AU632990B2 - U.v. stabilized article and process for making same - Google Patents

Description

37 AU-AI-11575/88 WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau PCT INTERNATIONAL APPLICATION P 4ISlED HtDE HILTy COOPERATION TREATY (PCT) (51) International Patent Classification 4 1 4 I)I nati7 Pubcation Number: WO 88/ 04581 BOSC 3/12, BO5B 5/00 Al 1/18, 3/10 (43) International Publication Date: 30 June 1988 (30.06.88) (21) International Application Number: PCT/US87/03478 (72) Inventors; and Inventors/Applicants (for US only) SILBERMANN, Joseph (22) International Filing Date: 23 December 1987 (23.12.87) [US/US]; 8 Pendleton Place, Old Bridge, NJ 08857 (US).

BURCHILL, Michael, T. [US/US]; 145 Princeton Arms S, (31) Priority Application Numbers: 945,595 Cranbury, NJ 08512 (US).

945,757 076,629 (74) Agents: PARKER, Sheldon, H. et al.; P.O. Box 1104, Rahway, 076,630 NJ 07065 (US).

076,648 109,556 (81) Designated States: AT (European patent), AU, BB, BE (European patent), BG, BJ (OAPI patent), BR, CF (OAPI patent), (32) Priority Dates: 23 December 1986 (23.12.86) CG (OAPI patent), CH (European patent), CM (OAPI pa- 23 December 1986 (23.12.86) tent), DE (European patent), DK, FI, FR (European pa- 23 July 1987 (23.07.87) tent), GA (OAPI patent), GB (European patent), HU, IT 23 July 1987 (23.07.87) (European patent), JP, KP, KR, LK, LU (European patent), 23 July 1987 (23.07.87) MC, MG, ML (OAPI patent), MR (OAPI patent), MW, NL 16 October 1987 (16.10.87) (European patent), NO, RO, SD, SE (European patent), SN (OAPI patent), SU, TD (OAPI patent), TG (OAPI patent), (33) Priority Country: US US.

Parent Application or Grant Published (63) Related by Continuation With international search report.

US 945,757 (CIP) Before the expiration of the time limit for amending the claims Filed on 23 December 1986 (23 12.86) and to be republished in the event of the receipt o amendments.

(71) Applicant (for all designated States except US): M&T CHEMI- AUSTRALIAN CALS INC. [US/US]; One Woodbridge Center, Woodbridge, NJ 07095 15 JUL 1988 A.O. 18 AUG 1988 PATENT OFFICE (54) Title: U.V. STABILIZED ARTICLE AND PROCESS FOR MAKING SAME 4t- 6 2 /UN 12 II lm :rr

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

i 6- WO 88/04581 PCT/US87/03478 -1- STABILTZED ARTICLE AND PROCESS FOR MAKING SAME 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 industry. Such U.V. degradation causes discoloration, embrittlement and deterioration of the article. Accordingly, U.V. absorber compounds have been incorporated into such polymeric articles 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 can 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.

WO 88104581 PCrUS7/03478 -2- However, none of these surface treatments has been very successful commercially. Another surface method comprises laminating the surface of the polymer with a layer of a film-forming matirial containing the U.V. stabilizer. This lamination approach, unfortunately, suffers from the problems of incompatibilities between polymer, U.V. stabilizer, and the filmforming 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 serious problem.

The-swelling method is described by Katz, et al. in an article in the "Proceedings of the A.C.S. Div. of Org. Coatings and Plastics'" 1, p. 202-205 (197C), entitled "Ultraviolet Protection of Transparent PVC by Diffusion Coatings'. Kats uses 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 carrier, and, thereafter heating the treated polymer in air at an elevated temperature to drive the stabilizer below the surface of the polymer and to remove residual solvent. Under these process conditions, however, only a small amount of stabilizer is absorbed into the surface region. Furthermore, the dip method produces a product in which both sides of the sheet are modified with ultraviolet absorber.

Jochanan, in Israeli Patent No. 39037, published Nov. 1975, entitled and Oxidation-Proof Products from Organic Plastics and their Manufacture", describes various methods of applying a solution or suspension of an ultraviolet light absorber 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 amount tt-' 1 I 1 WO 88/04581 PCr/US87/03478 -3of residual stabilizer article, whereupon the streaky, hazy, and has and solvent is left on the surface of the modified surface is observed to be runs or pock- marks thereon.

Humphrey, in U.S. 4,146,658, describes a process for producing an ultraviolet light stabilized polycarbonate article by dipping the polycarbonate sheet into an impregnating solution consisting of a selected combination of ultraviolet absorber and solvent. However, all the disadvantages of the conventional dip 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 method is unsatisfactory for providing surface modified PVC sheets having a high degree of surface perfection.

Ambcrski, in U.S. 3,043,709, discloses an organic polymeric article having an ultraviolet light absorber-compound incorporated adjacent to the surface of the article. The article is 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 heated in air to 115°C. and above to drive the absorber below the surface of the film and to remove the solvent. These processes, however, are disadvantageous because they require heat-treatment 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.

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r t: i:: b i 1~ WO 88/04581 PCT/US87/03478 -4- Fanning, in U.S. 3,297,462, discloses a process for rendering polymeric films resistant to the deteriorating effects of sunlight by immersing them in a solution of a benzophenone stabilizer 1A 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 many 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 in air. This procedure, however, is ineffective because some stabilizer remains on the treated surface of the object, which gives a 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 surface, is flowed over the heated surface. There is no indication in this patent, however, that the method is applicable to polyvinyl chloride.

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WO 88/04581 PC/US8703478 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 not 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, Shkolnik, S. and Rcn, i. in Soc. Plast. Eng.,~ 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 surface modification by applying a stabilizer solution in air, vaporizing the solvent, and condensing the evaporated solvent for 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

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i wo 88/04581 PCT/US87/03478 I -6with 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 useful 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 perfection which is acceptable in commercial use.

Accordingly, there is a present noed 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. stabilized PVC siding article preferably should have only one side surface modified with the stabilizer material. Furthermore, the exposed surface of the sheet should be substantially free of residual stabilizer and solvent material, and the appearance and degree of surface perfection of the modified aide should be the same as jI that of the unmodified side of the sheet.- In addition, the surface modification should be effected in situ to lesson environmental hazards.

Accordingly, it is an object of this invention to provide a surface modified, U.V. stabilized resin sheet article having both sides exposed to the air, wherein the surface is substantially fully modified in situ with a stabilizing amount of a U.V. stabilizer 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 substantially the same as that of the unmodified side.

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WO 88/04581 PCT/US87/03478 -7- It is another object of this invention to provide a method for incorporating various types of ingredients such as ultraviolet light stabilizers, antioxidants, anti-static articles, 'especially those fabricated from thermoplastic polymers such as PVC, SUMMARY OF THE TNVENTION 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 of the sheet is substantially fully modified in situ with a stabilizing amount of an ultraviolet light stabilizer material, while 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 substantially the same as that of the unmodified side of the sheet.

The surface region of the sheet extends for a depth of up to 200 microns from the surface. This region is fully modified in situ in this invention with a stabilizing amount of a ultraviolet light stabilizer comprising at least 0.3 g/m 2 of the surface of the sheet, preferably 0.5 g. to 6.0 g./m 2 At least 70% of this stabilizing amount is present within the first 100 microns of the surface region, and 0.1 to 0.6 g/m 2 is present in the first microns from the surface.

In accordance with the invention, the U.V. stabilized resin 25 article is made by"a continuous process comprising immersing a resin body in a suitable liquid media, and-contacting the surface of the immersed body through the liquid with a solution of a ill pCrUS8703478 WO 88/04581 PCT/US8703478 S ultraviolet light stabilizer in a suitable organic solvent and displacing residual stabilizer and solvent from the modified surface in situ, both step being carried out without exposing the modtfiea surface to the atmosphere.

4 5 The method of this invention thus involves incorporating at least on ingredient in a polymer fabricated from a polymer by the steps of: immersing the article in a liquid; and 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 immiscible 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 incorporating at least one ultraviolet light stabilizer in the surface region of an article fabricated from PVC by the steps of: transporting the article through an aqueous media; 0 contacting substantially only one surface of the artide 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 is non-aggressive with the article which is immiscible with the solvent; and displacing any residual solution remaining on the contacted 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.

wo 88/04581 PC/US87/03478 -9- The surface region extends up to a depth of about 200 microns and the amount of stabilizer incorporated in this region will be at least 0.3, preferably 0.5 to 6.0 g/m 2 of the surface of the PVC sheet, with at least 70% of such amount concentrated in the upper 100 microns of the surface region. This most preferred embodiment involves: transporting the sheet substantially horizontally through an upper water layer, there being a methylene chloride solution containing 1-60 wt.% of the stabilizer present as a layer beneath the water layer; flowing the solution from the bottom layer through the upper water layer onto substantially only one surface of the sheet as the sheet is being transported through the water layer sucL that the solution is in contact with the surface for a period of time ranging from 1 second to 2 minutes; and thereafter directing a jet of water onto the contacted surface to 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 stabil-zed PVC article in accordance with the present inventicn.

Fig. 3 shows the untreated surface of the sheet of Fig. 2.

Fig. 4 shows the -odified surface of Fig. 2 after weathering for 15 mos. in sun!-ht.

IL WO 88104581 WO 8804581PCr/US87/03478 Fig. 5 shows the untreated surface of Fig. 3 after weathering for 15 mos. in sunlight.

Fig. 6 is a schumatic representation of an apparatus for making the U.V. stabilized article of Fig. 1 by a continuous process.

DET1A~TT=EDoSCRIP'TON OF THE TNV~flTTON Referring now to the drawings, Fig. 1 shows the U.V. stabilized 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 both of which are exposed to the air. Each% exposed side has respective surfaces SUTR and SUR'. Side S has a surface region SR extending from surface S to a depth of about 200 micr ons 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 pref erably 0. 5 to 6. 0 g/m of the surface of the sheet, and most preferably about 1.8 g/m2 thereof.

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/mz is present in the first 20 microns. Stabilizer is substantially absent in the interior or bulk of the sheet, and surface SUR also is substantially free of residual stabilizer.

The uniformity, appearance and degree of surface perfection of the modified surface SUIR is substantially the same as that of the unmodified surface SUIR'. 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 stabilizer.

115 1I WO 88/04581 PCr/US87/03478 -11- Referring now to Figs. 2-5, there are shown scanning electron micrographs of the modified surface SUR of the U.V. stabilizedresin sheet (Fig. its corresponding unmodified surface SUR' (Fig. the modified surface after weathering (Fig.

and the unmodified surface after weathering (Fig. These micrographs illustrate that the surface of the treated resin article herein (Fig. 2) has substantially the same degree of surface perfection as that of its untreated surface (Fig In addition, the treated surface (Fig. 4) remains substantially unaffeeted by exposure to ultraviolet light for a protracted period of time, while the untreated surface (Fig. under similar conditions of exposure, has deteriorated perceptibly.

The shaped resin body itself is obtained by general mechanical processing techniques known to those skilled in the art. I1lustrative of such mechanical operations are compression, injection, jet, transfer molding, vacuum forming, extrusion and the like. Such bodies can range from flexible sheets to rigid structural members. However, the invention is aimed particularly at articles which are plagued by U.V. degradation accompanying outdoor 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, including ABS(acrylonitrile/butadiene/styrene) rubber, polypropylenes, polyacrylates, pol'.yethacrylates and polyesters, e.g.

polyethylene terephthlate and polybutylene terephthlate.

The resin article itself may be transparent, translucent, opaque or pigmented.

WO 88/04581 PCT/US87/03478 -12- 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 solution of an ultraviolet light stabilizer in a suitable organic V solvent, and displacing residual stabilizer and solvent from the treated surface in situ. Suitable solvents are those which swell I the resin effectively and are immiscible with the organic solvent ilO and non-aggressive towards the resin.

More particularly, the preferred in situ method of maki±g 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 organic solvent through the water into contact with the surface of the sheet to be modifid 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 0 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 particular direction will depend on the respective densities of the liquid and organic solvent employed. It is preferred to use liquids such as water cr aqueous solutions thereof, and organic solvents having a density greater than water or such solutions. Accordingly, the preferred arrangement of liquid and solution is a two-layered system, where water is the upper layer, and the solu- 3 tion of stabilizer in the organic solvent is the lower layer.

1 WO 88/04581 PCT/Us87/03478 -13- The organic solvent is selected among solvents which do not mix with the liquid media; otherwise, the solvent would not reach the-resin sheet but would simply dissolve therein. Another consideration in choice of solvent is an empirical one, namely, the desire to impregnate the resin article with the U.V. stabilizer within a minimum contact time. This property depends on a number of factors, particularly the ability of the solvent to effectively swell the resin surface.

The system shown in Fig. 6 is a two-layered system in which the liquid phase is the upper layer and the stabilizer solution is the lower layer, and the resin sheet is oriented in an immersed state in the upper layer. In operation of such a twolayered 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 then falls off the sheet by gravity to return to the lower layer. The 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 having a high degree of surface perfection, and for ecological reasons.

The apparatus of Fig. 6 includes tank 1 about 3/4 full with water 2 as the upper layer. Stabilizer solution 3 of a U.V. absorber in an organic solvent, e.g. methylene chloride, is present as the lower layer therein. A continuous resin strip 4 of extruded polyvinyl chloride, for example, is fed into the upper layer at a predetermined rate from below roller 5, which is positioned below surface 6 of the water.

Further ahead of roller 5, in what is referred to herein as the "application zone" A, a series of applicator nozzles 7 are -oriented below the surface level 6 of the water with their WO 88/04581 PCr/US87/03478 -14orifices 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 thusapplied stabilizer solution remains on the surface of the strip whereupon the surface region is modified effectively with stabilizer. The length of time the stabilizer solution remains on the surface of the sheet within the application zone is refarred to herein as the "contact time* of the process, defined hereinafter.

Downstream of the applicator zone is a "displacement zone" 0 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 displacement zone is defined herein as the "contact time m 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 terminating in slit 11 through which strip 4 is conveyed into the displacement zone.

SA 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 E' 1 I- C WO 88/04581 PCT/US87/03478 roller pullers (not shown) are positioned outside the tank to move the strip at a predetermined speed through and out of the v tank, wiere it can be stored on a suitable take-up roll.

The equipment and procedure described above also is applicable to organic solvents having a density which is less than one, e.g. ethyl acetate, 2-pentanone, 3-pentanone. and the like.

For such organic solvents, the stabilizer solution would constitute the top layer and water the bottom layer. The stabilizer solution then would rise in the water to contact the resin sheet from the underside, thereafter passing upwardly.

The ingradients which may be incorporated into the articles fabricated from such polymers include ultraviolet light stabilizers (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 with the solvent of choice. Of course, the ingredients must be sufficiently 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.

PREPARATTON OF U.V. STABILIZED ARTICLE OF INVENTTON Exammle 1 A solution of 7.5% by weight of Cyasorb U.V. 5411 stabilizer (a trademark of American Cyanamid Co.) in methylene chloride was applied onto the upper surface of a horizontally supported, f \V\ 'I 1' WO 88/04581 PCT/US87/03478 -16moving polyvinyl chloride resin strip immersed in water at The applicator nozzles were directed vertically towards the upper 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 bottom of the tank. The contact time was 24 seconds. Downstream of the applicator zone, a jet of water was applied to the treated surface to displace residual stabilizer and solvent still remaining on the treated surface. The U.V. stabilized article then exited IO the tank and was wound onto a take-up roll.

PROPERTIES OF U.V. STABTILZED ARTTC'~ The U.V. stabilized article prepared in Example 1 was microtimed into 20 ricron 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 high pressure liquid chromatography (HPLC) analysis. The results are given in Table I below.

I Li li a 1 t J CONCENTRATION PROFILE OF STABb ER IN SURFACE REGION AND BUILK OF siqxT

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Sect ion (microns) of Stabilizer In Section Amt. Of Stabilizer (g/m 2 Stabilizer at 2.42 %of Total Stabilizer at Given DejLIL_ 0-20 20-40 40-60 60-80 80-100) I410- 120 120-140 140-161) 160-180 180-200 2.30 1.91 1.70 1.47 1.40 1.30 1.17 0.62 0.32 0.14 0.64 0.52 0.47 0.40 0.38 0.36 0.32 0.17 0.09 0.04 UVY Stabilizer Soluto~n Stabilizer Cyasorb IJV 5411 (Trademark of the American Cyanamid Corp.) Chemical Name: 2(2' hydroxy 5't octyiphenyl) benzotriazole Soluion~ by wt. of stabilizer In methylene chloride Progess Conditions Temperatute 25 0

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Contact tiam 24 see.

Sheet speed 1.5 ft./min.

Thickness o[ PVC Sheet 1300 microns Composition of PVC sheet 0% T 1 0 2 solvent.

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WO 88104581 PCrfUS87/03478 -18- The test results in Table I show that 3.39 g/m 2 of the stabilizer 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 Smicronsb'f 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 I streaks of soliI material thereon, and retained to original planarity and hardness.

Example 3 Following the procedures of Examples 1 and 2, various-concentrations 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 UV.

light under these different process conditions is presented in Table II as changes in yellowness index )rAYI values.

The LYI values were determined upon accelerated U.V. exposure tests, according to ASTM G 53-84. The change from initial to final YI is designated AYI. A AYI value of zero (or minus) indicates minimal or complete absence of yellow; positive/YI values evidences increasing yellowness caused by U.V. exposure.

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Effect of Concentration of Stabilizer and Contact Time on Amount of Stabilizer Incorporated into Surface Reaion of Sheet and its U.V. Stability Stabilizer Amount of Sample Cone. Contact Time Stabilizer No. wt./vol) (sec.)fq/mi 1 2 30 1.78 2 3 30 2.67 3 3 60 3.38 4 5 15 5.16 5. 30 5.34 6 5 60 7.12 7 10 15 11.22 8 10 30 9.80 9 10 60 16.86 Control 0 0 0 aYI U.V. exposure (in weeks) 1 4- 1.3 4.1 -2.9 2.2 -0.4 -1.0 0.3 0.0 1.2 -0.8 0.7 -1.1 -1.0 0.9 -0.6 -1.4 29

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The results in Table II show that application of stabilizer solution having a concentration of 2 wt.% for 30 sec. provides an amount of stabilizer in the surface region of the sheet sufficient to afford excellent protection against U.V. light. At concentrations up to 10 wt.% of stabilizer, and for contact times up 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 cotained to determine the effect of the concentration of the stabilizer at different depths within the surface region, particularly within the first 20 microns, upon the changes in yellowness index.

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WO 88/04581 S88/04581 PCT/US87/03478 These experiments demonstrate that excellent weatherability is obtained when at least 0.1 g/m 2 preferably 0o1 to 0.6 g/mn of stabilizer is present within the first 20 microns from the surface of the sheet; and at least a total of 0.3 g/m a preferably 0.3 to 6 g/m a of stabilizer is present within the surface region of the sheet.

As described, the preferred liquid media in the method used 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 "incompatible" is defined herein to mean a liquid having a solubility of no more than about 15 percent by weight in the organic solvent and at ambient temperature and pressure. Such liquids include alkanols and other water miscible liquids.

Similarly, the solvent in the stabilizer solution should be '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 include 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 hydrcarbcns include methylene chloride, chloroform, 1,2-dichloroethane, 2-chloro-2-methylpropane and like chlorinated hydrocarbons. Exemplary ketones are 2-pentanone, 3-pentanone, 2hexanone, 2,4-pentanedione and the like. Suitable ethers include diethyl ether, diprcpyl ether, dimethoxy ethane, furan,

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j WO 88/04581 tetrahydropyran and the like. Mixtur ganic solvents can also be used. The are methylene chloride, 1,2-dichioro.

pentanone and 3-pentanone, and mixtur K 5 Suitable U.V. stabilizers includ available materials: Cyasorb U.V. 9: 2-hydroxy-4-meth of American Cyanamid) Cyasorb U.V. 531: 2-hydroxy-4-n- (Trademark of American Cyanamid) Cyasorb LT.V. 5411: 2(2'-hydroxybenzotriazole (Trademark of American Tinuvin-P: 2(2'hydroxy-5'-mathyl (Trademark of Ciba-Geigy) Tinuvin 326: 2-(3't-butyl-20-hyd chloraonzotriazole (Trademark of cib Sanduvor VSTJ: 2-ethyl-2-ethoxyan Corp.) Tinuvin 14,4 and 770: hindered am (Trademark of Ciba Geigy for HALS) H Irgastab 2002: a nickel phosphat Ciba-Geigy) The following is a partial list zophenones and triazoles which are su use herein.

2, 2'-dihydroxybeizphenone 2,2,4,4' -tetrahydroxybenzophenone 2,2' -dihydroxy-4, 4 -dimethoxybenzophe LI 2,2' -dihydroxy-4, 4 -diethoxybenzophen 2,2 '-dihydroxy-4, 4'-dipropoxybenzophe I IfA q A -A A I 4N PCr/US87/03478 es of mutually miscible orpreferred organic solvents thane, ethyl acetate, 2as of these solvents.

e the following commercially oxybenzophflone (Trademark octoxybenzophanone 5' -t-octylphenyl) Cyanamid) phanyl) benzotriazole xoxy-5 '-methylphenyl) a-Geigy) ilide (Trademark of Sandoz mne light stabilizers a (Trademark of of these and other benitable U.V. stabilivers for none Lone ~none ione izophenone I -x I- d.

2, 2'-dihydroxy-4-methoxy-4 '-ethoxyben W088/4581PCT/US87/03478 '1 -22-

I'

'4 4, Ii h~ ~2 0 2,2'-dihydroxy-4-mothoxy-4'-propoxyberizophenone 2-hydroxy-4, 4' 2-hydroxy-4 -ethoxy-4 '-methylbenzophenone 2-hydroxy-4 -ethoxy-4 '-ethylbenzophenone 2 -kydroxy-4 -etboxy-4 '-propylbenzophenone 2 -hydroxy-4 -ethoxy-4 '-methoxybenzophenoie 2-hydzroxy-4,4-diethoxybeflzophonone 2 -hydroxy-4-ethloXy-4 '-propoxybenzopheione 2-hydrcxy-4-ethoXy-4' -butoxybenzophenon.

2-hydroxy-4-.thoXy-4' -chlorobenzophenone 2 -1ydzroxy-4-athoxy-4; -bromobenizophenone 2- (2 -hydroxy-5' -methyiphenyl) benzotriazole 2- 2- (2 -hydroxy-3 '-methyl-5-t' -butyiphenyl) benzotriazole 2- (2 '-hydroxy-5' -cyclohexyiphenyl) benzotiazo1..- 2- (2 -hydroxy-3 5' -dimethyiphenyl) benzotriazoJA.

2- (2 '-hydroxy-5 -t-butylphonyl) -S-chlorobenzotriazole anid 2-(2'-hydroxy-3 '-di-t-butylphenyl)benzotriazole 2,2' -dihydroxy-4 -methoxy-4' -butoxyberizophenone 2,2' -dihydroXy-4 -ethoxy--4 -propoxybenzophenone 2,3 '-dihydroxy-4 ,4 '-dimethoxybenziophenone 2,3 '-dihydroxy-4-methoxy-4'-butoxybenzophenone 2,3' -dihydroxy-4 2-hydroxy-4 5 -trimethoxybeizophenorie 2-hydroxy-4, 4,6, '-tributoxybeizophenone 2-hydroxy-4-ethoxy-2, 4 -dibutylbeizophenone 2-hydroxy-4-propoxy-4 -dichioroberizophenone 2-hydroxy-4-propoxy-4' '-dibromoberizophenone 2, 4-dihydroxybenzcpheione 2-hydroxy-4 -metho xyben ophenorie 2-hydroxy-4-ethoxybenzophenone 2-hydroxy-4 -propoxybenzophenone 2-hydroxy-4-butoxyben zophenohe 2-hydroxy-4-methoxy-4 'methylberizophenone WO 88/04581 L-yr~-- 4 2-hydroxy-4-mi 2-hydroXY-4-m' 2-hydroxy-4-mi 2-hydroxy-4,4 2-1iydroxy-4-m 2 -hydroxy-4, 4 2-hydroxy-4,4 2 -hydroxy-acel The profi ticle of thej process temps~ jr may be used, certain usefu with increasi process tempe solvents. Si~ resin only mo fective for ii the surface ri ture.

Although herein has on~ it is underst directing jet 1 the resin she PCT/US87/03478 -23mthoxy-4' propylbenzophenone othoxy-4'butylbenzophenone ethoxy-4' -t-butylbenzophenone ethoxy-4' -chloraoenzophenone athoxy-2' -chlorobenzophenone athoxy-4 '-bromobenzophenone 1-dimethoxybenzophenone '-dimethoxy-3 -methylbenzophenone '-dimethoxy-3 -methylbenzophenone '-ethylbenzophenone tophenone erred temperature for making the U.V. stabilized arpresent invention is ambient temperature. However, ratures lower and higher than ambient temperature if desired. For example, the water solubility of L organic solvents, e.g. ethyl acetate, decreases aig temperature. Thus, it may be advantageous to use ratures higher than ambient temperature for such nilarly, organic solvents which swell a particular destly at room temperature can be rendered qu~ite efnfusion of the rem~uisite amount of stabilizer into egion of the resin by raising the treatment temperathe pre-ferred embodiment of the stabilizer article ly on~e side of the article modified with stabilizer, ood that both sides may be modified, if desired, by s of stabilizer solution towards both surfaces of et.

wo 88/04581 The article her such as a compound s sulfate or carbonate trioxide, magnesium sulfate and calcium Titanium dioxid tion in polyvinyl ch titanium dioxide is adverse effects of U persing or scatterin function of titanium that colored article colorants therein in PCT/US87/03478 -24sin may or may not include a white pigment elected from an inorganic metallic oxide, for example, titanium dioxide, antimony oxide, silicon dioxide, zinc oxide, barium carbonate.

e, which is a white pigment, has a dual funcloride articles. The first function of to stabilize polyvinyl chloride against the radiation by absorbing, reflecting, disg in the incident U.V. energy. The second dioxide is to render the article opaque so s may be produced, if desired,, by including an amount sufficient to overcome the white sent.

titanium dioxide pre Unfortunately, the amount of titanium dioxide necessary for effective U.V. stabilization, about 12 phr, precludes deep coloration of such articles. In fact, only colored articles of pastel shades can be obtained; deep shades of brown, blue and maroon, for example, are not readily attainable. Accordingly, it would be advantageous to provide U.V. stabilized polyvinyl chloride articles characterized by the substantial absence of any titanium dioxide therein.

I

Of course, the absence of titanium dioxide is accompanied by the loss of its U.V. stabilization function. Therefore, for such articles, it is necessary to provide an alternative means of U.V.

stabilization for such articles. Since titanium dioxide is such a cheap raw material, it is uneconomical to substitute an effective, but high priced organic U.V. stabilizer, such as a benzophenone or benzotriazole, in place of titanium dioxide.

i/ WO 88/04581 PCTIUS87/03478 Furthermore, since photodegradation is known to be surface phenomenon, bulk incorporation of such organic U.V. stabilizers is .infticient because the stabilizer is present substantially in the interior of the article, where it does not prevent surface photodegradation.

Suitalbly titanium dioxide can be absent or, if present herein, is included in an amount of 0.5 phr, preferably up to 8 phr, and optimally, about I to 6 phr, with or without a colored 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 understood that other modifications may be made within the'preview of the invention. For example, the solution of the modifier ingredient in a solvent may be applied to a resin article which passes through'the solution, with the displacing liquid being present either above the solution, or in side-by-side relationship. In the latter embodiment, the displacing liquid need not be necessary immiscible with the solution and its solvent. These and other modifications will be apparent to those skilled in the art.

II

I

Claims (26)

1. A method of incorporating a modifying substance into a polymeric article by contacting a surface of the polymeric article with a solution of the substance in a solvent such 'hat the substance penetrates into said surface, characterized in that the article and solution are contacted while said surface of the article is immersed in an immersion liquid which is non- aggressive to the polymeric article and immiscible with the solution

2. A method according to claim 1 further comprising displacing residual solution from the surface of the article using a displacing liquid after the contacting.

3. A method according to claim 2 in which the displacing comprises directing the displacing liquid under pressure against the surface of the polymeric article while the article remains immersed in the immersion liquid.

4. A method Eccording to claim 2 or claim 3 in which the immersion liquid and the dispiacing liquid are the same. A method according to any one of the preceding claims which is a continuous process in which the polymeric article is conveyed continuously through a tank containing the immersion liquid the solution being contacted with the surface of the polymeric article at an immersed application zone in the tank.

6. A method according to claim 5 in which displacing liquid is directed against the surface of the polymeric article at a displacement zone in the tank to displace residual solution from it.

7. A method according to any one of the preceding claims in which ((m :1 0 4 27 only one side of the article is contacted with the solution

8. A method according to claim 7 in which the article is in sheet form, and the solution is applied on an upwardly facing surface thereof.

9. A method according to any one of the preceding claims in which the immersion liquid is aqueous. A method according to any one of the preceding claims in which the solvent of the solution is capable of swelling the surface of the polymeric article with which it is contacted.

11. A method, according to any one of the preceding: claims in which the substance to be incorporated is a UV stabilizer, an antioxidant, an anti-static agent or a pigment.

12. A method according to claim 11 in which the substance to be incorporated is a UV stabilizer and the polymeric article is of polyvinyl Ij chloride.

13. A surface-nodified polymeric article obtained a method according to any one of claims .I to 12; having'a rpodifyin, substance incorporated into a surface region thereof characterized in that the surface of the polymeric article at said surface region is substantiallyfree of, and unmarked by, residual modifying substance.

14. An article according to claim 13 which is in sheet formr An article according to claim 14 which has a .surfade region (8) incorporating the modifying substance only on one side thereof.

16. An article according to any one of claims 13 to 15 which is of L_ IA, 11 U i' i t i 28 polyvinyl chloride.

17. An article according to any one of claims 13 to 16 in which the modifying substance comprises a UV light stabilizer.

18. An article according to any one of claims 13 to 17 in which the surface region is up to 200pm in depth, and has at least 0.3g/m 2 of the modifying substance.

19. An article according to claim 18 in which the surface region has at least 0.5 to 6.0g/m2 of the modifying substance. An articlW-according to claim 17 in-which at-least 70% of the modifying substance is present in the first 100 im depth of the surface.

21. An article according to any one of claims 17 to 19 in which at least 0.1g/m 2 of the depth modifying substance is present in the first 20pm depth from the surface.

22. An article according to clainr21 in which ateast 0.3g/m 2 of the modifying substance is presentin thefirst.20pril-depth frm the. surface

23. An article according to any one of clainms 13 to 22 in which the modifying substance comprises a pigment.

24. dioxide. An article according to claim.23 in which the pigment is titanium

25. Apparatus for incorporating a modifying substance into a polymeric article by a method according to claim 1, comprising a tank holding an immersion liquid which is non-aggressive to the polymeric article; 29 means for positioning the polymeric ,rticle on a processing path in said immersion liquid such that a surface of the polymeric article is immersed at an application zone a supply of a solution of the modifying substance in a solvent which is immiscible with the immersion liquid and means for applying the modifying substance solution from the supply thereof to the immersed surface of the polymeric article at the application zone

26. Apparatus according to claim 25 for carrying out a continuous process, with means 12) for moving a continuous said polymeric article (4) along the processing path through the immersion liquid

27. Apparatus according to claim 26 comprising a displacement zone on the processing path downstream of the application zone and means 10, 11) for displacing residual modifying substance from the surface of the polymeric article at the displacement zone

28. Apparatus according to claim 25 or 26 comprising means 11) for directing a jet of displacement liquid against the surface of the polymeric article to displace residual solution therefrom.

29. Apparatus according to claim 28 in which the displacement liquid and the immersion liquid are both aqueous. Apparatus according to any one of claims 25 to 29 in which the supply of solvent is contained in the tank and covered by the immersion liquid i 0.% CJ2 0 coo 0 z 0 C4 4W ca cc C~ CL do 0) C E- aU E .Oil 0 1 P~~ 10.1O ii 0PI i

31. Apparatus according to any one of claims 25 to 30 in which the modifying substance solution is applied to the top side of the polymeric article DATED this 5th day of November, 1992. M &T CHEMICALS INC WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA 1