WO2003018682A1 - Absorbeurs d'uv a faible coloration et compositions les contenant - Google Patents

Absorbeurs d'uv a faible coloration et compositions les contenant Download PDF

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Publication number
WO2003018682A1
WO2003018682A1 PCT/US2002/023805 US0223805W WO03018682A1 WO 2003018682 A1 WO2003018682 A1 WO 2003018682A1 US 0223805 W US0223805 W US 0223805W WO 03018682 A1 WO03018682 A1 WO 03018682A1
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WIPO (PCT)
Prior art keywords
thermoplastic
compound
polyester
molten formulation
group
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PCT/US2002/023805
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English (en)
Inventor
Xiaodong E. Zhao
Mary E. Mason
Todd D. Danielson
Jusong Xia
Daniel M. Connor
Eric B. Stephens
Jason D. Sprinkle
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Milliken & Company
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Priority claimed from US09/934,380 external-priority patent/US6596795B2/en
Priority claimed from US09/934,376 external-priority patent/US6559216B1/en
Priority claimed from US09/934,374 external-priority patent/US20030078328A1/en
Application filed by Milliken & Company filed Critical Milliken & Company
Priority to JP2003523537A priority Critical patent/JP2005501155A/ja
Priority to EP02744885A priority patent/EP1423461A4/fr
Priority to BR0211395-3A priority patent/BR0211395A/pt
Publication of WO2003018682A1 publication Critical patent/WO2003018682A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds

Definitions

  • This invention relates to novel ultraviolet absorbing compounds that are liquid in nature, are extremely low in color (and thus permit use without the concomitant necessity of adding large amounts of other coloring agents to combat any discoloring within clear, colorless applications), and are highly effective in providing protection in wavelength ranges for which previous attempts at low-color ultraviolet absorbers have failed.
  • Such compounds provide such excellent, inexpensive, and beneficial protection from ultraviolet exposure within various media, including, but not limited to, clear thermoplastics.
  • the particular compounds are generally polymeric in nature including various chain lengths of polyoxyalkylenes thereon and are liquid in nature to facilitate handling and introduction within the target media, hi addition, such ultraviolet absorbers also exhibit extremely low migratory properties thereby providing long-term protective benefits to the target media as well.
  • This invention also concerns the end products, specific broadly defined types of compounds providing such beneficial characteristics, methods of making such low-color compounds, and methods of producing such clear, UN protected end products.
  • Ultraviolet absorber compounds have been utilized for a number of protective applications, including within compositions for covering skin, on and within apparel and other types of textiles, within transparent plastic containers, and the like, to combat the harmful and degradable effects of certain wavelengths of light in the UN spectrum.
  • the best known UN absorbers are benzotriazoles, available from Ciba under the tradename Tinuvin®, and benzophenones, available from Cytec Industries under the trademark CyasorbTM.
  • Such compounds are highly effective in their UN absorber capacity; however, they are quite costly, can prove difficult to incorporate within different target media, and tend to migrate from within certain types of media (such as plastics).
  • these two well known types of UN absorbers present handling difficulties in that they are generally produced and utilized in powder form and have relatively low melting points.
  • the powder form of these compounds is problematic; a liquid is much easier to handle, does not require melting, and provides more effective and thorough mixing throughout the target plastic.
  • these previously utilized UN absorbers provide UN protection over a relatively narrow range of wavelengths ( ⁇ max from about 290 to about 340 nm for benzotriazoles; from 260 to 300 nm for benzophenones), which ultimately leaves a potentially damaging range of unprotected UN exposure (to about 400 nm).
  • Methine-based compounds in particular certain malonate derivatives, as in European Patent Abstract 350-386-A, to L'Oreal SA, are useful as UN absorbers in cosmetic sunscreen compositions, are generally inexpensive to make, and provide UN protection in the spectrum from about 280 to about 360 nm.
  • such compounds are highly soluble in organic solvents and would therefore easily migrate from solid compositions, such as plastics, upon introduction therein.
  • an effective UN absorber such as a malonate derivative
  • within plastics may be highly desirable, such has never been taught nor fairly suggested within the prior UN absorber art due to the great difficulty in producing such a stable, and thus highly effective, UN absorbing composition from such a methine-based source.
  • Pruett et al. teaches such UN absorbers for polyester end-uses. Again, however, such compounds exhibit very high extraction results unless they are added as to-be-polymerized reactants themselves with the ester monomers during the polymerization step, hi such an instance, these UN absorbers are actually integrated within the polymer, and not just mixed within the thermoplastic medium. As such, although such compounds do exhibit excellent results when polymerized within the target polyester, unfortunately such compounds are limited in their versatility since the only time during which effective introduction is permitted is during the aforementioned polymerization procedure.
  • the resultant composition is accorded protection from a great amount of potentially damaging UN radiation (from approximately 250 to about 400 nm). Additionally, such a combination is highly stable within the desired media, and thus provides long-term protection to the desired sample stored within the target treated plastic article.
  • such compounds are very low in color when prepared in accordance with certain procedures, most notably with certain alkoxylation catalysts, including, without limitation, metal hydroxides and other bases, both alone and in the presence of amine-based alkoxylation catalysts (particularly with affinities for available protons), as well as rare earth phosphate salts, such as those taught within U.S. Patent ⁇ os. 5,051,621, 5,057,628, 5,059,719, 5,118,870, 5,208,199.
  • Such low-color alternatives thus provide the basis for effective utilization within colorless (clear and transparent) applications, such as the desired clear plastics, while simultaneously providing the necessary effective UN protection.
  • Ciba compounds Although such compounds appear to provide very good ultraviolet protection both to the plastic itself and to any stored liquids, solids, etc., within a container made therewith such plastics, unfortunately such a class of compounds exhibits undesirable or problematic ' deficiencies, h particular, the breadth of protection within the UN spectrum is generally limited to from about 320 to about 375 nm with such compounds. Thus, they generally do not provide adequate UN protection to contents of plastic packaging over the entire range of UN wavelengths. Also, such Ciba compounds are generally naturally solid in nature and thus are either dispensed within target resins as solid powders or must be dispersed within liquids by the end-user at time very close to dispensing in order to be effective.
  • Ciba UN absorbers are in fact liquid, they still are limited in their breadth of UN protection in terms of wavelength ranges.
  • Ciba compounds exhibit relatively high extraction levels and migratory characteristics from within target plastic resins, particularly thermoplastics such as polyethylene terephthalates.
  • target plastic resins particularly thermoplastics such as polyethylene terephthalates.
  • Objects of the Invention It is therefore an object of this invention to provide novel low-color, low- thermoplastic-migrating (e.g., low-extraction), ultraviolet absorbing compounds, which may further be liquid when present in their pure, undiluted states at room temperature and that provide UV protection over a broad range of wavelengths up to at least 390 nm.
  • a further objective of this invention is to provide a polymeric UV absorber that can be used within various media and on different substrates as an effective UV filtering compound or within a suitable composition for protection against potentially harmful ultraviolet rays.
  • a further object of this invention is to provide a methine-based UN absorber that provides bright and clear plastic articles.
  • the present invention thus encompasses a clear thermoplastic article having an average thickness of at most 35 mils comprising at least one ultraviolet absorber compound exhibiting ultraviolet absorption characteristics over the range of wavelengths from about 300 to about 400 nm such that said article exhibits a UV transmission of at most 10% at the 390 nm wavelength; and wherein said at least one compound exhibits an extraction level from said thermoplastic article measured as the level of absorbance exhibited by a heated alcohol extract solution after 2 hours exposure of at most 0.1 absorbance units in a cell with a 10.0 cm optical path length, preferably 0.05, more preferably 0.025, and most preferably as low as 0.0; wherein said ultraviolet absorber comprises at least one poly(oxyalkylene) chain of at least six total moles of oxyalkylene, or alternatively wherein said ultraviolet absorber is introduced within said thermoplastic at any time during the production of said article, or also alternatively, wherein said at least one ultraviolet absorber is a liquid prior to incorporation within said thermoplastic article and at room temperature in
  • thermoplastic article also considered part of this invention is the same clear thermoplastic article as above wherein said thermoplastic article simultaneously exhibits a yellowness level of at most 2.5 and a brightness level of at least 90.
  • a liquid ultraviolet absorber compound exhibiting a Gardner color value of at most 11, wherein said ultraviolet absorber exhibits an extraction level from polyethylene terephthalate measured as the level of absorbance exhibited by a heated alcohol extract solution after 2 hours exposure of at most 0.1 absorbance units, preferably 0.05, more preferably 0.025, and most preferably as low as 0.0.
  • R la R 2 , R 3 , Rt, 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 Ri, R 2 , R 3 , R , 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 (_T)
  • 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- o 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?
  • polyoxyalkylene constituent is selected from the group consisting of at least three monomers of at least one C 2-20 alkyleneoxy group, glycidol, glycidyl, and any mixtures thereof, and R' is selected from the group consisting of hydrogen, C 1-20 alkoxy, C 1-20 alkyl, and C 1-20 esters; wherein the method comprises the sequential steps of a) reacting vanillin with at least one compound selected from the group consisting of at least one compound comprising at least one oxyalkylene-containing group selected from the group consisting of at least one C 2 -C 20 alkylene oxide, glycidol, and any mixtures thereof, in the presence of a catalyst; and b) reacting the reaction product of step "a" with at least one alkyl cyanoester
  • Such a novel compound should exhibit a Gardner color level of at most 10 when present within a methanol solution at a 5% concentration by volume and a maximum ultraviolet absorption within the range of wavelengths of 320 and 400 nm, with a measured ultraviolet transmission of at most 10%> at each wavelength under 400 nm, preferably under 390 nm, when incorporated at a loading of at most 0.5%) by weight within a polyester article having a thickness of at most 1 mm.
  • such a novel compound may also be liquid in its pure,undiluted state at room temperature, again to facilitate handling and introduction within desired media, such as, without limitation, thermoplastics.
  • this invention encompasses a method of forming a low-color ultraviolet absorber compound wherein said ultraviolet absorber compound conforms to structure represented by Formula (IV)
  • polyoxyalkylene constituent is selected from the group consisting of at least three monomers of at least one C 2 . 20 alkyleneoxy group, glycidol, glycidyl, and any mixtures thereof, and R' is selected from the group consisting of hydrogen, C 1-20 alkoxy, C 1-20 alkyl, and C 1- 0 esters; said method comprising the sequential steps of a) reacting resorcinol with a compound selected from the group consisting of at least one compound comprising at least one oxyalkylene-containing group selected from the group consisting of at least one C -C 20 alkylene oxide, glycidol, and any mixtures thereof, in the presence of a catalyst to produce a polyalkoxylated resorcinol; and b) reacting the reaction product of step "a” with a compound whereby said compound protects the polyalkoxylate hydroxyl groups; c) converting the product of step "b" to an aromatic aldehyde through the production of
  • Such a novel compound should exhibit a Gardner color level of at most about 11 when present within a methanol solution at a 5%> concentration by volume and a maximum ultraviolet absorption within the range of wavelengths of 320 and 400 nm, with a measured ultraviolet transmission of at most 10%> at each wavelength under 400 nm, preferably under 390 nm, when incorporated at a loading of at most 0.5%o by weight within a polyester article having a thickness of at most 1 mm.
  • such a novel compound may also be liquid in its pure,undiluted state at room temperature, again to facilitate handling and introduction within desired media, such as, without limitation, thermoplastics.
  • compositions comprising such compounds of (IH) and (IV) are also encompassed within this invention, particularly those comprising such compounds and bluing agents, as liquids or as pellets for further introduction within desired molten thermoplastic formulations.
  • thermoplastics comprising such compounds of (I), (IH), and (IN) are also contemplated within this invention.
  • thermoplastic is intended to encompass any synthetic polymeric material that exhibits a modification in physical state from solid to liquid upon exposure to sufficiently high temperatures.
  • preferred thermoplastic types of materials are polyolefins (i.e., polypropylene, polyethylene, and the like), polyester (i.e., polyethylene terephthalate, and the like), polyamides (i.e., nylon-1,1, nylon-1,2, nylon-6 or nylon-6,6), polystyrenes, polyurethanes, polycarbonates, polyvinyl halides (i.e., polyvinyl chloride and polyvinvyl difluoride, as merely examples), and the like.
  • Preferred thermoplastics within this invention are polyesters, and most preferred is polyethylene terephthalate.
  • thermoplastic articles include bottles, storage containers, sheets, films, fibers, plaques, hoses, tubes, syringes, and the like. Included within this list would be polyester, polystyrene and other like clear resinous materials in sheet form which are present within windows for strength and resiliency functions.
  • the low-color UN absorbers of this invention would provide or contribute to excellent UN protection for contents with target packaging articles (such as bottles, containers, and the like) or persons located indoors (such as within houses, buildings, cars, and the like, comprising windows with such additives included therein).
  • target packaging articles such as bottles, containers, and the like
  • persons located indoors such as within houses, buildings, cars, and the like, comprising windows with such additives included therein.
  • the possible uses for such a low-color, low- migratory UN absorber is voluminous and cannot easily be enveloped.
  • Other possible end- uses would include solvent systems, printing inks, textile treatment compositions (either on or within textiles, fibers, fabrics,
  • thermoplastics include, again without limitation, films, sheets, bottles, containers, vials, and the like.
  • Ultraviolet absorbers are typically added to such compositions during the injection molding (or other type of molding, such as blow molding), thereof, including, and without limitation, by mixing the liquid absorber with resin pellets and melting the entire coated pellets, or through a masterbatch melting step while the resin and absorber are pre-mixed and incorporated together in pellet form.
  • Such plastics include, again without limitation, polyolefins, polyesters, polyamides, polyurethanes, polycarbonates, and other well known resins, such as those disclosed within U. S.
  • thermoplastics are polyesters, such as, in one non-limiting embodiment, polyethylene terephthalate.
  • Plastic packaging thus encompasses containers, sheets, blister packages, and the like, utilized for storage purposes and which include the plastics in any combination as noted above.
  • pure, undiluted state indicates that the compounds themselves without any additives are liquid at room temperature. Thus, there is no need to add solvents, viscosity modifiers, and other like additives to the UN absorbers to effectuate such a desirable physical state.
  • Such inventive polymeric UN absorbers are very low in color [e.g., do not exhibit a b* value (indicating a degree of yellowing in this instance) above 2.5 on the CieLab scale].
  • b* value indicating a degree of yellowing in this instance
  • acid scavengers and other like additives, to the particular UN absorber to provide such desired low-color (low-yellowing) characteristics.
  • thermoplastic additives such as thermoplastic additives
  • other additives such as the aforementioned bluing agents, acid scavengers, antistatic agents, optical brighteners, and the like, may also be added to these compounds prior to, during, and/or after introduction within the desired end product medium (such as thermoplastic, for example).
  • the polymeric species maybe determined through destructive analysis (methanolysis, for example), and further spectrophotometric analysis thereof to locate any signatures of an aniline poly(oxyalkylene) comopund, as one example.
  • solvent systems encompasses any aqueous or organic liquid formulations.
  • ⁇ on-limiting examples of the intended aqueous systems include cleaning solutions, detergents, fabric softeners, marking inks and colorants, and keratin dyes.
  • ⁇ on-limiting examples of organic formulations include the non-aqueous types of cleaning solutions, detergents, fabric softeners, marking inks and colorants, keratin dyes, as well as descalers, surfactant formulations, hydrocarbon compositions, and the like.
  • inventive UN absorbers is accomplished through the mere addition of the liquid compound within the target solvent system with simultaneous and thorough mixing.
  • Printing inks include compositions utilized as colorants within, again, as merely examples, pens, including, but not limited to ball-point and fountain pens, dot-matrix printers, toners for standard copy machines, ink-jet applications, permanent markers, dry-erase markers, newsprint, magazine print, laser jet printers, and the like.
  • inventive UN absorbers is accomplished through the mere addition of the liquid compound within the target printing ink formulations with simultaneous and thorough mixing.
  • textile treatment compositions comprises both any formulations for application on textiles (and thus leaving at least a temporary UN absorbing coating, or the like, on the textile surface).
  • Incorporation of the inventive compounds within fibers of textiles is also encompassed within this term and thus within this invention.
  • Skin protectant and skin tanning formulations basically encompass any compositions comprising the novel UN absorbing compound which is utilized to protect skin from solar radiation.
  • inventive plastics do not exhibit such discolorations to such a degree and thus, even though some yellowing may be exhibited by such compounds, and thus within the target thermoplastics, the use of much lower amounts of bluing agents provides the needed clear, uncolored resin, thereby saving on cost and reducing the work needed to provide such a proper clear article as well as a brighter article. Because bluing agents not only aid in preventing yellowness within target media, but also contribute grayness therein as well, the utilization of large amounts of such agents is generally avoided.
  • inventive compounds thus provide clarity with low grayness levels due to the low-color aspects available therewith.
  • the desired clear plastics exhibit heretofore unattained brightness levels with simultaneously extensive and effective ultraviolet protection over a wide range of wavelengths (as discussed above). Furthermore, such effective UV absorbing characteristics are noticeable in terms of protection for certain contents of target thermoplastic storage articles. As discussed further below, such inventive
  • UN absorbers exhibit highly desirable ultraviolet absorption characteristics over the range of wavelengths from about 300 to about 400 nm such that an aqueous composition of riboflavin present within said clear thermoplastic article will exhibit a degradation rate of at most 75% after ultraviolet exposure over the wavelength range of 300 to 400 nm after 20 hours of exposure to high intensity UV light (e.g., and for all such experiments listed hereinafter, under at least 8 total Sylvania® 350 Blacklight bulbs, Model Number F40/350 BL, 40 watts each).
  • inventive compounds exhibit extremely low migratory (e.g., low- extraction) levels from plastics and other media.
  • the presence of poly(oxyalkylene) chains thereon provides a very versatile UV absorbing compound as a liquid or low viscosity additive that, exhibits thorough and effective mixing when introduced within the target thermoplastic and following molding and cooling also exhibits very low extraction levels therefrom.
  • Such resultant low extraction levels are exhibited by said inventive compound (as well as said inventive thermoplastic) no matter when the inventive UV absorber compound is introduced within the target thermoplastic during production thereof.
  • Handling is greatly improved thereby, and more thorough dispersion within the desired medium is accomplished as well. Again, costs are reduced due to simplicity and reliability is increased with more thorough mixing, etc., through utilization of such inventive compounds with simultaneous or concomitant reliability in terms of performance and low extraction characteristics.
  • such a highly reliable, easy-to-handle, low-color, and low-migratory (low-extraction) UN absorbing compound also provides a greater range of protection than the standard UV absorbers now provided within the industry.
  • standard UV absorbers are effective up to about 380 nm, even with an increase in amount of such a compound within the target medium (polyester, for example).
  • target media such as thermoplastics
  • the inventive compounds provide protection up to about 400 nm.
  • riboflavin (Vitamin B 2 ) meets such a description; in comparison with standard UV absorbers (Tinuvin® 234, for example), the protection accorded riboflavin within an aqueous solution and stored within a clear polyethylene terephthalate container and exposed to a UV source between 320 and 400 nm for 20 hours is significantly higher for the inventive vanillin- and resorcinol- based compounds.
  • inventive UV absorbing compounds then conform to the following structure (I) (I)
  • Ri, 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- 0 alkoxy, and B-A, wherein B is selected from the group consisting of N, O, S,
  • Alkyleneoxy constituent is selected from the group consisting of C 2-20 alkyleneoxy
  • R' is selected from the group consisting of hydrogen, C 1-2 o 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, .
  • R is defined as above for any of R ⁇ , R 2 , R 3 , j, and R 5 ; wherein at least one of R ⁇ , R 2 , R , R 4 , and R 5 is B-A; and at least one of said X and Y is either cyano or hydrogen.
  • X is an ester group
  • Y is cyano
  • B is O
  • Alkylene constituent is either oxyethylene, oxypropylene, or oxybutylene, with oxyethylene and oxypropylene most preferred (between 2 and 100 units of such monomers; preferably between 2 and 50; and most preferably, between 5 and 20); and R' is preferably hydrogen.
  • Such compounds thus must also exhibit the aforementioned low-color and low-migration (from the target medium, such as plastic) characteristics, as well as existing as a liquid when in its undiluted state at room temperature.
  • such a low-color ultraviolet absorbing compounds conform to the structures represented by Formulae (I), (El), and (IV), above.
  • Such compounds are poly(oxyalkylenated) in order to provide the desired low extraction levels from thermoplastics as discussed above.
  • the ability to provide such low-color species for structures conforming to Formulae (I) and (Iff), above, and thus not resorcinol-based compounds, is apparently controlled through the utilization of specific types of alkoxylation catalysts, including, without limitation, rare earth salts (such as lanthanum phosphates), particular metal hydroxides (such as potassium hydroxide both alone and in the presence of compounds having a strong affinity for free and/or available protons within the reaction medium itself, hereinafter referred to as "proton sponge"), and the like.
  • rare earth salts such as lanthanum phosphates
  • particular metal hydroxides such as potassium hydroxide both alone and in the presence of compounds having a strong affinity for free and/or available protons within the reaction medium itself, here
  • Such catalysts particularly the rare earth phosphates, apparently are configured in such a way that the levels of impurities and starting materials present within the reaction itself if drastically reduced in comparison with other standard alkoxylation catalysts (such as sodium hydroxide) (although the true reasons behind such beneficial low-color production is not completely understood).
  • proton sponge compounds include, without limitation, 1,8- bis(dimethylamino) naphthalene, l,8-bis(diethylamino)-2,7-dimethoxynaphthalene, 4,5- bis(dimethylamino)-fluorene, 4,5-bis(dimethylamino)phenantl rene, quino[7,8-n]quinoline, and the like, with l,8-bis(dimethylamino)naphthalene preferred.
  • the alkoxylated compounds include either ethylene oxide or propylene oxide, or mixtures of both, thereon having chain lengths from 2 to about 100; more preferably such a chain length if from about 2 to about 50; and most preferably such a chain length is from about 5 to about 10, with all ethylene oxide also highly preferred.
  • the vanillin-based UV absorbing compounds of structure of Formula (Hi) are thus preferred embodiments of structure of Formula (I).
  • the structures conforming with Formula (TV) are also preferred embodiments of the structure of Formula (I)] are produced as low-color poly(oxyalkylenates) through the above- noted modified formylation of a hydroxyl-protected alkoxylated resorcinol through Nilsmeier complexation and subsequently deacetylating such a compound, hi such an instance, the initial alkoxylation may be performed through catalysis with most standard alkoxylation catalysts.
  • the same types of oxyalkylenes and chain lengths thereof as noted above for the structures of Formulae (I) and (HI) are preferred as well for the structure of Formula (IV).
  • the starting material within the method of making such a compound is thus any resorcinol- based compound, preferably resorcinol itself.
  • a protecting compound for the free hydroxyls thereon maybe an ester anhydride, preferably at least one of C ⁇ -C 0 ester anhydride, more preferably acetic anhydride.
  • the protected compound is then formylated with a Vilsmeier complex formed from, for example, N,N-dimethyl formamide and phosphorous oxychloride and can be any standard compound of this type, including, without limitation disubstituted formamides reacted with either phosphorous oxychloride, phosgene, or triflic acid, as merely examples.
  • any other aldehyde-forming group will function within this method.in order to produce an aromatic aldehyde based on the protected resorcinol polyoxyalkylenated compound [such as resorcinol (6 moles of ethylene oxide aka EO) diacetate].
  • the formylation reaction is run at a lower temperature
  • hypophosphorous acid is a well known reducing agent and it is believed that its presence counters the formation of highly colored oxidized species. The exclusion of oxygen during the reaction thus is highly critical as well.
  • the protected hydroxyls are then liberated (e.g., deprotected) via base hydrolysis with any compound or mixture of compounds having a pH level of at least 12, such as NaOH, KOH, mixtures thereof, and the like. A mixture of the two bases is preferred.
  • Compositions comprising such compounds are also encompassed within this invention, particularly those of the compounds and bluing agents as liquids or as pellets. These broadly defined compounds as well as the more specific types thus provide the necessary characteristics for clear applications (again, clear plastics, as one non-limiting example) in terms of low color, low migration, liquid state, and effective and thorough mixing within the target medium.
  • the inventive UV absorber is added in an amount of from about 0.001 to about 1.5% by weight of the total plastic composition, preferably from about 0.01 to about 1.0%, and most preferably from about 0.05 to about 0.5%>.
  • plastics may include other standard additives, including antioxidants, clarifying agents, nucleators, acid scavengers, perfumes, colorants (for transparent, but colored applications), antistatic agents, and the like.
  • EXAMPLE 2 Four hundred and fifty-six grams of vanillin, one gram of KOH flake and four grams of proton sponge [l,8-bis(dimethylamino)naphthalene] were charged to an autoclave. The autoclave was then sealed, purged several times with nitrogen gas (to a pressure of 60 PSIG) and then pressurized to 5 PSIG of nitrogen. After heating the autoclave to 121°C, ethylene oxide was added to the reaction mixture until a total of 792 g were added over time. Once all of the ethylene oxide was added, the mixture was post-cooked for a total of thirty minutes. The mixture was then cooled to 93 °C and stripped at reduced pressure for fifteen minutes in order to remove un-reacted ethylene oxide. One thousand two hundred and fifty-three grams of product (yield 97% ⁇ ) is obtained as a pale yellow liquid with a hydroxyl number of 142.
  • the mixture was then filtered through a 5-micron filter to yield 80 g of light yellow liquid product that has a lambda max of 360 nm in methanol. Its color value in methanol, which is defined as absorption per gram of sample in 1000 ml of methanol, is 42 abs/g/1.
  • EXAMPLE 4 Eight hundred grams of resorcinol, 400 g of toluene and 4 g of sodium hydroxide pellets were charged to an autoclave. The autoclave was then sealed, purged several times with nitrogen gas (to a pressure of 60 PSIG) and then pressurized to 5 PSIG of nitrogen. After heating the autoclave to 121°C, ethylene oxide was added to the reaction mixture until a total of 1920 g were added over time. Once all of the ethylene oxide was added, the mixture was post-cooked for a total of thirty minutes. The mixture was then stripped at 100°C via rotovap in order to remove unreacted ethylene oxide and toluene (water was added periodically to aid in the removal of toluene). The final product had a hydroxyl number of 304.
  • the mixture was heated under a nitrogen atmosphere to 70°C and held for two hours. Subsequently, the mixture was cooled to room temperature and added to a solution containing 2492 g of water and 1566 g of 50%> sodium hydroxide solution. This mixture was heated under a nitrogen atmosphere to 75°C and phased. The product layer was combined with 876 g of water, 546 g of 50%» sodium hydroxide solution and 92 g of 45% potassium hydroxide solution. While under a nitrogen atmosphere, the mixture was heated to 70°C and held for three hours. After cooling to room temperature, lOOOg of water were added the mixture after it was neutralized with 93%> sulfuric acid solution to a pH of 7.
  • UV absorber One thousand grams was mixed with 8 g of ClearTint® PC Violet 480 from Milliken chemical. The UV blend was then used for the application testing.
  • the mixture was cooled to room temperature and added to a solution containing 369 g of water and 232 g of 50%> sodium hydroxide solution. This mixture was heated under a nitrogen atmosphere to 75°C and phased.
  • the product layer was combined with 153 g of water, 95 g of 50%) sodium hydroxide solution and 16 g of 45% potassium hydroxide solution. While under a nitrogen atmosphere, the mixture was heated to 70° C and held for three hours. After cooling to room temperature, 112 g of water were added the mixture after it was neutralized with 93%> sulfuric acid solution to a pH of 7. The resulting mixture was heated under a nitrogen atmosphere to 75°C and phased.
  • the product layer was stripped and passed through a filter leaving 110 g of a light orange liquid. A 5% aqueous solution of this liquid had a Gardner color (1953 series) of 7.
  • the mixture was cooled to room temperature and added to a solution containing 369 g of water and 232 g of 50% sodium hydroxide solution. This mixture was heated under a nitrogen atmosphere to 75°C and phased.
  • the product layer was combined with 153 g of water, 95 g of 50%) sodium hydroxide solution and 16 g of 45%> potassium hydroxide solution. Wlender under a nitrogen atmosphere, the mixture was heated to 95°C and held for three hours. After cooling to room temperature, 112 g of water were added the mixture after it was neutralized with 93% sulfuric acid solution to a pH of 7. The resulting mixture was heated under a nitrogen atmosphere to 75 °C and phased.
  • the product layer was stripped and passed through a filter leaving 107 g of a dark reddish brown liquid. A 5%> methanol solution of this liquid exhibited a Gardner color (1953 series) of 13.
  • the mixture was heated under a nitrogen atmosphere to 90°C and held for two hours. Subsequently, the mixture was cooled to room temperature and added to a solution containing 369 g of water and 233 g of 50%o sodium hydroxide solution. This mixture was heated under a nitrogen atmosphere to 75 °C and phased. The product layer was combined with 153 g of water, 95 g of 50%> sodium hydroxide solution and 16 g of 45%> potassium hydroxide solution. While under a nitrogen atmosphere, the mixture was heated to
  • COMPARATIVE EXAMPLE 6 Seventeen g of 3,4-dimethoxybenzaldehyde, 70 ml of toluene, 1 g of piperidine and 15 g of ethylcyanoacetate were charged to a 250 ml three neck flask. In the presence of a nitrogen atmosphere, the mixture was heated to 110°C and held for two hours. A precipitate formed on cooling. The precipitate was collected and recrystalhzed from 1 : 1 toluene: acetone. After drying in an oven set at 70°C, a light greenish-yellow solid remained winch has a lambda max of 357 nm in methanol.
  • COMPARATIVE EXAMPLE 7 Seventeen g of 2,4-dimethoxybenzaldehyde, 70 ml of toluene, 1 g of piperidine and 15 g of ethylcyanoacetate were charged to a 250 ml three neck flask. In the presence of a nitrogen atmosphere, the mixture was heated to 110°C and held for two hours. A precipitate formed on cooling. The precipitate was collected and recrystalhzed from 1 : 1 toluene: acetone. After drying in an oven set at 70°C, yellow needles remained. A methanol solution containing this substance has a lambda max of 368 nm. COMPARATIVE EXAMPLES 8 AND 9
  • Example 8 Vanillin (15.2 g, 0.1 mol), ethyl cyanoacetate (12.5 g, 1.1 eq) and ethanol (100 ml) were mixed in a 250-ml 3 neck round bottom flask equipped with a reflux condenser. While stirring, piperidine (1.5 g) was added and the whole mixture was refluxed for 2 hours. After cooling down to RT, the mixture was acidified to pH 5-6 by 10%> HCl. The precipitate formed was collected by filtration, washed several times with methanol and dried in air to result a bright yellow crystalline product (9 g) which had a absorption of 360 nm in acetone.
  • Example 9 Vanillin (15.2 g, 0.1 mol), ethyl cyanoacetate (12.5 g, 1.1 eq) and toluene (100 ml) were mixed in a 250-ml 3 neck round bottom flask equipped with a reflux condenser. While stirring, piperidine (1.5 g) was added and the whole mixture was refluxed for 2 hours. After cooling down to RT, the mixture was acidified by a few drops of 10%> HCl. The precipitate formed was collected by filtration, washed several times with methanol and dried in air to result a yellow crystalline product (19.2 g) which had a absorption of 360 nm in acetone.
  • Tinuvin® 234 was obtained from Ciba. Sample of Eastman Heatwave® UV concentrate was obtained and tested for comparative purposes as well. Such commercial samples were then introduced within certain thermoplastic end-uses as for the other Comparative Examples noted above.
  • the Eastman UN absorber was introduced by actually polymerizing the UN absorber with the thermoplastic itself.
  • the Ciba UN absorber was added as a powder within a molten thermoplastic formulation and then mixed thoroughly therein. Thermoplastic Composition Formation
  • the UV absorber was introduced within an injection molding operation for a polyester thermoplastic, for instance polyethylene terephthalate.
  • the liquid absorber was blended via agitation onto hot, dried polyethylene terephthalate resin (in pellet form) in a chamber, which minimized the adsorption of moisture, by the resin.
  • the blend of absorber and pellets was gravity fed into the feed throat of the machine. In the feed section, melting was accomplished though the utilization of a heated (heat transferred from the barrel of the machine) screw extruder which rotated. The rotation of the screw provided thorough mixing of the absorber and molten resin together producing a uniform plastic melt which was injected into a mold in order to form the intermediate thermoplastic article, for instance a parison.
  • the intermediate article (such as the parison) was allowed to equilibrate at normal room temperature and humidity before being processed further.
  • the article was positioned in front of a bank of infrared heaters that increased the temperature of the parison to its softening point.
  • the heated parison was then transferred to a mold where a rod was inserted into the parison stretching the end of the parison to the bottom of the mold. Subsequently, pressurized air was blown into the stretched parison pushing the walls of the parison against the mold to form the desired thermoplastic article, such as a bottle, having an average thickness of about 15-20 mils.
  • the fransmittance spectra of the PET bottle wall sections were measured from 250 nm to 450 nm in 5 nm increments. The results are as follows:
  • the inventive UV absorbers provide greater overall protection for the target PET resin.
  • the inventive UV absorbers provide much improved UN protection at longer wavelength range (between 370 -390 nm).
  • only the PET bottles with the inventive UN absorbers can meet the specification of transmission under 10% for wavelength below 390 nm.
  • the main objective to incorporate UN absorber into PET packaging is to protect the content from harmful UN damage. Such needs are more acute in food packaging. It is generally known that UN light would cause degradation of various nutrients, such as vitamins. It is now found that the inventive UV absorbers offer much improved protection against UV damage relative to the commercial UV absorbers.
  • the vitamin B group has a wide and varied range of functions in the human body. Most B vitamins are involved in the process of converting blood sugar into energy. Diets rich in B vitamins are particularly important for pregnant and breast-feeding women and for other people who require more energy, such as athletes and heavy-labor workers. Vitamin B 2 , Riboflavin, is very important in the production of energy. Vitamin B 2 can be found in milk, dried fortified cereals, and low fat yogurt. Deficiencies affect the skin and mucous membranes. Though riboflavin is quite stable to heat, it is very sensitive to light. It is particularly sensitive to ultraviolet light.
  • a stock solution of riboflavin was prepared by dissolving 50 mg/L in deionized water. The stock solutions were protected from light.
  • the PET bottles from previous experiment (listed in table 1) were used. The PET bottles were filled with the stock solution. The bottles were placed in a Q-Panel QUV Acelerated Weathering Tester with UVA-351 bulbs. The choice of UNA light bulbs is to simulate the exposure to fluorescent light during warehouse, supermarket or other indoor storage.
  • the degradation of the riboflavin was followed by monitoring the absorption of the visible absorption peak at 444 nm.
  • the control sample was covered with aluminum foil and was subjected to the same treatment.
  • the test data is summarized in table 3.
  • the Colorimetric data of the different PET bottle wall sections was measured on a Gretag-Macbeth ColorEye 7000A Spectrophotometer.
  • the Colorimetric data, using the CieLab scale, specifically L*, indicating the lightness/darkness, and b*, indicating yellowness/blueness of the PET bottle wall section are as follows:
  • Example 4 (1000 ppm) 93.89 2.10
  • Example 1 (1000 ppm) 93.79 2.22
  • Comparative Example 1 (1258 ppm) 95.51 6.25 Comparative Example 3 (873 ppm) 95.33 5.61
  • the comparative examples exhibit similar L* values (brightness) but with simultanouesly high yellowness (b* values). Measurements for these values are preferably at least 90 for L* and at most about 2.5 for b* to signify a low yellowing resin with very low amounts of graying bluing agents, and thus a very bright appearance.
  • Attempts to reduce the b* value (e.g., yellowness) of the comparative UN absorbers involved the addition of bluing agents which thus reduced the brightness (L*) of the target resins to values below the target value of 90.
  • Polyester plaques containing the UN absorber additives were prepared using standard compounding methods. Eachplaque had a surface area of 12.5 in 2 .
  • the PET plaques were made using ClearTuf® 8006 PET (from M&G Polymers) resin while the PEN plaques were prepared using PEN Hypertuf® (from M&G Polymers).
  • the extract solutions were then analyzed spectrophotometrically to determine if any UN absorbers had been extracted from the target resins.
  • the extracts were analyzed spectrophotometrically to determine the presence or absence of extracted colorant.
  • ABeckman® DU650 spectrophotometerwith a 10.00 cm path length cell was used. The instrument was first zeroed using the extract obtained from the uncolored polyester plaques. The extract from the extraction of the plaques containing the various additives was then scanned through the ultraviolet/visible range to determine the presence or absence of detectable peaks at the additives' ⁇ max and the corresponding absorbency. Higher absorption level at the additives' ⁇ m ax would indicate higher extraction level.
  • the term "heated alcohol extraction test" as it pertains to this invention encompasses such an analytical procedure as this in association with this invention.
  • inventive UN absorbers show much reduced extraction level that that of the comparative examples and the commercial UN absorbers.
  • inventive UN absorbers are more suitable for food contact applications, h the case of Comparative Examples 8 and 9, such results as noted above in Table 6 indicate that introduction of such UN absorbers (from the Pruett et al. patent) during the injection molding stage, rather than during the actual polymerization stage of the target thermoplastic results in highly undesirable extraction measurements, particularly in comparison with the polymeric UN absorbers of the instant invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention porte sur de nouveaux composés absorbant l'UV liquides, à très faible coloration (ce qui permet de les utiliser sans nécessiter l'adjonction d'importantes quantités d'autres colorants pour combattre la décoloration) et fournissant une protection très efficaces contre des plages d'UV que n'offraient pas les absorbeurs d'UV à faible coloration précédents. Lesdits composés assurent une protection excellente, peu onéreuse, et bénéfique contre l'exposition aux UV dans différents milieux, dont non exclusivement les plastiques transparents. Ce sont d'une manière générale des polymères comprenant différentes longueurs de chaînes de polyoxyalkylènes, et sous forme de liquides ce qui facilite leur manipulation et leur introduction dans les milieux cibles. Ils présentent de plus des propriété de de migration extrêmement lente ce qui assure une protection à long terme du milieu cible. L'invention porte également sur les produits finaux, sur une large gamme de types de produits spécifiques présentant ces caractéristiques bénéfiques, et sur les procédés de fabrication desdits composés, et sur des procédés de production de produits finaux transparents protégés contre les UV.
PCT/US2002/023805 2001-08-21 2002-07-26 Absorbeurs d'uv a faible coloration et compositions les contenant WO2003018682A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2003523537A JP2005501155A (ja) 2001-08-21 2002-07-26 低色調の紫外線吸収剤化合物およびその組成物
EP02744885A EP1423461A4 (fr) 2001-08-21 2002-07-26 Absorbeurs d'uv a faible coloration et compositions les contenant
BR0211395-3A BR0211395A (pt) 2001-08-21 2002-07-26 Compostos absorvedores de ultravioleta de fraca intensidade de cor e composições dos mesmos

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US09/934,380 2001-08-21
US09/934,380 US6596795B2 (en) 2001-08-21 2001-08-21 Low-color vanillin-based ultraviolet absorbers and methods of making thereof
US09/934,374 2001-08-21
US09/934,376 2001-08-21
US09/934,376 US6559216B1 (en) 2001-08-21 2001-08-21 Low-color ultraviolet absorber compounds and compositions thereof
US09/934,374 US20030078328A1 (en) 2001-08-21 2001-08-21 Low-color resorcinol-based ultraviolet absorbers and methods of making thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1419347A1 (fr) * 2001-08-21 2004-05-19 Milliken & Company Absorbeurs d'ultraviolets a faible couleur utilises dans des applications de protection grandes longueurs d'onde contre les uv
CN100424067C (zh) * 2003-04-28 2008-10-08 美利肯公司 改进的热塑性和热固性材料长紫外波长防护用低色度紫外线吸收剂
WO2009068492A2 (fr) * 2007-11-28 2009-06-04 Basf Se Mélange de stabilisants liquide
WO2016053662A1 (fr) * 2014-09-30 2016-04-07 Transitions Optical, Inc. Absorbeurs de lumière ultraviolette
CN113603834A (zh) * 2021-08-05 2021-11-05 深圳市辉灿科技有限公司 一种吸收led光源蓝光的液体的制备方法及低蓝光led灯具
CN114989409A (zh) * 2022-08-04 2022-09-02 北京金泰毅农作物科技有限公司 香草醛改性物及其制备吡唑醚菌酯·喹啉铜悬浮剂的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11638439B2 (en) * 2018-05-21 2023-05-02 Agthia Vitamin D-fortified water and method of manufacturing thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
US6207740B1 (en) * 1999-07-27 2001-03-27 Milliken & Company Polymeric methine ultraviolet absorbers

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US6207740B1 (en) * 1999-07-27 2001-03-27 Milliken & Company Polymeric methine ultraviolet absorbers

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See also references of EP1423461A4 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1419347A1 (fr) * 2001-08-21 2004-05-19 Milliken & Company Absorbeurs d'ultraviolets a faible couleur utilises dans des applications de protection grandes longueurs d'onde contre les uv
EP1419347A4 (fr) * 2001-08-21 2005-03-30 Milliken & Co Absorbeurs d'ultraviolets a faible couleur utilises dans des applications de protection grandes longueurs d'onde contre les uv
CN100424067C (zh) * 2003-04-28 2008-10-08 美利肯公司 改进的热塑性和热固性材料长紫外波长防护用低色度紫外线吸收剂
WO2009068492A2 (fr) * 2007-11-28 2009-06-04 Basf Se Mélange de stabilisants liquide
WO2009068492A3 (fr) * 2007-11-28 2009-10-15 Basf Se Mélange de stabilisants liquide
US8680183B2 (en) 2007-11-28 2014-03-25 Basf Se Liquid stabilizer mixture
WO2016053662A1 (fr) * 2014-09-30 2016-04-07 Transitions Optical, Inc. Absorbeurs de lumière ultraviolette
US10619098B2 (en) 2014-09-30 2020-04-14 Transitions Optical, Inc. Ultraviolet light absorbers
CN113122269A (zh) * 2014-09-30 2021-07-16 光学转变公司 紫外光吸收剂
CN113122269B (zh) * 2014-09-30 2024-05-28 光学转变公司 紫外光吸收剂
CN113603834A (zh) * 2021-08-05 2021-11-05 深圳市辉灿科技有限公司 一种吸收led光源蓝光的液体的制备方法及低蓝光led灯具
CN114989409A (zh) * 2022-08-04 2022-09-02 北京金泰毅农作物科技有限公司 香草醛改性物及其制备吡唑醚菌酯·喹啉铜悬浮剂的应用
CN114989409B (zh) * 2022-08-04 2022-11-25 北京金泰毅农作物科技有限公司 香草醛改性物在制备吡唑醚菌酯·喹啉铜悬浮剂中的应用

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BR0211395A (pt) 2004-08-17
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CN1545534A (zh) 2004-11-10
CN1255463C (zh) 2006-05-10
JP2005501155A (ja) 2005-01-13

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