese as the lower layer therein. A continuous resin strip 4 of ex- truded polyvinyl chloride, for example, is fed into the upper layer at a predetermined rate from below roller 5, which is pos tioned below surface 6 of the water. Further ahead of roller 5, in what is referred to herein a the "application zone" A, a series of applicator nozzles 7 are -oriented below the surface level 6 of the water with their orifices directed towards the surface of strip 4. The applicator nozzles continuously direct a stream of stabilizer solution 3 over the upper surface 8 of the moving resin strip 4. The thus- applied stabilizer solution remains on the surface of the strip whereupon the surface region is modified effectively with stabi¬ lizer. The length of time the stabilizer solution remains on the surface of the sheet within the application zone is referred to herein as the "contact time" of the process, defined hereinafter. Downstream of the applicator zone is a "displacement zone" B, in which residual stabilizer solution is removed in situ from the thus-treated surface of the strip. The term "in situ" means that the displacement step is carried out without exposing the treated surface to the ambient atmosphere; rather, the surface remains under water where the solvent cannot evaporate. Such evaporation would leave streaks of solid stabilizer material thereon which is highly undesirable. The duration of passage from the applicator zone to the dis¬ placement zone is defined herein as the "contact time" of the process. In the displacement zone, a jet element 9 directs a spray of displacing liquid, preferably water 2, at a pressure sufficient to displace residual stabilizer solution from the treated surface of the strip. Jet element 9 comprises a hollow, perforated rod 10 terminating in slit 11 through which strip 4 is conveyed into the displacement zone. A second roller 12 is located ahead of the displacement zone and below the level of the water to accept the thus-treated resin strip after it leaves the displacement zone. Variable speed nip roller pullers (not shown) are positioned outside the tank to move the strip at a predetermined speed through and out of the tank, wfiere it can be stored on a suitable take-up roll. The equipment and procedure described above also is ap¬ plicable to organic solvents having a density which is less tha one, e.g. ethyl acetate, 2-pentanone, 3-pentanone. and the like. For such organic solvents, the stabilizer solution would con¬ stitute the top layer and water the bottom layer. The stabilize solution then would rise in the water to contact the resin sheet from the underside, thereafter passing upwardly. The ingredients which may be incorporated into the articles fabricated from such polymers include ultraviolet light stabi¬ lizers (which are preferred) , anti-oxidants, anti-static agents, pigments and the like. The nature of such ingredients is not critical so long as they are compatible with the polymer and wit the solvent of choice. Of course, the ingredients must be suffi ciently soluble on the solvent of choice so as to cause the desired amount thereof to be incorporated in the polymer article The invention will be described now with the reference to the following examples, in which the U.V. stabilizer article of the present invention is prepared using the apparatus and system of Fig. 6. PREPARATION OF U.V. STABILIZED ARTICLE OF INVENTION Example 1 A solution of 7.5% by weight of Cyasorb U.V. 5411 stabilize (a trademark of American Cyanamid Co.) in methylene chloride was applied onto the upper surface of a horizontally supported, moving polyvinyl chloride resin strip immersed in water at 25°C. The applicator nozzles were directed vertically towards the uppe surface of the sheet from a position beneath the water level. Thereupon stabilizer was absorbed into the surface region of the upper surface of the sheet and excess solution fell to the botto of the tank. The contact time was 24 seconds. Downstream of th applicator zone, a jet of water was applied to the treated sur¬ face to displace residual stabilizer and solvent still remaining on the treated surface. The U.V. stabilized article then exited the tank and was wound onto a take-up roll. Exam lg 2 PROPERTIES OF U.V. STABTTYrZEn ARTTC___ / The U.V. stabilized article prepared in Example 1 was microtimed into 20 micron sections extending to a total depth of 200 microns from the surface. The amount of U.V. stabilizer present in each of these sections was determined by means of hig pressure liquid chromatography (HPLC) analysis. The results are given in Table I below. CONCENTRATION PROFILE OF STABILIZER IN SURFACE REGION AND BULK OF SHEET Section % Of Stabilizer A t. Of Stabilizer Total % of Total (microns) in Section (g/m 2 ) Stabilizer at Stabilizer at Given DeDth (erΛn^ Given Depth 0-20 2.30 0.64 20-40 1.91 0.52 40-60 1.70 0.47 60-80 1.47 0.40 80-100 1.40 0.38 2.42 71 100-120 1.30 0.36 120-110 1.17 0.32 140-160 0.62 0.17 160-180 0.32 0.09 180-200 0.14 0.04 3. 9 UV tabillzer _S_oJ_yj.ton Stabilizer Cyasorb UV 5411 (Trademark of the American Cyananiid Corp.) Chemical Name: 2(2' - hydroxy - 5't - octylphenyl) - benzotriazole Solution 7.5% by w It of stabilizer in methylene chloride solvent. i Process Conditions Temperature - 25°C. Contact time - 24 sec. Sheet speed - 1.5 ft./min. Thickness of PVC Sheet - 1300 microns Composition of PVC sheet - 0% T j Og The test results in Table I show that 3.39 g/m 2 of the sta¬ bilizer is deposited within the surface region of one side of the sheet, i.e. within a depth of 200 microns from the surface, and 71% of this amount, or 2.42 g/m 2 , is present within the first 100 microns " Ha the surface region. Within the interior or bulk of the sheet, i.e. from 200 to 1300 microns (the thickness of the sheet) substantially no stabilizer is present. Furthermore, residual stabilizer and solvent (less than 1% of each) are not present on the modified surface of the sheet. The resultant product had a uniform treated surface which was non-tacky, had no streaks of solid material thereon, and retained to original planarity and hardness. Sxaro le 3 Following the procedures of Examples 1 and 2, variouβ-con- centrations of stabilizer solutions were applied.onto the upper surface of the PVC sheet during predetermined contact times. Table II shows the amount of the stabilizer incorporated into the surface region of the resin sheet for such various stabilizer concentrations and contact times using methylene chloride as the solvent. The protection of the article against deterioration by U.V. light under these different process conditions is presented in Table II as changes in yellowness index (YI) , orZΛYI values. The __ΛYI values were deteriαined upon accelerated U.V. exposure tests, according to ASTM G 53-84. The change from initial to final YI is designated ΛYI. A ZΛYI value of zero (or minus) in¬ dicates minimal or complete absence of yellow; positiveZΛ I values evidences increasing yellowness caused by U.V, exposure. -19- Table II Effect of Concentration of Stabilizer and Contact Time o Amount of Stabilizer Incorporated into Surface Region of Sheet and its U.V. stabilit y Stabilizer Amount of U.V. exposur Samnle onC t _ Contact Time Stabilizer fin weeks ) NO. f% wt./volϊ (sec.ϊ fσ i> 1 4 1 2 30 1.78 1.3 4. 2 3 30 2.67 -2.9 -2.0 3 3 60 3.38 2.2 -0.4 4 5 15 5.16 -1.0 0.3 5 5 30 5.34 0.0 . 1.2 6 5 60 7.12 -0.8 -1. 7 10 15 11.22 0.7 -1. 8 10 30 9.80 -1.0 0.9 9 10 60 16.86 -0.6 -1.4 Control 0 0 0 29 50 The results in Table II show that application of stabili solution having a concentration of 2 wt.% for 30 sec. provide amount of stabilizer in the surface region of the sheet suffi cient to afford excellent protection against U.V. light. At centrations up to 10 wt.% of stabilizer, and for contact time to 1 min. , even more effective U.V. protection is achieved. The depth profiles of a series of PVC articles surface modified in controlled laboratory experiments simulating the process of the invention were obtained to determine the effec the concentration of the stabilizer at different depths withi the surface region, particularly within the first 20 microns, upon the changes in yellowness index. These experiments demonstrate that excellent weatherabilit is obtained when at least 0.1 g/m 2 , preferably 0.1 to 0.6 g/m 2 o stabilizer is present within the first 20 microns from the sur¬ face of the sheet; and at least a total of 0.3 g/m 2 , preferably 0.3 to 6 g/m 2 , of stabilizer is present within the surface regi of the sheet. As described, the preferred liquid media in the method use herein is water or an aqueous solution or emulsion thereof. Other liquids, however, can be used as long as they are "incompatible* with the organic solvent. The term "incompatibl is defined herein to mean a liquid having a solubility of no mo than about 15 percent by weight in the organic solvent and as a bient temperature and pressure. Such liquids include alkanols and other water miscible liquids. Similarly, the solvent in the stabilizer solution should b "liquid-immiscible solvent", which also is defined as a solubility in liquid at ambient temperature and pressure of no more than about 15 per cent by volume. Accordingly, organic solvents suitable for use herein in- elude water-immiscible organic solvents, as for example, halogenated hydrocarbons having up to six, preferably three, carbon atoms in the chain; ketones, both aliphatic and cycloaliphatic; aliphatic esters and the like. Representative halogenated hydrocarbons include methylene chloride, chloroform 1,2-dichloroethane, 2-chloro-2-methylpropane and like chlorinat hydrocarbons. Exeπtpl y ketones are 2-pentanone, 3-pentanone, hexanone, 2,4-pentanedione and the like. Suitable ethers inclu diethyl ether, diprcpyl ether, dimethoxy ethane, furan, tetrahydropyran and the like. Mixtures of mutually miscible ganic solvents can also be used. The preferred organic solve are methylene chloride, 1,2-dichloroethane, ethyl acetate, 2- pentanone and 3-pentanone, and mixtures of these solvents. Suitable U.V. stabilizers include the following commerci available materials: Cyasorb U.V. 9: 2-hydroxy-4-methoxybenzophenone (Tradema of American Cyanamid) Cyasorb U.V. 531: 2-hydroxy-4-n-octoxybenzophenone (Trademark of American Cyanamid) Cyasorb U.V. 5411: 2(2'-hydroxy-5'-t-octylphenyl)- benzotriazole (Trademark of American Cyanamid) Tinuvi P: 2(2'hydroxy-S'-methylphenylJbenzotriazolβ (Trademark of Ciba-Geigy) Tinuvin 326: 2-(3't-butyl-2'-hydroxy-5'-me hylphenyl)-5- chlorobenzotriazole (Trademark of Ciba-Geigy) Sanduvor VSU: 2-ethyl-2-ethoxyanilide (Trademark of Sando Corp.) Tinuvin 144 and 770: hindered amine light stabilizers (Trademark of Ciba Geigy for HALS) Irgastab 2002: a nickel phosphate (Trademark of Ciba-Geigy) The following is a partial list of these and other ben- zophenones and triazoles which are suitable U.V. stabilizers f use herein. 2,2'-dihydroxybenzphenone 2,2,4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-di ethoxybenzophenone 2,2'-dihydroxy-4,4'-diethoxybenzophenone 2,2'-dihydroxy-4,4'-dipropoxybenzophenone 2,2'-dihydroxy-4,4'-dibutoxybenzophenone 2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone 2-hydroxy- , ',5'-trimethoxybenzophenone 2-hydroxy-4-ethoxy-4'-methylbenzophenone 2-hydroxy-4-ethoxy-4'-ethylbenzophenone 2-hydroxy-4-ethoxy-4'-propylbenzophenone 2-hydroxy-4-ethoxy- '-methoxybenzophenone 2-hydroxy-4, -diethoxybenzophenone 2-hydroxy-4-ethoxy- '-propoxybenzophenone 2-hydroxy-4-ethoxy-4'-butoxybenzophenone 2-hydroxy-4-ethoxy-4'-chlorobenzophenone 2-hydroxy-4-ethoxy- ; -bromobenzophenone 2-(2'-hydroxy-5'-methylphenyl)benzotriazole 2-( '-hydroxy-5'-t-butylphenyl)benzotriazole 2-(2'-hydroxy-3'-methyl-5-t'-butylphenyl)benzotriazole 2-(2'-hydroxy-5'-cyclohexylphenyl)benzotriazola.- 2-(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole 2-(2'-hydroxy-5'-t-butylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3'-di-t-butylphenyl)benzotriazole 2,2'-dihydroxy- -methαxγ-4'-butoxybenzophenone 2,2'-dihydroxy-4-ethoxy- '-propoxybenzophenone 2,3'-dihydroxy- , '-dimethoxybenzophenone 2,3'-dihydroxy- -methoxy-4'-butoxybenzophenone 2,3'-dihydroxy-4,4,5'-trimethoxybenzophenone 2-hydroxy-4,4,5'-trimethoxybenzophenone 2-hydroxy-4,4,6,'-tributoxybenzophenone 2-hydroxy-4-ethoxy-2,4'-dibutylbenzophenone 2-hydroxy-4-propoxy-4,6'-dichlorobenzophenone 2-hydroxy-4-propαxy-4' ,6'-dibro obenzophenone 2,4-dihydroxybenzcphenone 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-ethoxyben_ophenone 2-hydroxy-4-propoxybenzαphenone 2-hydroxy-4-butoxybenzophenohe 2-hydroxy-4-methoxy-4'πiethylbenzophenone -23- 2-hydroxy-4-methoxy- 'propylbenzophenone 2-hydroxy-4-methoxy- 'butylbenzophenone 2-hydroxy-4-methoxy-4'-t-butylbenzophenone 5 2-hydroxy- -methoxy-4'-chlorobenzophenone 2-hydroxy-4-methoxy-2'-chlorobenzophenone 2-hydroxy-4-methoxy-4'-bromobenzophenonβ 2-hydroxy-4,4'-dimethoxybenzophenone 2-hydroxy-4,4'-dimethoxy-3-methylbenzophenone "Lo 2-hydroxy-4,4'-dimethoxy-3-methylbenzophenone 2-hydroxy-4,4'-2'-ethylbenzophenone 2-hydroxy-acetophenone The preferred temperature for making the U.V. stabilize ticle of the present invention is ambient temperature. Howe 5 process temperatures lower and higher than ambient temperatu may be used, if desired. For example, the water solubility o certain useful organic solvents, e.g. ethyl acetate, decrease with increasing temperature. Thus, it may be advantageous to process temperatures higher than ambient temperature for such 0 solvents. Similarly, organic solvents which swell a particul resin only modestly at room temperature can be rendered quite fective for infusion of the requisite amount of stabilizer in the surface region of the resin by raising the treatment temp ture. 5 Although the preferred embodiment of the stabilizer arti herein has only one side of the article modified with stabili it is understood that both sides may be modified, if desired, directing jets of stabilizer solution towards both surfaces o the resin sheet. -24- The article herein may or may not include a white pigmen such as a compound selected from an inorganic metallic oxide, sulfate or carbonate, for example, titanium dioxide, antimony trioxide, magnesium oxide, silicon dioxide, zinc oxide, bariu sulfate and calcium carbonate. Titanium dioxide, which is a white pigment, has a dual f tion in polyvinyl chloride articles. The first function of titanium dioxide is to stabilize polyvinyl chloride against t adverse effects of U.V. radiation by absorbing, reflecting, d persing or scattering in the incident U.V. energy. The secon function of titanium dioxide is to render the article opaque that colored articles may be produced, if desired,,.by includi colorants therein in an amount sufficient to overcome the whi titanium dioxide present. Unfortunately, the amount of titanium dioxide necessary effective U.V. stabilization, about 12 phr, precludes deep coloration of such articles. In fact, only colored articles pastel shades can be obtained; deep shades of brown, blue and maroon, for example, are not readily attainable. Accordingly would be advantageous to provide U.V. stabilized polyvinyl chloride articles characterized by the substantial absence of titanium dioxide therein. Of course, the absence of titanium dioxide is accompanie the loss of its U.V. stabilization function. Therefore, for articles, it is necessary to provide an alternative means of stabilization for such articles. Since titanium dioxide is s a cheap raw material, it is uneconomical to substitute an eff tive, but high priced organic U.V. stabilizer, such as a ben- zophenone or benzotriazole, in place of titanium dioxide. -25- Furthβrmorβ, since photodegradation is known to be surface phenomenon, bulk incorporation of such organic U.V. stabili is .inef icient because the stabilizer is present substantia the interior of the article, where it does not prevent surf photodegradation. Suitably titanium dioxide can be absent or, if present herein, is included in an amount of 0.5 phr, preferably up phr, and optimally, about 1 to 6 phr, with or without a col pigment, in the surface modified article of the invention. While the invention has been described with particular. reference to certain preferred embodiments it will be under that other modifications may be made within the preview of invention. For example, the solution of the modifier ingre in a solvent may be applied to a resin article which passes through the solution, with the displacing liquid being prese either above the solution, or in side-by-side relationship. the latter embodiment, the displacing liquid need not be necessary immiscible with the solution and its solvent. The and other modifications will be apparent to those skilled in art.

Claims: TN THE CLAIMS 1. A U.V. stabilized article comprising a resinous arti having at least one surface exposed to sunlight and at least sides exposed to the air, the surface region of one side of s sheet being modified with a stabilizing amount of an ultravio light stabilizer, the exposed surfaces being substantially fr of stabilizer material, and the uniformity, appearance and de of surface perfection of said modified side as a result of sa modification being substantially the same as that of the unmodified side of the sheet, wherein the degree of surface perfection is characterized by being substantially non-racxy, non-streaking and having substantially its original shape and hardness. 2. A U.v. stabilized PVC sheet according to Claim 1 whe said stabilizing amount is 0.3 to 0.6 g/m 2 of the surface of s sheet, and said surface region extends to a depth of up to 20 microns from said surface, and at least 70% of said stabilizi amount is present in the first 100 microns of said region. 3. A U.V. stabilized article according to Claim 1 in wh 0.1 to 0.6 g/m 2 of said stabilizer is present in the first 20 microns of said sheet. 4. A U.V. stabilized article according, to Claim 1 where said stabilized amount is at least 1.8 g/m 2 of the surface of said sheet. 5. A U.V. stabilized sheet according to Claim 2 wherein said PVC resinous sheet is transparent, translucent, opaque and/or pigmented. 6. A U.V. stabilized article according to Claim 1 whic a rigid sheet ordinarily susceptible to outdoor weathering. 7. A U.V. stabilized article according to Claim 1 which a residential siding article. 8. A U.V. stabilized article according to Claim 1 which includes at least 0.5 phr of a white pigment, preferably 0.5 t phr, selected from an inorganic metallic oxide, sulfate, or ca bonate, preferably titanium dioxide, antimony trioxide, magnes oxide, silicon dioxide, zinc dioxide, barium sulfate or calciu carbonate, optionally with a colored pigment also included therein. 9. A U.V. stabilized article according to Claim 1 furth characterized by the substantial absence of titanium dioxide therein. 10. A method of incorporating at least one ingredient in article fabricated from a polymer selected from polyvinyl chloride, polyethylene, polypropolyene, polystyrene, polycar¬ bonates, thermoplastic polyesters, thermoplastic acrylonitrile/butadiene/styrene copolymers, polyacrylates and polymethacrylates which comprises immersing the article with solution of the ingredient selected from ultraviolet light sta lizers, antioxidants, anti-static agents and pigments in a sol vent, said liquid being one which is non-aggressive towards th article and which is immiscible with the solvent, and displaci any residual solution remaining on the contacted surface while avoiding escape of solvent into the atmosphere. 11. The method of Claim 10 wherein the liquid is water. -28- 12. The method of Claim 10 wherein the solvent is methyl chloride. 13. The method,-of-Claim -10 wherein th^stalsiliapr is present in the solvent in a concentration of afitrafc 1. to about by weight. 14. The method of claim 10 wherein ttw-serticlβ is dispos in the liquid such that the solution on one surface thereof. 15. The method of claim 10 which is carried out in a con¬ tinuous manner. 16. A continuous method of i corpor tionaftsleaϋfe one ultraviolet light stabilizer in the surface region of an artic fabricated from polyvinyl chloride which comprises the steps o (a) transporting the article through an aqueous media; (b) contacting substantially only one surface of the ar- tide with a solution of the stabilizer in an organi solvent while the article is being transported throu the aqueous media, said media being one which is non aggressive towards the article and which is immiscib with the solvent; and (c) displacing any residual solution remaining on the co tacted surface. 17. A process for incorporating at least one ingredient i a polymer article which comprises applying a solution of said gredient in a solvent to a surface of said article, and displa ing residual ingredient and solvent from the thus-treated surface; both steps being carried out in a environment which avoids escape of any significant amount of said solvent into t atmosphere. 18. Apparatus for incorporating at least one ingredient an article fabricated from a polymer which comprises: (a) means for immersing the article in liquid, (b) means for applying a solution of the ingredient on solvent to said immersed article, said liquid being non-aggressive towards the article and immiscible w the solvent, and (c) means for displacing any residual eαlution remainin the contacted surface. 19. Apparatus according to Claim 18 wherein said ingredi is an ultraviolet light stabilizer and said liquid is water, a said means of displacing residual solution includes a jet of*s liquid. 20. Apparatus for incorporating at least one ultraviolet light stabilizer into the surface region of an article fabrica from polyvinyl chloride which comprises: (a) means for continuously transporting the article thro an aqueous media; (b) means for applying a solution of said ultraviolet li stabilizer in a solvent into the surfaee of the arti in said aqueous media, said aqueous media being non- aggressive towards the article and immiscible with t solvent, and (c) jet means downstream of said applying means for dire ing a spray of an aqueous media onto said treated su face to displace any residual solution remaining on treated surface. 21. Apparatus for incorporating at least one ultraviolet light stabilizer . into the surface region of a sheet fabricated from polyvinyl chloride which comprises: (aj means for transporting said sheet continuously and s stantially horizontally at a predetermined rate thro an upper water layer, a UV stabilizer being present a second immiscible layer beneath said water layer; (b) pumping means for flowing said solution from the bot layer through the upper water layer to substantially only one surface of the sheet as the sheet is transported through the water layer; (c) nozzle means for applying the solution to said surfa (d) displacing means for directing a jet of water onto.t contacted surface to displace any residual solution such surface; and (e) means for removing the thus-treated sheet from said water layer. 22. Apparatus according to claim 21 wherein said jet mea includes a hollow perforated rod terminating in a slit through which said article is conveyed into the displacing zone.

Inventors: BURCHILL MICHAEL T, SILBERMANN JOSEPH, BURCHILL, MICHAEL, T., SILBERMANN, JOSEPH
Applicants: M & T CHEMICALS INC, M&T CHEMICALS INC.
Application year: 1987
Main classification: B05C3
IPC codes: B05C3, B05C9, B05D1, B05D7, C08J7