the present invention relates to uv - barrier formulations comprising polyethylene naphthalate ( pen ) and a polyoxyalkylene uv absorber , and polyester formulations comprising one or more polyesters , polyethylene naphthalate and a polyoxyalkylene uv absorber ( or clearshield ). these formulations blend a polyoxyalkylene based uv absorber with a pen component to reduce uv transmission to around 10 % at uv wavelengths up to about 390 nm . the advantages of these formulations are both economical and functional . the pen is the less costly additive , but it only provides uv protection up to about 360 nm , with little uv absorbance effect at higher wavelengths . clearshield ( a preferred polyoxyalkylene uv absorber ), a more costly additive , can provide protection from about 360 nm to about 390 nm . the use of pen to provide uv protection at lower wavelengths provides a significant cost saving versus using only clearshield , by permitting the use of less clearshield than normally needed in order to obtain the same level of uv absorbance for the overall composition . the use of both of these additives together , provides a very economical formulation with an unexpected improvement in uv resistance , above what would be expected based on the combination of these additives . in particular , one improvement seen is an increase in the level of uv absorbance up to about 390 nm when the pen and polyoxyalkylene uv absorber are combined , even though only one of the components actually has a significant measurable absorbance at 390 nm . thus , while one might expect some absorbance at 390 nm due to the polyoxyalkylene uv absorber component , the level of absorbance would be expected to be significantly lower , as the pen does not normally absorb at that wavelength . the present inventors have found , however , that by combining the two uv absorbing components , there is a significant increase in absorbance at about 390 nm ( i . e . significant reduction in uv transmission at about 390 nm ) that would not be present using either component alone . while the present inventors do not wish to be bound by any particular theory on the mechanism of action for the present invention , it appears that there is either an interaction or an actual chemical reaction , for example , the formation of a chemical bond , between the pen and polyoxyalkylene uv absorber components ( and possibly an interaction or chemical reaction with either or both of these components and the polyester matrix ) that causes the uv absorbance at wavelengths up to about 390 nm to significantly increase at a given level of the uv absorber . the formulations of the invention may be prepared in the melt state using conventional techniques known in the art , including melt extrusions from batch , semi - continuous or continuous . it is preferable to add the polyoxyalkylene uv absorber as late as possible in the melt process due to its potential sensitivity to discoloration . in one embodiment of the invention , a composition comprising a polyester matrix is prepared having an amount of uv absorbing composition sufficient to provide a uv transmission of about 20 % or less at about 390 nm , and where the uv absorbing composition comprises polyethylene naphthalate ( pen ) and the polyoxyalkylene uv absorber . in another embodiment , the above composition provides a uv transmission of about 15 % or less , more preferably 10 % or less , and even more preferably 5 % or less , at about 390 nm . in another preferred embodiment of the invention about 1000 ppm ( 0 . 1 wt %) clearshield and about 0 . 2 wt % pen are mixed with a polyester matrix comprises predominantly pet . the amounts of these components are based on the total weight of the polyester formulation or composition . this combination provides uv protection in the pet product , and also provides an economical uv barrier with good appearance in the final product . it has been determined that adding more than 0 . 2 % pen will not further improve the uv barrier of pet , but adding less than 0 . 1 % will reduce the uv barrier . the equivalent uv barrier of about 10 % transmission at about 390 nm , using both pen and clearshield , could be provided by using 2000 ppm clearshield without pen . however , this formulation would considerably increase the cost of providing the same uv barrier protection as the pen / clearshield combination . in another embodiment of the invention , the additives are incorporated into a polyester resin , such as pet resin , by injection into the molten polyester in the transfer line , downstream of the last polymerization vessel and upstream of the pelletizers . this injection can occur using a twin screw extruder to melt the pen polymer and combine it with the polyoxyalkylene uv absorber , for example , liquid clearshield 390b or 390r . the molten mixture is then injected into the transfer line using a metering pump . after the pen / clearshield formulation is injected into the polyester melt stream , it is mixed using both dispersive and distributive mixing to ensure a good mix with the pet melt stream . the mixture is then pelletized . the pellets may be solid state polymerized to further raise the intrinsic viscosity ( iv ) of the resulting resin . this may involve holding the pellets at temperatures above about 200 ° c . for greater than about 12 hours . the pellets should not degrade or significantly change color during the solid stating process . in another embodiment , a concentrated masterbatch of pen and the polyoxyalkylene uv absorber is produced and then dry blended with a polyester resin . the uv absorber of the present invention is a polymeric uv absorber having various chain lengths of polyoxyalkylenes , as described in u . s . pat . no . 6 , 602 , 447 , the contents of which are hereby incorporated by reference . within the context of the present invention , the uv absorber as described in u . s . pat . no . 6 , 602 , 447 is denoted herein as a “ polyoxyalkylene uv absorber ”, although it may contain other types of groups in the backbone of the polymeric compound , with oxyalkylene groups being present with at least 6 total moles of oxyalkylene units per molecule of uv absorber , as in the above noted &# 39 ; 447 patent . an embodiment of the polyoxyalkylene uv absorber of the present invention is that described in the &# 39 ; 447 patent , which is an ultraviolet compound conforming to the structure represented by formula ( i ) wherein r 1 , r 2 , r 3 , r 4 , and r 5 are the same or different and are selected from the group consisting of c 1 - 20 alkyl , halo , hydroxyl , hydrogen , cyano , sulfonyl , sulfo , sulfato , aryl , nitro , carboxyl , c 1 - 20 alkoxy , and b - a , wherein at least one of r 1 , r 2 , r 3 , r 4 and r 5 is b - a wherein b is selected from the group consisting of n , o , s , so 2 , so 3 , co 2 , and a is represented by the formula ( ii ) wherein ‘ polyoxyalkylene constituent ’ is selected from the group consisting of at least three monomers of at least one c 2 - 20 alkyleneoxy group , glydicol , glycidyl , or mixtures thereof , r ′ is selected from the group consisting of hydrogen , c 1 - 20 alkoxy , c 1 - 20 alkyl , and c 1 - 20 esters ; wherein if b is n , then z is 2 , and if b is other than n , then z is 1 ; x and y are the same or different and are selected from the group consisting of hydrogen , cyano , c ( o ) or , c ( o ) r , c ( o ) nr ″ r ′″, c 1 - 20 alkyl , and c 1 - 20 alkoxy , or x and y are combined to form a ring system , and r , r ″, and r ′″ are defined as above for any of r 1 , r 2 , r 3 , r 4 , and r 5 ; and wherein if x and y are not combined to form a ring system then at least one of said x and y is either cyano or hydrogen . a preferred embodiment of the uv absorber is a commercially available product trade - named clearshield ( available from milliken ), most preferably clearshield 390b or 390r . the polyesters of the invention may include , but are not limited to , polyester synthesized from aliphatic , aromatic or cyclic ( aliphatic or aromatic ) dicarboxylic acids , or an aliphatic , aromatic or cyclic ( aliphatic or aromatic ) ester , with an aromatic , aliphatic or cyclic ( aliphatic or aromatic ) diol ; or an esters prepared from two or more aliphatic , aromatic or cyclic ( aliphatic or aromatic ) esters . examples of polyesters include , but are not limited to , polyethylene terephthalate , polyethylene naphthalate , polyethylene isophthalate , polypropylene terephthalate , polybutylene terephthalate , poly ( 1 , 4 - cyclohexylene dimethylene terephthalate ) and polyethylene - 2 , 6 - naphthalene dicarboxylate , and mixtures thereof . copolymers , blends and mixtures thereof are also included . preferred embodiments of the present invention use polyethylene terephthalate polymers having copolymerized therewith from 0 to 5 wt % of isophthalic acid ( or the dialkyl isophthalate counterpart , depending on whether the polyester is produced from a terephthalic acid or dimethyl ( or dialkyl ) terephthalate based process ) and from 1 to 3 wt % of diethylene glycol . such copolymers are commonly used as resins for the formation of various bottles and other containers , most commonly in the production of soda bottles . the term “ polyesters ,” “ polyester matrix ” or “ polyester resins ,” as used herein , refers to all of the above , and includes polyesters prepared from one or more monomers , and blends of one or more of such polyesters . the term “ polymer or polymers ,” “ polymeric ” or “ resin or resins ,” as used herein , refers to both homopolymers and copolymers prepared from one or more monomeric constituents , and to crosslinked systems thereof and branched systems thereof , including , but not limited to , grafted systems thereof . dicarboxylic acids include , but are not limited to , aromatic dicarboxylic acids , such as terephthalic acid , isophthalic acid , phthalic acid and 2 , 6 - naphthalenedicarboxylic acid ; aliphatic dicarboxylic acids , such as adipic acid , azelaic acid , sebacic acid and decanedicarboxylic acid ; and alicyclic dicarboxylic acids , such as cyclohexanedicarboxylic acid . diols include , but are not limited to , aliphatic diols such as 1 , 4 - butanediol , 1 , 3 - propanediol , 1 , 6 - hexanediol , monoethylene glycol , diethylene glycol , triethylene glycol and polyethylene glycol ; alicyclic diols , such as 1 , 4 - cyclohexanedimethanol ; and aromatic diols such as bisphenol a . these diacids and diols may be used alone or in combination of two or more . other polyester components include , but are not limited to , phthalic anhydride , trimellitic acid , pyromellitic acid , dimeric acid and 5 - sodiumsulfoisophthalic acid . the polyesters can be produced by condensation reactions and / or ester exchange reactions , and other methods known in the art . products of the invention include , but are not limited to , bottles , various - shaped containers , sheets , films , fibers , tubes , and the like . products also include packaging materials , such as containers , sheets , blister packages , and the like , which can be utilized for storage purposes . products of the invention may include one or more polyesters , optionally in combination with one or more different thermoplastics , in any combination . other additives may optionally be added to the formulations of the invention to effectuate a desirable physical state . these additives include , but are not limited to solvents , viscosity modifiers , fillers , colorants , acid scavengers , antistatic agents and other uv absorbers . additives may be added prior to , during , and / or after introduction of the uv - barrier formulation within the desired polyester matrix . having generally described this invention , a further understanding can be obtained by reference to certain specific examples , which are provided herein for purposes of illustration only , and are not intended to be limiting , unless otherwise specified . twenty pounds of a pen / pet copolymer containing 90 wt % polyethylene terephthalate and 10 wt % polyethylene naphthalate were compounded with one pound of clearshield 390b ( available from milliken ) in a twin screw extruder . the compounded mixture was pelletized into a masterbatch . the masterbatch was dry blended with virgin pet polymer pellets at a 46 . 6 to 1 letdown ratio and the dry blend was used to injection mold preforms . the preforms were then stretch blow molded . the final concentration of pen in the bottles was 0 . 200 %. the final concentration of clearshield 390b in the bottles was 0 . 100 %. transmission testing of the sidewall of the bottles produced demonstrated that at the concentration used this formulation provided uv protection up to 10 % transmission at 390 nm . fig1 is a transmission profile comparing a preferred formulation of the invention with other conventional formulations . the corresponding data for this figure is listed in table 1 . obviously , additional modifications and variations of the present invention are possible in light of the above teachings . it is therefore to be understood , that within the scope of the appended claims , the invention may be practiced otherwise than as specifically described herein .
the invention provides uv - barrier formulations which result in products which effectively resist the transmission of ultraviolet light therethrough . the invention also provides uv - barrier formulations which result in products with improved resistance to ultraviolet light . in particular , the invention provides uv barrier formulations for polyester resins that have improved resistance to ultraviolet radiation , and significantly reduce ultraviolet light transmission in the resulting resin products . the invention also provides products and manufacturing processes based on the above formulations .