AU710738B2

AU710738B2 - Composition and method for treating a vinyl surface against environmental exposure

Info

Publication number: AU710738B2
Application number: AU47545/96A
Authority: AU
Inventors: Neal K Hutchinson; James R. Tucker
Original assignee: Armor All Products Corp
Current assignee: Energizer Auto Inc
Priority date: 1995-01-06
Filing date: 1996-01-04
Publication date: 1999-09-30
Anticipated expiration: 2016-01-04
Also published as: GB2311238B; GB9714107D0; GB2311238A8; AU4754596A; WO1996021696A1; DE19681106T1; JPH10512317A; GB2311238A

Description

WO 96/21696 PCT/US96/00423 .1.

COMPOSITION AND METHOD FOR TREATING A VINYL SURFACE AGAINST ENVIRONMENTAL

EXPOSURE

FIELD OF THE INVENTION This invention relates to a composition and method for topical treatment of plastics for protection against environmental exposure and deterioration caused by ultraviolet light.

BACKGROUND OF THE INVENTION Polyvinyl chloride (PVC) protectants, which have been commercialized over the years, are often comprised of solutions or emulsions of polydimethyl siloxane and various other additives such as those described in U.S. Pat. Nos. 3,956,174 and 5,183,845. These products are commonly used for automotive interior and exterior PVC (vinyl) parts as well as household vinyl products to improve the appearance of the vinyl by providing gloss, and to protect the vinyl by improving durability and water repellency. While these products provide temporary improvements to vinyl surfaces, testing has shown that single applications of these products do not effectively protect vinyl from extended weathering and exposure to ultraviolet (UV) light.

In order to provide a treatment for vinyl surfaces to protect from UV light, UV absorbers (UVAs) have been incorporated into silicone-based protectants, for example, as described in Canadian Patent No. 1,176,828. However, it has been found that these products do not provide adequate protection from UV exposure.

U.S. Pat. No. 4,728,540 discloses the use of plasticizers for the delivery of active ingredients to vinyl films. The formulations described in this patent are designed to allow the active ingredient to be incorporated into the interior of the vinyl product.

After treatment, the vinyl must remain undisturbed for extended periods of time, up to thirty days, until the formulation is fully absorbed. Therefore, these formulations are not suited for uses where it is desired to use the vinyl within a relatively short time period after treatment, or where it may be aesthetically unacceptable to have material remaining on the surface of the vinyl.

Efforts have been made to manufacture vinyl products that are resistant to the deleterious effects of ultraviolet light by incorporating additives such as UVAs and/or hindered amine light stabilizers (HALS) directly into the vinyl resin durin~g the manufacturing process. For example, the use of hindered amines in the manufacture of a variety of organic polymers is described in U.S. Pat. Nos. 4,472,547, 4,547,537, and 5,241,067. The hindered amines are incorporated into the organic polymers prior to the manufacture of shaped articles therefrom. Hindered amines have also been incorporated into polyurethane and acrylic coatings used on painted automotive surfaces, to prevent degradation of the coating itself. However, these additives do not afford the long-term protection to the substrate that is needed for vinyl products that are constantly exposed to ultraviolet light, such as automobile upholstery, vinyl cartops, etc.

at alow ThAneo dvantageously, h neto provides copstian method for trating alreadyodcttht rmaufcttued iny t rotetvnyld surfaces frothe efhorfte ofutravioetgt.

Ahs n te dvantageouslyatre o the invention prvdsamthdowraingavl prcoducppet t low the skle*nteatfrmtefloigdtalddsrpinan peddcam P:\OPER\AXD\1914507.RS1 26//99 -2A- According to one aspect of the present invention, there is provided a composition for the topical protection of already manufactured vinyl comprising from 0.01 to 20 weight percent of at least one hindered amine light stabilizer, and a delivery vehicle comprising from 0.2 to weight percent of a vinyl plasticizer, and from 50 to 99.8 weight percent of a protectant base comprising an active agent selected from the group consisting of polydimethyl siloxanes, cyclomethicones and phenyl dimethicones.

According to another aspect of the present invention, there is provided a method of treating a vinyl surface comprising applying to said surface a coating of a composition comprising from about 0.01 to 20 weight percent of at least one hindered amine light stabilizer dispersed in a delivery vehicle comprising from 0.2 to 50 weight percent of a vinyl plasticizer and to 99.8 weight percent of a protectant base comprising an active agent selected from the group consisting of polydimethyl siloxanes, cyclomethicones and phenyl dimethicones.

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3 DETAILED DESCRIPTION OF THE INVENTION The present invention provides a composition for topical application to already manufactured vinyl. The composition protects vinyl from the deleterious effects of exposure to ultraviolet light.

The composition comprises at least one hindered amine light stabilizer that has been solubilized or emulsified in a suitable delivery vehicle. Hindered amine light stabilizers (HALS) are a well known class of compounds known to prevent and retard the degradation of polymers in which they are incorporated. HALS do not absorb UV light, but are believed to act as light-stable free radical scavengers. It is believed that the HALS oxidize to form nitroxy radicals which, in turn, react with other free radicals. The complete reaction mechanism is not clearly understood, however theories assume a cyclical process that regenerates the nitroxyl species, *fl.

accounting for the efficacy and longevity of these materials.

":HALS are commercially available from a variety of S sources, including but not limited to Ciba-Geigy 25 Corporation Tinuvin 123, 292 or 440L (all RTMs)), Sandoz Chemical Corporation Sanduvor 3055, 3056 or 3058 (all RTMs)) and BASF Corporation Uvinul 4050 H, or 5050 H (all RTMs)). The formulas for various HALS are provided in U.S. Patent 30 Nos. 5,241,067, 4,472,547, and 4,728,540, all incorporated herein by reference. Prior to the present invention, the only known method of utilizing HALS for UV protection was by the incorporation of HALS into the material to be stabilized. There is no suggestion from the prior art that HALS can provide any benefit at the surface of a vinyl product. Surprisingly, it has been discovered that a topical treatment of the 3asurface of already formed vinyl products with HALS can result in increased protection from the effects of ultraviolet light.

The specific chemical name for Tinuvin 123 is decanedioic acid bis [2,2,6,6-tetramethyl-l- (octyloxy)-4-piperidinyl] ester.

The specific chemical name for Tinuvin 292 is bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

HALS are extremely viscous. Therefore, they are diluted with a delivery vehicle that can reduce viscosity to suitable levels and that detackifies the HALS, thus allowing .e S*

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4 for a non-objectable surface feel soon after application, when applied in appropriate amounts.

Thus, after treatment with the compositions of the invention, the vinyl surface can be subject to normal use contact usually within 30 minutes after application vinyl upholstery can be used). The composition can comprise from about 0.01 up to about weight percent HALS. At levels above 20% HALS it becomes difficult to reduce the viscosity and detackify the system. However, cost is a factor and at levels greater than about 5 weight percent HALS there is not a significant increase in benefit with increasing amounts of HALS. The composition preferably comprises from about 0.01 to about 5 weight percent HALS, more preferably about 0.06 to about 3 weight percent HALS, and even more preferably from about 0.01 to about 1 weight percent HALS. The composition may comprise from about 0.2 to about 2 weight percent

HALS.

The delivery vehicle can be any material or combination of materials that can dissolve or uniformly disperse the HALS, and be applied to the plastic without physically or chemically attacking it.

25 Various materials including, but not limited to, polydimethyl siloxanes, cyclomethicones, phenyl dimethicones, vinyl plasticizers, and polymers used in *coatings such as polyurethanes and polyacrylates, meet these criteria and can be used as delivery vehicles 30 either as solutions, solutions in other volatile carriers, or emulsions. The composition of the delivery vehicle may be selected to provide other specific attributes or benefits, including but not limited to shine, color enhancement, ozone protection, cleaning, clarity, etc.

4a Plasticizers are particularly suitable because they facilitate the handling of the HALS by readily cutting viscosity and since they comprise components of vinyl and they are nonreactive with the vinyl. Particularly preferred plasticizers are dioctyl adipate and di-nhexyl azelate. The composition may comprise HALS with the balance being the plasticizer. In a preferred embodiment, the delivery vehicle also comprises a silicone protectant base, for example an aqueous solution or emulsion of polydimethyl siloxane, which is known to condition and impart gloss to vinyl surfaces. A preferred delivery vehicle comprises from about 0.2 to about 50 weight percent plasticizer and about 50 to about 99.8% protectant base. A particularly preferred delivery vehicle comprises from about .5 to about 5 weight percent plasticizer and about 95 to about 99.5 weight percent protectant base.

SVarious other additives can be incorporated into the delivery vehicle that impart additional properties to r, 20 the composition. For example

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c, 5 antioxidants and UV absorbers can also be added. UV absorbers may be used in amounts of from about 0.01 to about 5 weight percent. Antioxidants and UVA absorbers TINUVIN 384, TINUVIN 328 and TINUVIN 1130 (all RTMs), available from Ciba-Geigy Corporation) are preferably used in amounts ranging from about 0.05 to about 5 weight percent. The specific chemical names for Tinuvins 384 and 328 are 3-(2H-benzotriazol-2-yl)- 5-(1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid and 2-(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole respectively.

The composition of the present invention provides effective protection of vinyl substrates from the effects of weathering and specifically UV irradiation.

The composition can be applied by spraying, with either a pump or aerosol, or by wetting a cloth, sponge or brush with the composition and wiping the surface to be treated. It is desirable to apply a S: 20 sufficiently thin coating of the composition with no excess fluid remaining on said vinyl surface so that the vinyl surface can be used for its intended purpose within one hour after treatment, and preferably within minutes after treatment. Any excess fluid can be removed by wiping with a dry cloth. Typically, the composition is applied at a rate of about 0.05 cc composition per 100 square cm of vinyl surface to e ;about 0.5 cc per 100 square cm. Preferably, about 0.05 to about 0.2 cc composition is applied per 100 square 30 cm of vinyl surface. When HALS is incorporated directly into vinyl products during manufacturing it is used at amounts of about 0.15% relative to the total weight of the vinyl. Topical application of HALS uses significantly less HALS yet is surprisingly more effective. Thus, the present invention provides the additional benefit of being more cost effective.

In order that the invention described herein may be more fully understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention in any manner.

Example 1: Compositions comprising HALS in a silicone protectant base/plasticizer delivery vehicle The 9 formulas shown in Table I were prepared by adding hindered amine light stabilizers and other additives to a polydimethyl siloxane protectant base (which is an emulsion comprised primarily of polydimethyl siloxane, water, and emulsifiers). The following additives were used: hindered amine light stabilizers (Tinuvin 123 and 292 (both RTMs)), ultraviolet absorbers (Tinuvin 384, 328 and 1130 (all RTMs)), antioxidants (Cyguard AO-711 (RTM)), *oo* WO 96/21696 PCTIUS96/00423 -6and plasticizers (dioctyl adipate). Amounts are in percent by weight, the protectant base forming the balance of the composition. All of the additives, which are liquids, were mixed together with moderate agitation until homogeneous. The additive mixture was then added to the liquid protectant base and mixed for 30 minutes with moderate agitation, forming an emulsion.

TABLE I #1 #2 #3 #4 #5 #6 #7 #8 #9 Tinuvin 123 0.20 0.25 0.06 Tinuvin 292 0.54 0.35 0.29 0.27 0.27 1.70 Tinuvin 384 0.10 0.18 0.24 0.09 0.09 Tinuvin 328 0.13 0.088 0.15 Tinuvin 1130 3.30 Cyguard AO-711 0.10 Dioctyl Adipate 1.00 2.00 1.00 1.00 1.00 1.00 1.00 1.00 5.00 Protectant Base to to to to to to to to to 100% 100% 100% 100% 100% 100% 100% 100% 100% RATING 3 3+ 3 3 2 3 3 3 4 Formulas 1 to 8 were tested for their ability to protect vinyl from weathering and UV exposure. Various commercial protectant bases without any of the above additives were used as controls. The compositions were applied to vinyl samples cut from instrument panel skins that were obtained from United Technologies, a supplier of instrument panel skins to the domestic automotive industry. The compositions were applied at a rate of 0.1 cc per 15 square inches of vinyl surface, a rate determined by observing the usage of vinyl protectants by consumers on instrument panels.

The treated vinyl panels were then exposed to weathering under the conditions of the Society of Automotive Engineers (SAE) Method J-1885, Accelerated Exposure of Automotive Interior Trim Components using a Controlled Irradiance Water Cooled Xenon-Arc Apparatus. This is a standard method utilized by U.S. automakers to project resistance of interior vinyl parts to weathering. The samples were observed for signs of degradation. After 1300 kilojoules of exposure (about 700 hours), obvious visual degradation of the control samples was observed, the vinyl had begun to blacken extensively. The samples treated with HALS-containing protectants showed little or no blackening.

WO 96/21696 PCTUS96/00423 -7- After visual inspection, Formulas 1 to 8 were rated for their protective abilities according to the following values (shown in Table I).

0 no protection, blackening of vinyl 1 some protection, fair, slight blackening 2 good protection, no blackening, some discoloration 3 very good protection, slight discoloration 4 excellent protection, no change from unexposed.

Another set of samples were similarly treated and exposed. Elasticity of the samples was measured after 900 kilojoules of exposure (about 500 hours). The samples treated with HALS-containing protectants had significantly less loss of elasticity 'than untreated samples or those treated with control products. For reference, the Ford Motor Company specifies that instrument panel plastic materials be subject to the conditions of SAE Method J-1885 for up to 1993 kilojoules exposure (about 1000 hours).

Formula 9 was tested on automotive interior upholstery vinyl under the conditions of J-1885 and compared with no treatment and treatment with protectant base. Vinyl treated with Formula 9 showed no change from unexposed material after approximately 2000 kilojoules exposure, and scored a 4 in the scale described above.

The protectant base-treated vinyl scored a 1, and the untreated vinyl scored a 0.

Example 2: Compositions comprising HALS in solution :Formulas 10 and 11 shown in Table II are representative ccnpositions 2 corprising HALS in solution.

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a *5 25 cycome,.con* 78.65 Polydimethyl Siloxaee. 35C 20.00 10.00 Cstk Pheiyl Dimethtucorw 10.00 Hydrogenated Polyisobutene__ Ooctyl Adipate 1.00 Oi-n-hexyl Azelate 4. HALS I0.25 UVA 0-.10 0-15 -8- Example 3: Composition comprising HALS in an emulsion Formula 12 shown in Table III is a representative composition comprising HALS in emulsion systems.

TABLE III #12 Water to 100% Emulsifier as req'd Cyclomethicone 5.00 Polydimethyl 10.00 siloxane, 350 Cstk Di-n-hexyl azelate 10.00 HALS 0.25 9

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Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.

Claims

1. A composition for the topical protection of already manufactured vinyl comprising from 0.01 to 20 weight percent of at least one hindered amine light stabilizer, and a delivery vehicle comprising from 0.2 to 50 weight percent of a vinyl plasticizer, and from 50 to 99.8 weight percent of a protectant base comprising an active agent selected from the group consisting of polydimethyl siloxanes, cyclomethicones and phenyl dimethicones.

2. A composition as claimed in claim 1 comprising from 0.01 to 5 weight percent of at least one hindered amine light stabilizer. S4

3. A composition as claimed in claim 1 comprising from 0.06 to 3 weight percent of at least one S. 20 hindered amine light stabilizer.

4. A composition as claimed in claim 1 comprising from 0.1 to 1 weight percent of at least one hindered amine light stabilizer.

5. A composition as claimed in claim 1 comprising from 0.2 to 2 weight percent of at least one hindered amine light stabilizer. 4 30

6. A composition as claimed in any one of the preceding claims wherein said hindered amine light stabilizer is selected from the group consisting of decanedioic acid bis(2,2,6,6- tetramethyl-l-(octyloxy)-4-piperidinyl) ester and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. 10

7. A composition as claimed in any one of the preceding claims wherein said delivery vehicle comprises from 0.5 to 5 weight percent of a vinyl plasticizer and from 95 to 99.5 weight percent of a protectant base comprising an active agent selected from the group consisting of polydimethyl siloxanes, cyclomethicones and phenyl dimethicones.

8. A composition as claimed in any one of the preceding claims wherein the vinyl plasticizer is selected from dioctyl adipate and di-n-hexyl azelate

9. A composition as claimed in any one of the preceding claims which further comprises an ultraviolet absorber.

10. A composition as claimed in claim 9 which 20 comprises from 0.01 to 5 weight percent of an Sultraviolet absorber.

11. A composition as claimed in claim 9 which comprises from 0.05 to 5 weight percent of an S 25 ultraviolet absorber.

12. A composition as claimed in any one of claims 9 ov* 2 to 11 wherein said ultraviolet absorber is selected from 3-(2H-benzotriazol-2-yl)-5-(1,1- 30 dimethylethyl)-4-hydroxy-benzenepropanoic acid and 2-(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole.

13. A composition as claimed in any one of the preceding claims which further comprises an antioxidant. P:\OPER\AXD\1914507.RS 26/7/99 -11-

14. A composition as claimed in claim 13 which comprises from 0.05 to 5 weight percent of an antioxidant.

A composition for the topical protection of already manufactured vinyl substantially as hereinbefore described with reference to any one of examples 1, 2 or 3.

16. A method of treating a vinyl surface comprising applying to said surface a coating of a composition comprising from about 0.01 to 20 weight percent of at least one hindered amine light stabilizer dispersed in a delivery vehicle comprising from 0.2 to 50 weight percent of a vinyl plasticizer and 50 to 99.8 weight percent of a protectant base comprising an active agent selected from the group consisting of polydimethyl siloxanes, cyclomethicones and phenyl dimethicones.

17. The method of claim 16 wherein said composition comprises from 0.2 to about 2 15 weight percent of at least one hindered amine light stabilizer.

18. The method of claim 16 or 17 wherein said hindered amine light stabilizer is selected from the group consisting of decanedioic acid bis [2,2,6,6-tetramethyl-l-(octyloxy)-4- piperidinyl] ester and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

19. The method of any one of claims 16 to 18 wherein said delivery vehicle comprises from 0.5 to 5 weight percent of said vinyl plasticizer, and 95 to 99.5 weight percent of said protectant base. S 25

20. The method of any one of claims 16 to 19 wherein said vinyl plasticizer is selected from dioctyl adipate and di-n-hexyl azelate.

21. The method of any one of claims 16 to 20 wherein said composition further comprises an ultraviolet absorber. I P:\OPER\AXD\1914507.RS1 -26F7/99 12-

22. The method of claim 21 wherein said composition comprises 0.01 to 5 weight percent of said ultraviolet absorber.

23. The method of claim 21 or 22 wherein said ultraviolet absorber is selected from 3- (2H-benzotriazol-2-yl)-5-(1, 1-dimethylethyl)-4-hydroxy-benzenepropanoic acid and 2-(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole.

24. The method of any one of claims 16 to 23 wherein said composition further comprises an antioxidant.

The method of claim 24 wherein the composition comprises from 0.5 to 5 weight percent of said antioxidant.

26. The method of any one of claims 16 to 25 wherein the amount of said composition applied to said vinyl surface is limited to a level at which said vinyl surface is suitable for normal use contact within one hour after treatment.

27. The method of any one of claims 16 to 25 wherein the amount of said composition applied to said vinyl surface is from 0.05 to 0.5 cc per 100 square centimeters.

28. A method of treating a vinyl surface substantially as hereinbefore described with reference to any one of examples, 1, 2 or 3. DATED this 26th day of JULY, 1999 00 00o 0 S S O*O S OOO 0 @600 S *0 S 000 0 00 00 o r 0 Sees 6000 OS @0 OS* 0 S. 00 *50 S 0 0000 00 *S S 00* 0 0 ARMOR ALL PRODUCTS CORPORATION by DAVIES COLLISON CAVE Patent Attorneys for the Applicant(s) Li, 1 ;LL