CA2205099A1 - Fluorescent polymers and coating compositions - Google Patents
Fluorescent polymers and coating compositionsInfo
- Publication number
- CA2205099A1 CA2205099A1 CA002205099A CA2205099A CA2205099A1 CA 2205099 A1 CA2205099 A1 CA 2205099A1 CA 002205099 A CA002205099 A CA 002205099A CA 2205099 A CA2205099 A CA 2205099A CA 2205099 A1 CA2205099 A1 CA 2205099A1
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- Canada
- Prior art keywords
- fluorescent
- methacrylate
- polymer
- group
- ethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Luminescent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Disclosed is a method of preparing a fluorescent polymer, whereby an ethylenically unsaturated monomer is copolymerized with a polynuclear aromatic hydrocarbon or a substituted aromatic derivative thereof, such that the resultant polymer is fluorescent. Also disclosed are coating compositions containing such fluorescent polymers.
Description
CA 0220~099 1997-0~-12 FLUORESCENT POLYMERS AND COATING COMPOSITIONS
BACKGROUND OF THE ~VErNTlON
The present invention relates to a method for preparing fluorescent polymers, and coating compositions containing such fluorescent polymers. In particular, the 5 present method relates to the inclusion of fluorescent compounds in the preparation of polymers useful in coating compositions such that the resultant compositions are detectable by fluorescent means.
A method for preparing a fluorescent polymer is disclosed in US 5,125,929 (Amey). There, a Michael addition reaction produces a linear aminoacid polymer 10 which is fluorescent. In this case, the fluorescence is produced by the polymer backbone. This method is limited by the nature of its chemistry. Moreover, most polymers produced by a Michael addition reaction will not have fluorescence.
US 5,043,406 (Fong) discloses a method for incorporating fluorescent moieties into acrylamide polyrners by copolymerizing acrylamide monomers with monomers 15 containing pendant fluorescent moieties. The principal limitation to this method is the lack of commercially available monomers containing pendant fluorescent moieties. Even if other monomers could be modified to incorporate pendant fluorescent moieties, the increased cost of doing so would make the cost of suchfluorescent polymers prohibitive.
Both the methods described by Amey and Fong are limited in applicability, either by virtue of the nature of the chemistry involved, or by the lack of available fluorescent starting materials. What is needed is a method for incorporating fluorescence into a broad variety of polymers, thus permitting broader usage of such fluorescent polymers.
STATEMENT OF THE INVENTION
A first embodiment of the present invention is directed to a method for preparing a fluorescent polymer, comprising copolymerizing one or more ethylenically unsaturated monomers with a fluorescent compound selected from thegroup consisting of polynuclear aromatic hydrocarbons and their substituted aromatic derivatives; wherein the resultant polymer contains a fluorescent group.
A second embodiment of the present invention is directed to a coating composition having enhanced UV durability, comprising a fluorescent polymer prepared by copolymerizing an ethylenically unsaturated monomer with a fluorescent compound selected from the group consisting of: polynuclear aromatic CA 0220~099 1997-0~-12 hydrocarbons and their substituted aromatic derivatives; and ethylenically unsaturated monomers having pendant fluorescent functionality.
A third embodiment of the present invention is directed to a method for identifying and quantifying the amount, if any, of fluorescent polymer contained in 5 a coating composition, such method comprising the steps of: (a) obtaining a sample of the coating composition or resulting coating to be tested; (b) detecting the fluorescence; and (c) measuring the intensity or the wavelength of the fluorescence of the fluorescent polymer contained in the sample.
DETAILED DESCRIPTION OF THE ~VENTION
As used in this specification, the following terms have the following definitions, unless the context dearly indicates otherwise. "Latex" or "latex composition" refers to a dispersion of a water-insoluble polymer which may be prepared by conventional polymerization techniques such as, for example, by emulsion polymerization. "Latex" also refers to polymer dispersed in an aqueous 15 composition, wherein the polymer can be prepared directly in the aqueous medium, or first prepared in a non-aqueous medium (e.g., using solution polymerization) and then subsequently dispersed in the aqueous medium. "Fluorescent" or "fluorescence" refers to a compound which, when excited by radiation, occupies asecond excited state which is said to "fluoresce" or emit radiation at a lower energy 20 (longer wavelength) than the original excited state. "Chromophore" refers to a compound having fluorescence which is capable of being covalently attached to a polymer. "Backbone" refers to the main chain of a polymer exclusive of pendant or end groups; "pendant" refers to a group suspended from the main chain of a polymer; and "end" refers to a group suspended from the end of a polymer chain.
25 "PVC" used in reference to paint means pigment volume concentration. The terms "group" and "moiety" are used interchangeably. The following abbreviations are used: cm = centimeter, mm = millimeters, nm = nanometers, mL = milliliters, HPLC= high pressure liquid chromatography, UV = ultraviolet, ai = active ingredient.Ranges specified are to be read as inclusive, unless specifically identified otherwise.
It has now been discovered that certain weak polymerization inhibitors can be used to incorporate fluorescent moieties into a broad variety of polymers by free radical copolymerization of the polymerization inhibitors with the appropriate monomers. These polymerization inhibitors can be broadly classified as polynuclear aromatic hydrocarbons. Examples of such polynuclear aromatic hydrocarbon chromophores can be found in Russian Patent 478839 (Gladyshev) and "Polymerization Inhibition by Aromatic Compounds," T. Polymer Sci., 52:31 (1961).
CA 02205099 1997-0~-12 It has also been found that substituted aromatic derivatives of such polynucleararomatic hydrocarbons can also be used in this fashion. Such derivatives are those wherein the polynuclear aromatic hydrocarbon is substituted without loss of aromaticity. These substituents include but are not limited to: C1 12 branched or straight chain alkyl or aryl groups optionally substituted with heteroatoms;
carboxylic acids and esters thereof; sulfonic acids and derivatives thereof; cyano groups; and halogens. Preferred polynuclear aromatic hydrocarbons include:
naphthalene, anthracene, phenanthrene, fluoranthene, acridine, carbazole, pyrene, chrysene, triphenylene, perylene, and their substituted aromatic derivatives. It is 10 especially preferred to use naphthalene, anthracene, phenanthrene, fluoranthene, and their substituted aromatic derivatives. Combinations of chromophores can also be used.
In another embodiment of the present invention, the fluorescent polymers are used as markers for product identification. In this respect, other types of fluorescent 15 polymers can be utilized. For example, such polymers can be prepared by copolymerizirlg the appropriate monomers with an ethylenically unsaturated monomer having pendant fluorescent functionality.
Detection of the fluorescent polymers is accomplished by taking a sample of the coating composition or the resulting (applied) coating, and analyzing the sample 20 to determine the fluorescence wavelength, and the intensity of the fluorescence emission. HPLC or GPC analysis may be used to determine whether or not the fluorescent moiety is covalently attached to the polymer. (See, for example, S.
Sosnowski et al., T. Polymer Sci., Part A: Polymer Chemistry 32: 1497 (1994).) If a sample of the applied coating is used, it may be useful to extract the polymer from 25 the other coating components prior to analysis, in accordance with methods known to those skilled in the art.
Examples of ethylenically unsaturated monomers having pendant fluorescent functionality can be found in: US 5,043,406 (Fong), S. Sosnowski et al., J. Polymer ~, Part A: Polymer Chemistry 32: 1497 (1994), C. L. Zhao et al., Macromolecules,30 23:4082 (1990), E. M. Boczar et al., Macromolecules, 26:5772 (1993), M. A. Fox et al., Macromolecules, 23:4533 (1990), and C. Simionescu et al., J. Polymer Sci., 23:2089 (1985). Preferred ethylenically unsaturated monomers having pendant fluorescent functionality include: naphthylmethyl methacrylate, naphthylethyl methacrylate, 9-anthryl methacrylate, 9-anthrylmethyl methacrylate, 2-(9-anthryl)ethyl methacrylate, 35 1'-(9-anthryl)ethyl methacrylate, 3-hydroxy-2-methylene-3-(1-naphthyl)propionic acid, N-dibenzosuberenyl acrylamide, (9-phenanthryl)methyl methacrylate, and 9-vinyl phenanthrene. It is especially preferred to use naphthylethyl methacrylate, 9-CA 0220~099 1997-0~-12 1- DN ~6 ()35 anthryl methacrylate, 3-hydroxy-2-methylene-3-(1-naphthylpropionic acid, (9-phenanthryl)methyl methacrylate, 9-vinyl phenanthrene, or combinations thereof.
Regardless of whether the chromophore being incorporated into the polymer is a polynuclear aromatic hydrocarbon or an ethylenically unsaturated monomer 5 having pendant fluorescent functionality, the method of incorporation is similar.
The chromophore is treated as another component in the free radical polymerization process, and is generally added to the monomers at the start of the reaction;
however, variations from this procedure are known to those skilled in the art. The polymerization can be conducted in any medium, including aqueous media, polar or10 non-polar organic solvents, or combinations thereof. Such polymerization techniques are well known to those skilled in the art, and will not be further discussed herein.
The amount of chromophore utilized in the preparation of the fluorescent polymers of the present invention will vary, depending on the type of chromophore 15 and how the chromophore is attached to the resultant polymer (whether it is apendant or end group, or ir.serted into the polymer backbone); however, the chromophores will typically be added to the monomer mixture in an amount between 0.001 and 3.0 wt%. It is preferred to add chromophore in an amount between 0.005 and 1.0 wt%, and most preferred to add between 0.01 and 0.5 wt%.
Typical comonomers that are useful in this invention are those that are capable of undergoing free radical polyrnerization. The choice of comonomer willvary, depending on the choice of chromophore. As used in this specification, theterm "acrylic" is used in a general sense to describe polymers wherein at least one of the monomers is of the acrylic or methacrylic type, including acrylic and methacrylic acids, esters of acrylic acid or methacrylic acid, and substituted derivatives thereof.
"(Meth)acryl-" includes both acrylic and methacrylic derivatives. Such monomers are well known in the art. Examples of such acrylic monomers include: alkyl (meth)acrylates such as methyl methacrylate, ethyl acrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, isopropylacrylate, isobutyl acrylate, n-amyl acrylate, n-propyl acrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, neopentyl acrylate, n-tetradecyl acrylate, n-tetradecyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, cyclopentyl methacrylate, n-decyl methacrylate, and the like; other acrylate and methacrylate esters such as 2-bromoethyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-methoxybutyl acrylate, 2-methoxybutyl methacrylate, CA 0220~099 1997-0~-12 DN 96{)35 and 2-n-butoxyethyl methacrylate; active hydrogen-functional monomers induding hydroxy-substituted (meth)acrylates such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate; (meth)acrylate including sulfonic acids such as sulfoethyl methacrylate, and sulfopropyl acrylate; and phosphoric acids such as 2-5 phosphoethyl (meth)acrylate.
Additional comonomers which can be used in the present invention include:
butadiene, styrene, alpha-methyl styrene, sodium styrene sulfonate, vinyl toluene, acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, ethyl acrylonitrile, methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl 10 vinyl ether, 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-butaneglycol divinyl ether, diethyleneglycol divinyl ether, vinyl esters such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl 2-ethylhexonate and vinyl decanoate; allyl chloride, methallyl chloride, vinylidene chloride, vinyl chloride, vinyl fluoride, vinylidene fluoride, sodium vinyl sulfonate, 15 butyl vinyl sulfonate, phenyl vinyl sulfone, methyl vinyl sulfone, N-vinyl pyrrolidinone, N-vinyl oxazolidinone, acrolein, acrylamide, methacrylamide, N,N-dimethyl(meth)acrylamide, methylolacrylamide, N-butoxy(meth)acrylamide, isobutoxy(meth)acrylamide and the like, allyl triethoxysilane, allyl tris(trimethylsiloxy) silane, 3-acryloxypropyltrimethoxy silane, and the like; other 20 ethylenically unsaturated carboxylic acids and their esters, such as dialkyl and trialkyl esters of di-and tri-carboxylic acids such as itaconic acid and the like, including di(2-ethylhexyl) maleate, dibutyl maleate, dimethyl fumarate, dimethylitaconate, diethyl citraconate, trimethyl aconitate, diethyl mesaconate, di(2-ethylhexyl) itaconate, di-(2-chloroethyl) itaconate, maleic acid, maleic anhydride, 25 fumaric acid, itaconic acid; and olefins, such as diisobutylene, 1-octene, 1-decene, 1-hexadecene and the like.
These types of monomers are typically polymerized in the presence of water-soluble or oil-soluble initiators. Examples of useful initiators include: persulfates, peroxides, hydroperoxides, percarbonates, peracetates, perbenzoates, azo-functional 30 compounds and other free-radical generating species.
Surfactants are commonly used in emulsion or dispersion polymerization to provide stability, as well as to control particle size. Conventional surfactants include anionic or nonionic emulsifiers or their combination. Typical anionic emulsifiers include but are not limited to: alkali or ammonium alkyl sulfates, alkali or 35 ammonium alkylether sulfates, alkali or ammonium alkylarylether sulfates, alkyl sulfonates, salts of fatty acids, esters of sulfosuccinic acid salts, alkyl diphenylether disulfonates, and salts or free acids of complex organic phosphate esters. Typical CA 0220~099 1997-0~-12 ~ DN 96 035 nonionic emulsifiers include but are not limited to: polyethers, e.g. ethylene oxide and propylene oxide condensates which include straight and branched chain aL~yl and alkylaryl polyethylene glycol and poly~ro~ylene glycol ethers and thioethers, alkyl phenoxypoly(ethyleneoxy) ethanols having aL~cyl groups containing from about 7 to about 18 carbon atoms and having from about 4 to about 100 ethyleneoxy units, and polyoxyalkylene derivatives of hexitol, including sorbitans, sorbides, mannitans, and mannides. Surfactants may be employed in the polymer compositions of the present invention at levels of 0.1 - 3 wt% or greater, based on the total weight of the final composition.
In preparing the fluorescent polymers of the present invention, any chain-transfer agent, or mixtures thereof, may be used to control molecular weight.
Suitable chain transfer agents include, for example, Cl l2 alkyl or functional alkyl mercaptans, aL~cyl or functional alkyl mercaptoaL~anoates, or halogenated hydrocarbons, and may be employed in the poiymer at levels of 0.01 - 10 wt%, based on 15 the weight of the polymer.
It is also sometimes useful to increase molecular weight of the resulting polymers. This can be accomplished by addition of ethylenically unsaturated monomer comprising at least two sites of ethylenically unsaturation. Examples of such compounds include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 20 triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolethane trimethacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dimethallyl chlorendate, diallyl chlorendate, diallyl fumarate, diallyl itaconate, diallyl phthalate, 25 diallyl isophthalate, triallyl isocyanate, triallyl trimellitate, 1,6-hexanediol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, allyl methacrylate, and divinyl benzene. Such compounds may be employed in the polymer at levels of 0.01 -10 wt%, based on the weight of the polymer.
Other optional components that can be included in this invention include co-solvents, pigments, fillers, dispersants, curing agents, wetting agents, anti-foam agents, UV absorbers, antioxidants, biocides, and stabilizers.
The coating compositions of the present invention can be used to provide coatings on suitable substrates such as wood and reconstituted wood products, 35 concrete, asphalt, fiber cement, stone, marble, clay, plastics (for example, polystyrene, polyethylene, ABS, polyurethane, polyethylene terphthalate, polybutylene terphthalate, CA 0220~099 1997-0~-12 polypropylene, polyphenylene, polycarbonate, polyacrylate, polyvinyl chloride, Noryl~), and polysulfone), paper, cardboard, textiles, leather, and metal (ferrous as well as non-ferrous). It has surprisingly been discovered that the inclusion of the fluorescent polymers of the present invention in coating compositions produces in enhanced W5 durability of the resultant coatings. The coating compositions of the present invention are therefore ~l eferdbly used to coat substrates that are routinely subjected to W light (e.g., outdoor applications).
The coating compositions of the present invention can be applied to desired substrates using conventional application techniques such as conventional or airless 10 spray, roll, brush, curtain, flood, and dip-coating methods. Once applied to the substrate, the coating compositions can be cured at ambient or elevated temperatures.
Test Methods Gloss Retention--Films of each test paint were drawn down on Leneta(~) 5C
charts using a 3 mil (0.076 mm) Bird(~) Film Applicator. The films were allowed to 15 dry for seven days at 25 ~C and 50% relative humidity. Then initial readings were taken of the 20~ and 60~ gloss (the light reflected at angles of 20~ and 60~ from the perpendicular) using a Glossgard~) II Glossmeter. The 20~ and 60~ gloss readingswere repeated after Weather-O-meter(~) exposure and reported as a percent retention of the original value. Loss of gloss is a measure of poor durability; thus a higher 20 percent retention indicates better durability.
Dirt Pick-up Resistance--Films of each test paint were drawn down on aluminum "Q" panels (Alodine(~ 1200S) using a 3 mil (0.076 mm) Bird(~ Film Applicator. The films were allowed to dry for seven days at 25 ~C, 50% relative humidity before Weather-O-meter~) exposure. After exposure, a reflectometer was 25 used to measure the Y reflectance of the paint film. The panels were then "soiled"
using an iron oxide slurry (250 g water, 2 drops of an anionic dispersant, 125 g of iron oxide, well dispersed), air dried three hours and oven dried at 60 ~C for one hour. After the panels had cooled to room temperature, the paint films were washed under running water using a cheesecloth pad, and air dried for four hours. The 30 reflectometer was used to remeasure the Y-reflectance over the soiled area, which was reported as a percent of the original reading. A higher percent retention indicates cleaner paint films, which indicates better durability.
The following examples are presented to illustrate further various aspects of the present invention, but are not intended to limit the scope of the invention in any 35 respect. The abbreviations listed below are used throughout the examples.
CA 0220~099 1997-0~-12 AA = Acrylic Acid MMA = Methyl Methac~yla~e BA = Bu~l Acrylate S~ = S~7rene BMA = Butyl Methaaylate AnMA = 9-Anthryl Methacrylate EA = Ethyl Aclylate NEMA = 1-Naphthylethyl Methacrylate MAA= MethaaylicAcid Example 1: Preparation of acrylic latex with ~ -nthryl methacrylate Composition: 47 BA/52 MMA/1 AnMA
The polymerization is carried out in a 1 liter, four-neck, round bottom glass flask equipped with a mechanical blade stirrer, a thermocouple to monitor temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 200 g of deionized water and 0.5 g of sodium dodecylbenzene sulfonate, and then heated to 85 ~C. A monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate,118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.5 g of 9-anthryl methacrylate. The pre-emulsion (12.5 g) was added to the flask, followed by 0.75 g of ammonium persulfate (APS) dissolved in 5 g of water. Fifteen minutes later, a 2.5 hour, linear feed of the remaining pre-emulsion and 0.4 g of APS dissolved in 75 g of deionized water was begun. Heating and cooling were applied as necessary to maintain the reaction temperature at 85 ~C. When the additions were complete, 30 g of deionized water were used to rinse the pre-emulsion container into the flask.After 30 minutes, the flask was cooled to 60 ~C, and 0.003 g of FeSO4 x 7 H2O, 1.5 g of 70% aqueous t-butyl hydroperoxide, and 0.9 g of sodium formaldehyde sulfoxylate in a total of 33.5 g of deionized water were added to the flask mixture.
The reaction mixture was cooled to room temperature and filtered. A polymer latex with a solids content of 41.0 % by weight (wt%), a particle size of 83 nm, and a pH of 2.5 was obtained. The polymer fluoresced at 413 nm (ex 364 nm).
Example 2: Preparation of acrylic latex with l-naphthylethyl methacrylate Composition: 47 13A/52.1 MMA/0.9 NEMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.3 g of naphthylethyl methacrylate. A polymer latex with a solids content of 41.4 wt%, a particle size of 103 nm, and a pH of 2.3 was obtained. The polymer fluoresced at 340 nm (ex 280 nm).
CA 0220~099 1997-0~-12 9 DN ~6{)35 Example 3: Preparation of styrene acrylic latex with 9-anthryl methacrylate Composition: 50 BA/49 Sty/l AnMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodiurn 5 dodecylbenzene sulfonate, 125 g of butyl acrylate, 122.5 g of styrene and 2.3 g of 2.5 g of 9-anthryl methacrylate, and at the end of the reaction 0.003 g of FeSO4 x 7 H2O, 2.5 g of t-butyl hydroperoxide, and 1.5 g of sodium formaldehyde sulfoxylate in a total of 54.5 g of deionized water were added. A polymer latex with a solids content of 34.8 wt%, a particle size of 91 nm, and a pH of 2.2 was obtained. The polymer fluoresced at 413 nm (ex 365 nm).
Example 4: Preparation of styrene acrylic latex with l-naphthylethyl methacrylate Composition: 50 BA/49.1 Sty/0.9 NEMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 125 g of butyl acrylate, 123 g of styrene and 2.3 g ofnaphthylethyl methacrylate. A polymer latex with a solids content of 40.5 wt%, aparticle size of 86 nm, and a pH of 2.2 was obtained. The polymer fluoresced at 340 nm (ex 280 nm).
Example 5: Preparation of acrylic latex with 9-anthryl methacrylate Composition: 99EA/lAnMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 247.5 g of ethyl acrylate, and 2.5 g of 9-anthryl methacrylate. A polymer latex with a solids content of 40.0 wt%, a particle size of 87 nm, and a pH of 2.7 was obtained. The polymer fluoresced at 413 nm (ex 364 nm).
Example 6: Prep~ratinn of acrylic latex with anthracene Composition: 100 BMA//l.0 anthracene The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 250 g of butyl methacrylate and 2.5 g of anthracene (which were stirred together until the anthracene was nearly dissolved), 90 g ofdeionized water and 0.5 g of sodium dodecylbenzene sulfonate. A polymer latex with a solids content of 40.6 wt%, a particle size of 112 nm, and a pH of 1.9 was obtained. The polymer fluoresced at 426 nm (ex 364 nm).
CA 0220~099 1997-0~-12 -1(} DN 96 (135 Example 7: Preparation of acrylic latex with anthracene Composition: 55 BA/43.5 MMA/ 1.5 MAA//l.0 anthracene The polymerization is carried out in a 3 liter, four-neck, round bottom glass flask equipped wi~ a mechanical blade stirrer, a thermocouple to monitor temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 580 g of deionized water, 5.3 g of an ammonium alkylphenol ethoxylate sulfate surfactant (AAESS) 60% ai, and 4.0 g of sodium carbonate. This mixture was then heated to 83 ~C. A monomer pre-emulsion was prepared from 550 g butyl acrylate, 435 g methyl methacrylate, 15 g methacrylic 10 acid, and 10 g anthracene (which were stirred together until the anthracene was nearly dissolved), and 252.5 g deionized water, 17 g of AAESS 60% ai, and 1.0 g of sodium lauryl sulfate. The pre-emulsion (55 g) was added to the flask, followed by 3.0 g of APS dissolved in 17 g of water. Fifteen minutes later, a 3.0 hour feed of the remaining pre-emulsion and 1.5 g of APS dissolved in 90 g of deionized water was15 begun. Heating and cooling were applied as necessary to maintain the reactiontemperature at 83 ~C. When the additions were complete, 35 g of deionized water was used to rinse the pre-emulsion container into the flask. After 30 minutes, the flask was cooled to 65 ~C and 0.012 g of FeSO4 x 7 H2O, 0.012 g of tetrasodium ethylenediaminetetraacetic acid, 4.0 g of 70% aqueous t-butyl hydroperoxide, and20 2.0 g of isoascorbic acid in a total of 132 g of deionized water were added. The pH
was raised with 6.7 g of 28% ammonium hydroxide. The reaction mixture was then cooled to room temperature and filtered. A polymer latex with a solids content of 46.7 wt%, a particle size of 130 nm, and a pH of 6.6 was obtained. The polymer fluoresced at 422 nm (ex 364 nm). Gel permeation chromatography (GPC) using a 25 W detector and a refractive index detector in tandem was used to determine that the fluorescent moieties were covalently attached to the polymer chains.
Example 8: Preparation of acrylic latex with anthracene Composition: 55 BA/43.5 MMA/ 1.5 MAA//0.5 anthracene The procedure of Example 7 was followed except that 5 g of anthracene were 30 used in the pre-emulsion and 2.0 g of t-butyl hydroperoxide and 1.0 g of isoascorbic acid in a total of 68 g of deionized water were used at the end of the polymerization.
A polymer latex with a solids content of 48.9 wt%, a particle size of 126 nm, and a pH of 8.7 was obtained. The polymer fluoresced at 422 nm (ex 364 nm).
CA 0220~099 1997-0~-12 -11- DN '36 035 Example 9 (Comparative): Prep~r~tion of conventi~n-l acrylic latex Composition: 55 BA/43.5 MMA/1.5 MAA
The procedure of Example 7 was followed except that the pre-emulsion was prepared from 175 g deionized water, 17 g of AAESS 60% ai, 550 g butyl acrylate,5 435 g methyl methacrylate, and 15 g of methacrylic acid, and at the end of the polymerization 0.006 g of FeSO4 x 7 H2O, 0.006 g of tetrasodium ethylenediaminetetraacetic acid, 1.0 g of 70% aqueous t-butyl hydroperoxide, and0.5 g of isoascorbic acid in a total of 35 g of deionized water were added. A polymer latex with solids content of 52.2 wt%, a particle size of 124 nm, and a pH of 9.6 was 10 obtained. The polymer did not exhibit fluorescence.
Example 10: Prep~ration of a styrene-acrylic latex with anthracene Composition: 50 BA/46 Sty/4.0 MAA//0.5 anthracene Tne polymerization is carried out in a 3 ~iter, four-neck, round bottom glass flask equipped with a mechanical blade stirrer, a thermocouple to monitor 15 temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 400 g of deionized water and heated to 83 ~C. 3.5 g of ammonium persulfate dissolved in 12 g of deionized water and 18 g (solids basis) of a 60 nm seed latex with 41.5 g deionized water were added. A monomer pre-emulsion was prepared from 500 g butyl acrylate, 460 g styrene, 40 g methacrylic20 acid, and 5 g anthracene (which were stirred together until the anthracene was dissolved), and 295 g deionized water, 8.5 g of AAESS 35% ai, and 3.2 g of sodium lauryl sulfate. The monomer pre-emulsion and 1.2 g of ammonium persulfate in 90 g of deionized water were added to the flask over a three hour period. Heating and cooling were applied as necessary to maintain the reaction temperature at 83 ~C.25 When the additions were complete, 25 g of deionized water was used to rinse the pre-emulsion container into the reaction flask. After 30 minutes, the flask was cooled to 65 ~C and 0.01 g of FeSO4 x 7 H2O, 2.0 g of 70% aqueous t-butyl hydroperoxide, and 1.0 g of isoascorbic acid in a total of 46 g of deionized water were added. The reaction mixture was cooled to room temperature and filtered. A
30 polymer latex with a solids content of 52.7 wt%, a particle size of 216 nm, and a pH
of 2.5 was obtained. The polymer fluoresced at 418 nm (ex 364 nm).
Example 11: Preparation and Evaluation of Semigloss Paints The latex polymers from Examples 7, 8, and 9 were formulated into semigloss paints which were evaluated before and after accelerated weathering. The recipes CA 0220~099 1997-0~-12 for the paint formulations are shown in Table I, and the paint properties are shown in Table II.
Table I: 24 PVC Paint Formulations (all quantities are in grams) Ingredients Paint A Paint B Paint C~
Water n 72 72 Anionic dispersant 3.7 3.7 3.7 Nonionic wetting agent 2.0 2.0 2.0 Hydroxyethyl cellulose (2.5%) 50 50 50 Defoamer 1.0 1.0 1.0 RutileTiO2 264.7 264.7 264.7 Latex 7 518.4 - ---Latex 8 --- 494.9 --Latex 9 -~ --- 463.6 Defoamer 1.0 1.0 1.0 Nonionic wetting agent 3.6 3.6 3.6 Nonionic thickener (20% ai) 15.0 15.0 15.0 Hydroxyethyl cellulose (2.5%) 32 27 27 Water 102.8 127.8 162 Antimicrobialagent 3.0 3.0 3.0 ~Comparative Evaluation of the paints films for exterior durability was done using an Atlas Weather-O-meter(~) for accelerated aging of the films. Gloss retention was determined after 840 hours exposure in the Weather-O-meter(g), and dirt pick-up resistance was determined after 408 hours exposure in the Weather-O-meter(~). The results are summarized in the table below.
Table II: Paint Properties Property Paint A Paint B Paint C*
Initial Gloss 20~ Gloss 31 16 16 60~Gloss 67 59 56 % Gloss Retention 20~ Gloss 110 98 60 60~ Gloss 116 101 89 Dirt Pick-up Resistance 89% 74% 71%
Comparative CA 0220~099 1997-0~-12 The data above show that Paints A and B, each contairling attached anthryl moieties, exhibit improved exterior durability over Paint C, containing no anthryl moieties.
Example 12: Evaluation of Chromophore Moieties Bound to Polymer Samples of polymers prepared with anthracene added during polymerization, and samples of polymers with anthracene added post polymerization were analyzed for free anthracene using reverse phase HPLC. The base polymer had a composition of 41.2 BA/57.5 MMA/1.3 MAA.
The samples were diluted 1:10 with methanol and shaken for two hours. The 10 diluted samples were then centrifuged at 45,000 rpm for 15 minutes, and the supernatant analyzed. (Further dilution of the sample may be required if the level in the sample is outside the calibration range.) The analysis was done using a Perkin-Elmer(~3 Series 4 HPLC with a Supelco(~) LC-18-DB column (25 cm x 4 mm) using a mobile phase of acetonitrile/water (95/5) at a flow rate of 1 mL/min. Detection was 15 by fluorescence with an excitation wavelength of 250 nm and a fluorescence detection wavelength of 398 nm.
Added Anthracene (ppm)1 Sample DuringPolym~ri7~tion PostPolym~n7.~tion Free Anthracene (ppm) ppm based on total emulsion weight
BACKGROUND OF THE ~VErNTlON
The present invention relates to a method for preparing fluorescent polymers, and coating compositions containing such fluorescent polymers. In particular, the 5 present method relates to the inclusion of fluorescent compounds in the preparation of polymers useful in coating compositions such that the resultant compositions are detectable by fluorescent means.
A method for preparing a fluorescent polymer is disclosed in US 5,125,929 (Amey). There, a Michael addition reaction produces a linear aminoacid polymer 10 which is fluorescent. In this case, the fluorescence is produced by the polymer backbone. This method is limited by the nature of its chemistry. Moreover, most polymers produced by a Michael addition reaction will not have fluorescence.
US 5,043,406 (Fong) discloses a method for incorporating fluorescent moieties into acrylamide polyrners by copolymerizing acrylamide monomers with monomers 15 containing pendant fluorescent moieties. The principal limitation to this method is the lack of commercially available monomers containing pendant fluorescent moieties. Even if other monomers could be modified to incorporate pendant fluorescent moieties, the increased cost of doing so would make the cost of suchfluorescent polymers prohibitive.
Both the methods described by Amey and Fong are limited in applicability, either by virtue of the nature of the chemistry involved, or by the lack of available fluorescent starting materials. What is needed is a method for incorporating fluorescence into a broad variety of polymers, thus permitting broader usage of such fluorescent polymers.
STATEMENT OF THE INVENTION
A first embodiment of the present invention is directed to a method for preparing a fluorescent polymer, comprising copolymerizing one or more ethylenically unsaturated monomers with a fluorescent compound selected from thegroup consisting of polynuclear aromatic hydrocarbons and their substituted aromatic derivatives; wherein the resultant polymer contains a fluorescent group.
A second embodiment of the present invention is directed to a coating composition having enhanced UV durability, comprising a fluorescent polymer prepared by copolymerizing an ethylenically unsaturated monomer with a fluorescent compound selected from the group consisting of: polynuclear aromatic CA 0220~099 1997-0~-12 hydrocarbons and their substituted aromatic derivatives; and ethylenically unsaturated monomers having pendant fluorescent functionality.
A third embodiment of the present invention is directed to a method for identifying and quantifying the amount, if any, of fluorescent polymer contained in 5 a coating composition, such method comprising the steps of: (a) obtaining a sample of the coating composition or resulting coating to be tested; (b) detecting the fluorescence; and (c) measuring the intensity or the wavelength of the fluorescence of the fluorescent polymer contained in the sample.
DETAILED DESCRIPTION OF THE ~VENTION
As used in this specification, the following terms have the following definitions, unless the context dearly indicates otherwise. "Latex" or "latex composition" refers to a dispersion of a water-insoluble polymer which may be prepared by conventional polymerization techniques such as, for example, by emulsion polymerization. "Latex" also refers to polymer dispersed in an aqueous 15 composition, wherein the polymer can be prepared directly in the aqueous medium, or first prepared in a non-aqueous medium (e.g., using solution polymerization) and then subsequently dispersed in the aqueous medium. "Fluorescent" or "fluorescence" refers to a compound which, when excited by radiation, occupies asecond excited state which is said to "fluoresce" or emit radiation at a lower energy 20 (longer wavelength) than the original excited state. "Chromophore" refers to a compound having fluorescence which is capable of being covalently attached to a polymer. "Backbone" refers to the main chain of a polymer exclusive of pendant or end groups; "pendant" refers to a group suspended from the main chain of a polymer; and "end" refers to a group suspended from the end of a polymer chain.
25 "PVC" used in reference to paint means pigment volume concentration. The terms "group" and "moiety" are used interchangeably. The following abbreviations are used: cm = centimeter, mm = millimeters, nm = nanometers, mL = milliliters, HPLC= high pressure liquid chromatography, UV = ultraviolet, ai = active ingredient.Ranges specified are to be read as inclusive, unless specifically identified otherwise.
It has now been discovered that certain weak polymerization inhibitors can be used to incorporate fluorescent moieties into a broad variety of polymers by free radical copolymerization of the polymerization inhibitors with the appropriate monomers. These polymerization inhibitors can be broadly classified as polynuclear aromatic hydrocarbons. Examples of such polynuclear aromatic hydrocarbon chromophores can be found in Russian Patent 478839 (Gladyshev) and "Polymerization Inhibition by Aromatic Compounds," T. Polymer Sci., 52:31 (1961).
CA 02205099 1997-0~-12 It has also been found that substituted aromatic derivatives of such polynucleararomatic hydrocarbons can also be used in this fashion. Such derivatives are those wherein the polynuclear aromatic hydrocarbon is substituted without loss of aromaticity. These substituents include but are not limited to: C1 12 branched or straight chain alkyl or aryl groups optionally substituted with heteroatoms;
carboxylic acids and esters thereof; sulfonic acids and derivatives thereof; cyano groups; and halogens. Preferred polynuclear aromatic hydrocarbons include:
naphthalene, anthracene, phenanthrene, fluoranthene, acridine, carbazole, pyrene, chrysene, triphenylene, perylene, and their substituted aromatic derivatives. It is 10 especially preferred to use naphthalene, anthracene, phenanthrene, fluoranthene, and their substituted aromatic derivatives. Combinations of chromophores can also be used.
In another embodiment of the present invention, the fluorescent polymers are used as markers for product identification. In this respect, other types of fluorescent 15 polymers can be utilized. For example, such polymers can be prepared by copolymerizirlg the appropriate monomers with an ethylenically unsaturated monomer having pendant fluorescent functionality.
Detection of the fluorescent polymers is accomplished by taking a sample of the coating composition or the resulting (applied) coating, and analyzing the sample 20 to determine the fluorescence wavelength, and the intensity of the fluorescence emission. HPLC or GPC analysis may be used to determine whether or not the fluorescent moiety is covalently attached to the polymer. (See, for example, S.
Sosnowski et al., T. Polymer Sci., Part A: Polymer Chemistry 32: 1497 (1994).) If a sample of the applied coating is used, it may be useful to extract the polymer from 25 the other coating components prior to analysis, in accordance with methods known to those skilled in the art.
Examples of ethylenically unsaturated monomers having pendant fluorescent functionality can be found in: US 5,043,406 (Fong), S. Sosnowski et al., J. Polymer ~, Part A: Polymer Chemistry 32: 1497 (1994), C. L. Zhao et al., Macromolecules,30 23:4082 (1990), E. M. Boczar et al., Macromolecules, 26:5772 (1993), M. A. Fox et al., Macromolecules, 23:4533 (1990), and C. Simionescu et al., J. Polymer Sci., 23:2089 (1985). Preferred ethylenically unsaturated monomers having pendant fluorescent functionality include: naphthylmethyl methacrylate, naphthylethyl methacrylate, 9-anthryl methacrylate, 9-anthrylmethyl methacrylate, 2-(9-anthryl)ethyl methacrylate, 35 1'-(9-anthryl)ethyl methacrylate, 3-hydroxy-2-methylene-3-(1-naphthyl)propionic acid, N-dibenzosuberenyl acrylamide, (9-phenanthryl)methyl methacrylate, and 9-vinyl phenanthrene. It is especially preferred to use naphthylethyl methacrylate, 9-CA 0220~099 1997-0~-12 1- DN ~6 ()35 anthryl methacrylate, 3-hydroxy-2-methylene-3-(1-naphthylpropionic acid, (9-phenanthryl)methyl methacrylate, 9-vinyl phenanthrene, or combinations thereof.
Regardless of whether the chromophore being incorporated into the polymer is a polynuclear aromatic hydrocarbon or an ethylenically unsaturated monomer 5 having pendant fluorescent functionality, the method of incorporation is similar.
The chromophore is treated as another component in the free radical polymerization process, and is generally added to the monomers at the start of the reaction;
however, variations from this procedure are known to those skilled in the art. The polymerization can be conducted in any medium, including aqueous media, polar or10 non-polar organic solvents, or combinations thereof. Such polymerization techniques are well known to those skilled in the art, and will not be further discussed herein.
The amount of chromophore utilized in the preparation of the fluorescent polymers of the present invention will vary, depending on the type of chromophore 15 and how the chromophore is attached to the resultant polymer (whether it is apendant or end group, or ir.serted into the polymer backbone); however, the chromophores will typically be added to the monomer mixture in an amount between 0.001 and 3.0 wt%. It is preferred to add chromophore in an amount between 0.005 and 1.0 wt%, and most preferred to add between 0.01 and 0.5 wt%.
Typical comonomers that are useful in this invention are those that are capable of undergoing free radical polyrnerization. The choice of comonomer willvary, depending on the choice of chromophore. As used in this specification, theterm "acrylic" is used in a general sense to describe polymers wherein at least one of the monomers is of the acrylic or methacrylic type, including acrylic and methacrylic acids, esters of acrylic acid or methacrylic acid, and substituted derivatives thereof.
"(Meth)acryl-" includes both acrylic and methacrylic derivatives. Such monomers are well known in the art. Examples of such acrylic monomers include: alkyl (meth)acrylates such as methyl methacrylate, ethyl acrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, isopropylacrylate, isobutyl acrylate, n-amyl acrylate, n-propyl acrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, neopentyl acrylate, n-tetradecyl acrylate, n-tetradecyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, cyclopentyl methacrylate, n-decyl methacrylate, and the like; other acrylate and methacrylate esters such as 2-bromoethyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-methoxybutyl acrylate, 2-methoxybutyl methacrylate, CA 0220~099 1997-0~-12 DN 96{)35 and 2-n-butoxyethyl methacrylate; active hydrogen-functional monomers induding hydroxy-substituted (meth)acrylates such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate; (meth)acrylate including sulfonic acids such as sulfoethyl methacrylate, and sulfopropyl acrylate; and phosphoric acids such as 2-5 phosphoethyl (meth)acrylate.
Additional comonomers which can be used in the present invention include:
butadiene, styrene, alpha-methyl styrene, sodium styrene sulfonate, vinyl toluene, acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, ethyl acrylonitrile, methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl 10 vinyl ether, 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-butaneglycol divinyl ether, diethyleneglycol divinyl ether, vinyl esters such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl 2-ethylhexonate and vinyl decanoate; allyl chloride, methallyl chloride, vinylidene chloride, vinyl chloride, vinyl fluoride, vinylidene fluoride, sodium vinyl sulfonate, 15 butyl vinyl sulfonate, phenyl vinyl sulfone, methyl vinyl sulfone, N-vinyl pyrrolidinone, N-vinyl oxazolidinone, acrolein, acrylamide, methacrylamide, N,N-dimethyl(meth)acrylamide, methylolacrylamide, N-butoxy(meth)acrylamide, isobutoxy(meth)acrylamide and the like, allyl triethoxysilane, allyl tris(trimethylsiloxy) silane, 3-acryloxypropyltrimethoxy silane, and the like; other 20 ethylenically unsaturated carboxylic acids and their esters, such as dialkyl and trialkyl esters of di-and tri-carboxylic acids such as itaconic acid and the like, including di(2-ethylhexyl) maleate, dibutyl maleate, dimethyl fumarate, dimethylitaconate, diethyl citraconate, trimethyl aconitate, diethyl mesaconate, di(2-ethylhexyl) itaconate, di-(2-chloroethyl) itaconate, maleic acid, maleic anhydride, 25 fumaric acid, itaconic acid; and olefins, such as diisobutylene, 1-octene, 1-decene, 1-hexadecene and the like.
These types of monomers are typically polymerized in the presence of water-soluble or oil-soluble initiators. Examples of useful initiators include: persulfates, peroxides, hydroperoxides, percarbonates, peracetates, perbenzoates, azo-functional 30 compounds and other free-radical generating species.
Surfactants are commonly used in emulsion or dispersion polymerization to provide stability, as well as to control particle size. Conventional surfactants include anionic or nonionic emulsifiers or their combination. Typical anionic emulsifiers include but are not limited to: alkali or ammonium alkyl sulfates, alkali or 35 ammonium alkylether sulfates, alkali or ammonium alkylarylether sulfates, alkyl sulfonates, salts of fatty acids, esters of sulfosuccinic acid salts, alkyl diphenylether disulfonates, and salts or free acids of complex organic phosphate esters. Typical CA 0220~099 1997-0~-12 ~ DN 96 035 nonionic emulsifiers include but are not limited to: polyethers, e.g. ethylene oxide and propylene oxide condensates which include straight and branched chain aL~yl and alkylaryl polyethylene glycol and poly~ro~ylene glycol ethers and thioethers, alkyl phenoxypoly(ethyleneoxy) ethanols having aL~cyl groups containing from about 7 to about 18 carbon atoms and having from about 4 to about 100 ethyleneoxy units, and polyoxyalkylene derivatives of hexitol, including sorbitans, sorbides, mannitans, and mannides. Surfactants may be employed in the polymer compositions of the present invention at levels of 0.1 - 3 wt% or greater, based on the total weight of the final composition.
In preparing the fluorescent polymers of the present invention, any chain-transfer agent, or mixtures thereof, may be used to control molecular weight.
Suitable chain transfer agents include, for example, Cl l2 alkyl or functional alkyl mercaptans, aL~cyl or functional alkyl mercaptoaL~anoates, or halogenated hydrocarbons, and may be employed in the poiymer at levels of 0.01 - 10 wt%, based on 15 the weight of the polymer.
It is also sometimes useful to increase molecular weight of the resulting polymers. This can be accomplished by addition of ethylenically unsaturated monomer comprising at least two sites of ethylenically unsaturation. Examples of such compounds include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 20 triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolethane trimethacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dimethallyl chlorendate, diallyl chlorendate, diallyl fumarate, diallyl itaconate, diallyl phthalate, 25 diallyl isophthalate, triallyl isocyanate, triallyl trimellitate, 1,6-hexanediol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, allyl methacrylate, and divinyl benzene. Such compounds may be employed in the polymer at levels of 0.01 -10 wt%, based on the weight of the polymer.
Other optional components that can be included in this invention include co-solvents, pigments, fillers, dispersants, curing agents, wetting agents, anti-foam agents, UV absorbers, antioxidants, biocides, and stabilizers.
The coating compositions of the present invention can be used to provide coatings on suitable substrates such as wood and reconstituted wood products, 35 concrete, asphalt, fiber cement, stone, marble, clay, plastics (for example, polystyrene, polyethylene, ABS, polyurethane, polyethylene terphthalate, polybutylene terphthalate, CA 0220~099 1997-0~-12 polypropylene, polyphenylene, polycarbonate, polyacrylate, polyvinyl chloride, Noryl~), and polysulfone), paper, cardboard, textiles, leather, and metal (ferrous as well as non-ferrous). It has surprisingly been discovered that the inclusion of the fluorescent polymers of the present invention in coating compositions produces in enhanced W5 durability of the resultant coatings. The coating compositions of the present invention are therefore ~l eferdbly used to coat substrates that are routinely subjected to W light (e.g., outdoor applications).
The coating compositions of the present invention can be applied to desired substrates using conventional application techniques such as conventional or airless 10 spray, roll, brush, curtain, flood, and dip-coating methods. Once applied to the substrate, the coating compositions can be cured at ambient or elevated temperatures.
Test Methods Gloss Retention--Films of each test paint were drawn down on Leneta(~) 5C
charts using a 3 mil (0.076 mm) Bird(~) Film Applicator. The films were allowed to 15 dry for seven days at 25 ~C and 50% relative humidity. Then initial readings were taken of the 20~ and 60~ gloss (the light reflected at angles of 20~ and 60~ from the perpendicular) using a Glossgard~) II Glossmeter. The 20~ and 60~ gloss readingswere repeated after Weather-O-meter(~) exposure and reported as a percent retention of the original value. Loss of gloss is a measure of poor durability; thus a higher 20 percent retention indicates better durability.
Dirt Pick-up Resistance--Films of each test paint were drawn down on aluminum "Q" panels (Alodine(~ 1200S) using a 3 mil (0.076 mm) Bird(~ Film Applicator. The films were allowed to dry for seven days at 25 ~C, 50% relative humidity before Weather-O-meter~) exposure. After exposure, a reflectometer was 25 used to measure the Y reflectance of the paint film. The panels were then "soiled"
using an iron oxide slurry (250 g water, 2 drops of an anionic dispersant, 125 g of iron oxide, well dispersed), air dried three hours and oven dried at 60 ~C for one hour. After the panels had cooled to room temperature, the paint films were washed under running water using a cheesecloth pad, and air dried for four hours. The 30 reflectometer was used to remeasure the Y-reflectance over the soiled area, which was reported as a percent of the original reading. A higher percent retention indicates cleaner paint films, which indicates better durability.
The following examples are presented to illustrate further various aspects of the present invention, but are not intended to limit the scope of the invention in any 35 respect. The abbreviations listed below are used throughout the examples.
CA 0220~099 1997-0~-12 AA = Acrylic Acid MMA = Methyl Methac~yla~e BA = Bu~l Acrylate S~ = S~7rene BMA = Butyl Methaaylate AnMA = 9-Anthryl Methacrylate EA = Ethyl Aclylate NEMA = 1-Naphthylethyl Methacrylate MAA= MethaaylicAcid Example 1: Preparation of acrylic latex with ~ -nthryl methacrylate Composition: 47 BA/52 MMA/1 AnMA
The polymerization is carried out in a 1 liter, four-neck, round bottom glass flask equipped with a mechanical blade stirrer, a thermocouple to monitor temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 200 g of deionized water and 0.5 g of sodium dodecylbenzene sulfonate, and then heated to 85 ~C. A monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate,118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.5 g of 9-anthryl methacrylate. The pre-emulsion (12.5 g) was added to the flask, followed by 0.75 g of ammonium persulfate (APS) dissolved in 5 g of water. Fifteen minutes later, a 2.5 hour, linear feed of the remaining pre-emulsion and 0.4 g of APS dissolved in 75 g of deionized water was begun. Heating and cooling were applied as necessary to maintain the reaction temperature at 85 ~C. When the additions were complete, 30 g of deionized water were used to rinse the pre-emulsion container into the flask.After 30 minutes, the flask was cooled to 60 ~C, and 0.003 g of FeSO4 x 7 H2O, 1.5 g of 70% aqueous t-butyl hydroperoxide, and 0.9 g of sodium formaldehyde sulfoxylate in a total of 33.5 g of deionized water were added to the flask mixture.
The reaction mixture was cooled to room temperature and filtered. A polymer latex with a solids content of 41.0 % by weight (wt%), a particle size of 83 nm, and a pH of 2.5 was obtained. The polymer fluoresced at 413 nm (ex 364 nm).
Example 2: Preparation of acrylic latex with l-naphthylethyl methacrylate Composition: 47 13A/52.1 MMA/0.9 NEMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 118 g of butyl acrylate, 130 g of methyl methacrylate, and 2.3 g of naphthylethyl methacrylate. A polymer latex with a solids content of 41.4 wt%, a particle size of 103 nm, and a pH of 2.3 was obtained. The polymer fluoresced at 340 nm (ex 280 nm).
CA 0220~099 1997-0~-12 9 DN ~6{)35 Example 3: Preparation of styrene acrylic latex with 9-anthryl methacrylate Composition: 50 BA/49 Sty/l AnMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodiurn 5 dodecylbenzene sulfonate, 125 g of butyl acrylate, 122.5 g of styrene and 2.3 g of 2.5 g of 9-anthryl methacrylate, and at the end of the reaction 0.003 g of FeSO4 x 7 H2O, 2.5 g of t-butyl hydroperoxide, and 1.5 g of sodium formaldehyde sulfoxylate in a total of 54.5 g of deionized water were added. A polymer latex with a solids content of 34.8 wt%, a particle size of 91 nm, and a pH of 2.2 was obtained. The polymer fluoresced at 413 nm (ex 365 nm).
Example 4: Preparation of styrene acrylic latex with l-naphthylethyl methacrylate Composition: 50 BA/49.1 Sty/0.9 NEMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 125 g of butyl acrylate, 123 g of styrene and 2.3 g ofnaphthylethyl methacrylate. A polymer latex with a solids content of 40.5 wt%, aparticle size of 86 nm, and a pH of 2.2 was obtained. The polymer fluoresced at 340 nm (ex 280 nm).
Example 5: Preparation of acrylic latex with 9-anthryl methacrylate Composition: 99EA/lAnMA
The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 90 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 247.5 g of ethyl acrylate, and 2.5 g of 9-anthryl methacrylate. A polymer latex with a solids content of 40.0 wt%, a particle size of 87 nm, and a pH of 2.7 was obtained. The polymer fluoresced at 413 nm (ex 364 nm).
Example 6: Prep~ratinn of acrylic latex with anthracene Composition: 100 BMA//l.0 anthracene The procedure of Example 1 was followed, except that the monomer pre-emulsion was prepared from 250 g of butyl methacrylate and 2.5 g of anthracene (which were stirred together until the anthracene was nearly dissolved), 90 g ofdeionized water and 0.5 g of sodium dodecylbenzene sulfonate. A polymer latex with a solids content of 40.6 wt%, a particle size of 112 nm, and a pH of 1.9 was obtained. The polymer fluoresced at 426 nm (ex 364 nm).
CA 0220~099 1997-0~-12 -1(} DN 96 (135 Example 7: Preparation of acrylic latex with anthracene Composition: 55 BA/43.5 MMA/ 1.5 MAA//l.0 anthracene The polymerization is carried out in a 3 liter, four-neck, round bottom glass flask equipped wi~ a mechanical blade stirrer, a thermocouple to monitor temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 580 g of deionized water, 5.3 g of an ammonium alkylphenol ethoxylate sulfate surfactant (AAESS) 60% ai, and 4.0 g of sodium carbonate. This mixture was then heated to 83 ~C. A monomer pre-emulsion was prepared from 550 g butyl acrylate, 435 g methyl methacrylate, 15 g methacrylic 10 acid, and 10 g anthracene (which were stirred together until the anthracene was nearly dissolved), and 252.5 g deionized water, 17 g of AAESS 60% ai, and 1.0 g of sodium lauryl sulfate. The pre-emulsion (55 g) was added to the flask, followed by 3.0 g of APS dissolved in 17 g of water. Fifteen minutes later, a 3.0 hour feed of the remaining pre-emulsion and 1.5 g of APS dissolved in 90 g of deionized water was15 begun. Heating and cooling were applied as necessary to maintain the reactiontemperature at 83 ~C. When the additions were complete, 35 g of deionized water was used to rinse the pre-emulsion container into the flask. After 30 minutes, the flask was cooled to 65 ~C and 0.012 g of FeSO4 x 7 H2O, 0.012 g of tetrasodium ethylenediaminetetraacetic acid, 4.0 g of 70% aqueous t-butyl hydroperoxide, and20 2.0 g of isoascorbic acid in a total of 132 g of deionized water were added. The pH
was raised with 6.7 g of 28% ammonium hydroxide. The reaction mixture was then cooled to room temperature and filtered. A polymer latex with a solids content of 46.7 wt%, a particle size of 130 nm, and a pH of 6.6 was obtained. The polymer fluoresced at 422 nm (ex 364 nm). Gel permeation chromatography (GPC) using a 25 W detector and a refractive index detector in tandem was used to determine that the fluorescent moieties were covalently attached to the polymer chains.
Example 8: Preparation of acrylic latex with anthracene Composition: 55 BA/43.5 MMA/ 1.5 MAA//0.5 anthracene The procedure of Example 7 was followed except that 5 g of anthracene were 30 used in the pre-emulsion and 2.0 g of t-butyl hydroperoxide and 1.0 g of isoascorbic acid in a total of 68 g of deionized water were used at the end of the polymerization.
A polymer latex with a solids content of 48.9 wt%, a particle size of 126 nm, and a pH of 8.7 was obtained. The polymer fluoresced at 422 nm (ex 364 nm).
CA 0220~099 1997-0~-12 -11- DN '36 035 Example 9 (Comparative): Prep~r~tion of conventi~n-l acrylic latex Composition: 55 BA/43.5 MMA/1.5 MAA
The procedure of Example 7 was followed except that the pre-emulsion was prepared from 175 g deionized water, 17 g of AAESS 60% ai, 550 g butyl acrylate,5 435 g methyl methacrylate, and 15 g of methacrylic acid, and at the end of the polymerization 0.006 g of FeSO4 x 7 H2O, 0.006 g of tetrasodium ethylenediaminetetraacetic acid, 1.0 g of 70% aqueous t-butyl hydroperoxide, and0.5 g of isoascorbic acid in a total of 35 g of deionized water were added. A polymer latex with solids content of 52.2 wt%, a particle size of 124 nm, and a pH of 9.6 was 10 obtained. The polymer did not exhibit fluorescence.
Example 10: Prep~ration of a styrene-acrylic latex with anthracene Composition: 50 BA/46 Sty/4.0 MAA//0.5 anthracene Tne polymerization is carried out in a 3 ~iter, four-neck, round bottom glass flask equipped with a mechanical blade stirrer, a thermocouple to monitor 15 temperature, a reflux condenser, means to heat and cool, and a nitrogen atmosphere.
The flask was charged with 400 g of deionized water and heated to 83 ~C. 3.5 g of ammonium persulfate dissolved in 12 g of deionized water and 18 g (solids basis) of a 60 nm seed latex with 41.5 g deionized water were added. A monomer pre-emulsion was prepared from 500 g butyl acrylate, 460 g styrene, 40 g methacrylic20 acid, and 5 g anthracene (which were stirred together until the anthracene was dissolved), and 295 g deionized water, 8.5 g of AAESS 35% ai, and 3.2 g of sodium lauryl sulfate. The monomer pre-emulsion and 1.2 g of ammonium persulfate in 90 g of deionized water were added to the flask over a three hour period. Heating and cooling were applied as necessary to maintain the reaction temperature at 83 ~C.25 When the additions were complete, 25 g of deionized water was used to rinse the pre-emulsion container into the reaction flask. After 30 minutes, the flask was cooled to 65 ~C and 0.01 g of FeSO4 x 7 H2O, 2.0 g of 70% aqueous t-butyl hydroperoxide, and 1.0 g of isoascorbic acid in a total of 46 g of deionized water were added. The reaction mixture was cooled to room temperature and filtered. A
30 polymer latex with a solids content of 52.7 wt%, a particle size of 216 nm, and a pH
of 2.5 was obtained. The polymer fluoresced at 418 nm (ex 364 nm).
Example 11: Preparation and Evaluation of Semigloss Paints The latex polymers from Examples 7, 8, and 9 were formulated into semigloss paints which were evaluated before and after accelerated weathering. The recipes CA 0220~099 1997-0~-12 for the paint formulations are shown in Table I, and the paint properties are shown in Table II.
Table I: 24 PVC Paint Formulations (all quantities are in grams) Ingredients Paint A Paint B Paint C~
Water n 72 72 Anionic dispersant 3.7 3.7 3.7 Nonionic wetting agent 2.0 2.0 2.0 Hydroxyethyl cellulose (2.5%) 50 50 50 Defoamer 1.0 1.0 1.0 RutileTiO2 264.7 264.7 264.7 Latex 7 518.4 - ---Latex 8 --- 494.9 --Latex 9 -~ --- 463.6 Defoamer 1.0 1.0 1.0 Nonionic wetting agent 3.6 3.6 3.6 Nonionic thickener (20% ai) 15.0 15.0 15.0 Hydroxyethyl cellulose (2.5%) 32 27 27 Water 102.8 127.8 162 Antimicrobialagent 3.0 3.0 3.0 ~Comparative Evaluation of the paints films for exterior durability was done using an Atlas Weather-O-meter(~) for accelerated aging of the films. Gloss retention was determined after 840 hours exposure in the Weather-O-meter(g), and dirt pick-up resistance was determined after 408 hours exposure in the Weather-O-meter(~). The results are summarized in the table below.
Table II: Paint Properties Property Paint A Paint B Paint C*
Initial Gloss 20~ Gloss 31 16 16 60~Gloss 67 59 56 % Gloss Retention 20~ Gloss 110 98 60 60~ Gloss 116 101 89 Dirt Pick-up Resistance 89% 74% 71%
Comparative CA 0220~099 1997-0~-12 The data above show that Paints A and B, each contairling attached anthryl moieties, exhibit improved exterior durability over Paint C, containing no anthryl moieties.
Example 12: Evaluation of Chromophore Moieties Bound to Polymer Samples of polymers prepared with anthracene added during polymerization, and samples of polymers with anthracene added post polymerization were analyzed for free anthracene using reverse phase HPLC. The base polymer had a composition of 41.2 BA/57.5 MMA/1.3 MAA.
The samples were diluted 1:10 with methanol and shaken for two hours. The 10 diluted samples were then centrifuged at 45,000 rpm for 15 minutes, and the supernatant analyzed. (Further dilution of the sample may be required if the level in the sample is outside the calibration range.) The analysis was done using a Perkin-Elmer(~3 Series 4 HPLC with a Supelco(~) LC-18-DB column (25 cm x 4 mm) using a mobile phase of acetonitrile/water (95/5) at a flow rate of 1 mL/min. Detection was 15 by fluorescence with an excitation wavelength of 250 nm and a fluorescence detection wavelength of 398 nm.
Added Anthracene (ppm)1 Sample DuringPolym~ri7~tion PostPolym~n7.~tion Free Anthracene (ppm) ppm based on total emulsion weight
Claims (10)
1. A method of preparing a fluorescent polymer, comprising copolymerizing one or more ethylenically unsaturated monomers with a fluorescent compound selected from the group consisting of polynuclear aromatic hydrocarbons, and their substituted aromatic derivatives; wherein the resultant polymer contains a fluorescent group.
2. The method of claim 1, wherein the fluorescent compound is selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluoranthene, acridine, carbazole, pyrene, chrysene, triphenylene, and perylene, and their substituted aromatic derivatives.
3. A coating composition having enhanced UV durability, comprising a fluorescent polymer prepared by copolymerizing an ethylenically unsaturated monomer with a fluorescent compound selected from the group consisting of:
polynuclear aromatic hydrocarbons and their substituted aromatic derivatives; and ethylenically unsaturated monomers having pendant fluorescent functionality.
polynuclear aromatic hydrocarbons and their substituted aromatic derivatives; and ethylenically unsaturated monomers having pendant fluorescent functionality.
4. The method of claim 3, wherein the amount of fluorescent compound is between 0.001 and 3.0 wt% based on the total weight of the monomers.
5. The coating composition of claim 3, wherein the fluorescent compound is selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluoranthene, acridine, carbazole, pyrene, chrysene, triphenylene, perylene, and their substituted aromatic derivatives; and naphthylmethyl methacrylate, naphthylethylmethacrylate, 9-anthryl methacrylate, 9-anthrylmethyl methacrylate, 2-(9-anthryl)ethyl methacrylate, 1'-(9-anthryl)ethyl methacrylate, 3-hydroxy-2-methylene-3-naphthyl)propionic acid, N-dibenzosuberenyl acrylamide, (9-phenanthryl)methyl methacrylate, and 9-vinyl phenanthrene.
6. The coating composition of claim 5, wherein the fluorescent compound is selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluoranthene, and their substituted aromatic derivatives; and naphthylethyl methacrylate, 9-anthryl methacrylate, 3-hydroxy-2-methylene-3-(1-naphthyl)propionic acid, (9-phenanthryl)methyl methacrylate, 9-vinyl phenanthrene, and combinations thereof.
7. A method for identifying and quantifying the amount, if any, of fluorescent polymer contained in a coating composition, such method comprising the steps of:
a) obtaining a sample of the coating composition or resulting coating to be tested;
b) detecting the fluorescence; and c) measuring the intensity or wavelength of the fluorescence of the fluorescent polymer contained in the sample.
a) obtaining a sample of the coating composition or resulting coating to be tested;
b) detecting the fluorescence; and c) measuring the intensity or wavelength of the fluorescence of the fluorescent polymer contained in the sample.
8. The method of claim 7, wherein the method further comprises the step of extracting or separating the fluorescent polymer from the other components of the sample.
9. The method of claim 7, wherein the fluorescent polymer is prepared by copolymerizing an ethylenically unsaturated monomer with a fluorescent compound selected from the group consisting of: polynuclear aromatic hydrocarbons and their substituted aromatic derivatives; and ethylenically unsaturated monomers having pendant fluorescent functionality.
10. The method of claim 9, wherein the amount of fluorescent compound is between 0.001 and 3.0 wt% based on the total weight of the monomers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1823396P | 1996-05-24 | 1996-05-24 | |
| US60/018,233 | 1996-05-24 |
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| Publication Number | Publication Date |
|---|---|
| CA2205099A1 true CA2205099A1 (en) | 1997-11-24 |
Family
ID=21786904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002205099A Abandoned CA2205099A1 (en) | 1996-05-24 | 1997-05-12 | Fluorescent polymers and coating compositions |
Country Status (14)
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| US (2) | US5897811A (en) |
| EP (2) | EP0808855B1 (en) |
| JP (2) | JPH1053607A (en) |
| CN (1) | CN1145649C (en) |
| AU (1) | AU717795B2 (en) |
| BR (1) | BR9703315A (en) |
| CA (1) | CA2205099A1 (en) |
| DE (1) | DE69713954T2 (en) |
| ES (1) | ES2179276T3 (en) |
| ID (1) | ID17365A (en) |
| MY (1) | MY119180A (en) |
| NZ (1) | NZ314817A (en) |
| PL (1) | PL320156A1 (en) |
| TW (1) | TW455625B (en) |
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| AU717795B2 (en) * | 1996-05-24 | 2000-03-30 | Rohm And Haas Company | Fluorescent polymers and coating compositions |
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1997
- 1997-05-12 AU AU20147/97A patent/AU717795B2/en not_active Expired
- 1997-05-12 CA CA002205099A patent/CA2205099A1/en not_active Abandoned
- 1997-05-14 NZ NZ314817A patent/NZ314817A/en unknown
- 1997-05-16 EP EP97303349A patent/EP0808855B1/en not_active Expired - Lifetime
- 1997-05-16 DE DE69713954T patent/DE69713954T2/en not_active Expired - Lifetime
- 1997-05-16 EP EP01130854A patent/EP1205500A3/en not_active Withdrawn
- 1997-05-16 ES ES97303349T patent/ES2179276T3/en not_active Expired - Lifetime
- 1997-05-19 MY MYPI97002168A patent/MY119180A/en unknown
- 1997-05-21 US US08/861,355 patent/US5897811A/en not_active Expired - Lifetime
- 1997-05-23 CN CNB971110522A patent/CN1145649C/en not_active Expired - Lifetime
- 1997-05-23 ID IDP971715A patent/ID17365A/en unknown
- 1997-05-23 PL PL97320156A patent/PL320156A1/en unknown
- 1997-05-26 JP JP9149873A patent/JPH1053607A/en active Pending
- 1997-05-26 BR BR9703315A patent/BR9703315A/en not_active IP Right Cessation
- 1997-06-25 TW TW086108867A patent/TW455625B/en not_active IP Right Cessation
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1999
- 1999-01-13 US US09/231,386 patent/US6344654B1/en not_active Expired - Lifetime
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| JPH1053607A (en) | 1998-02-24 |
| TW455625B (en) | 2001-09-21 |
| EP0808855A2 (en) | 1997-11-26 |
| EP0808855B1 (en) | 2002-07-17 |
| EP1205500A2 (en) | 2002-05-15 |
| JP2007277581A (en) | 2007-10-25 |
| EP1205500A3 (en) | 2002-07-24 |
| US5897811A (en) | 1999-04-27 |
| BR9703315A (en) | 1998-08-11 |
| DE69713954D1 (en) | 2002-08-22 |
| MY119180A (en) | 2005-04-30 |
| EP0808855A3 (en) | 1998-04-01 |
| CN1145649C (en) | 2004-04-14 |
| ID17365A (en) | 1997-12-24 |
| PL320156A1 (en) | 1997-12-08 |
| CN1169439A (en) | 1998-01-07 |
| AU2014797A (en) | 1997-11-27 |
| DE69713954T2 (en) | 2003-01-23 |
| US6344654B1 (en) | 2002-02-05 |
| NZ314817A (en) | 1999-08-30 |
| AU717795B2 (en) | 2000-03-30 |
| JP5216263B2 (en) | 2013-06-19 |
| ES2179276T3 (en) | 2003-01-16 |
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