USOO6683124B2 (12) United States Patent (10) Patent No.: US 6,683,124 B2 Webster (45) Date of Patent: Jan. 27, 2004
(54) FLUORESCENT PIGMENT COMPOSITIONS OTHER PUBLICATIONS (75) Inventor: Joseph R. Webster, Charlotte, NC A. E. N. 5,777. (US) CAS Registry No. 18600–59–4. (73) Assignee: Clariant Finance (BVI) Limited, CAS Registry No. 23949–668. Tortola (VG) CAS Registry No.: 35001-52–6. CAS Registry No.: 82493–14-9. (*) Notice: Subject to any disclaimer, the term of this CAS Registry No. 6759.6. patent is extended or adjusted under 35 CAS Registry No.: 4221-80–1. CAS Registry No.: 7443–25–6. CAS Registry No.: 6337–43–5. (21) Appl. No.: 09/965,689 CAS Registry No.: 96478-09-0. (22) Filed: Sep. 27, 2001 CAS Registry No.: 103597-45–1. O O CAS Registry No. 2725-22-6. (65) Prior Publication Data CAS Registry No.: 42774-15-2. US 2003/0111641 A1 Jun. 19, 2003 CAS Registry No. 980-26-7. 7 CAS Registry No.: 3089–17–6. (51) Int. Cl.' ...... C08K 5/34 CAS Registry No.: 3573-01-1. (52) U.S. Cl...... 524/99: 524/90; 524/102; CAS Registry No.: 6197-30–4. 524/103 CAS Registry No.: 147783–69–5. (58) Field of Search ...... 524/90, 99, 102, CAS Registry No.: 137759–38–7. 524/103 CAS Registry No.: 65816–20–8. CAS Registry No.: 57834–33–0. (56) References Cited Polyamides (General), vol. 19, pp. 454-584. Industrial Organic Pigments, W. Herbst, K. Hunger, 1993; p. U.S. PATENT DOCUMENTS 8, 447, 456-460. 3.969,302 A * 7/1976 Wegmann et al...... 523/333 Patent Abstract for JP 4141025. 4,042,591 A 8/1977 Kaul ....., ..., 260/272 Patent Abstract for WO/9012839. 4,049,376 A 9/1977 Le Pape ------8/162 R Patent Abstract for JP 3047846. 4,067,879 A 1/1978 Vladuchick ...... 260/302 F Patent Abstract for AU 9054330. 4,153,618 A 5/1979 Desai ...... 260/345.2 4.299.959 A 11/1981. Desai ...... 544/283 Each As f 78. 4,335,155. A 6/1982 Blake et al...... 426/565 CASCO 4,405,749 A 9/1983 Nelsen ...... Soo Patent Abstract for JP 01111075. 4,455,424 A 6/1984 Kaul ...... 544/218 Patent Abstract for CA1064500; BR 7607075; AU 7618915; 4,528,311 A 7/1985 Beard et al...... 524/91 AU 5O1592. 4,911,830 A 3/1990 Bromley et al...... 252/301.16 127:24.9416 CA. 4,975,220 A 12/1990 Streitel et al...... 252/301.35 93:16869 CA. 5,051.459 A 9/1991 Slongo et al...... 524/100 90:105588 CA. 5,094,777 A 3/1992 DiPietro ...... 252/301.35 90:24765 CA. 5,236,621 A 8/1993 DiPietro ...... 252/301.35 5,278.216 A 1/1994 Asanuma et al...... 524/394 S& 5,294,664 A 3/1994 Morrison, Jr. et al...... 524/560 5.439,968 A 8/1995 Hyche ...... 524/504 * cited by examiner 5.439,971 A 8/1995 Hyche ...... 524/763 - - - - 5,470,921. A 11/1995 Kaul et al...... 525,432 Primary Examiner-Kriellion A. Sanders 5.880,176 A 3/1999 Kamoto et al. ... 523/172 (74) Attorney, Agent, Or Firm- Anthony A. Bisulca 5,932,353 A 8/1999 Huaring et al. .... 428/423.5 (57) ABSTRACT 5,932,640 A 8/1999 Kaul et al...... 524/102 5,965,261. A 10/1999 Webster ...... 428/364 Fluorescent yellow pigment compositions comprising Pig
5,969,014 A 10/1999 Webster et al...... 524/100 ment Violet 19 or Pigment Yellow 192 and a polyamide, a 5,989,453 A 11/1999 Marcq et al...... 252/301.35 process for the making thereof, and a process for making an 6,110,566 A 8/2000 White et al...... 428/172 article comprising Said fluorescent yellow pigment compo FOREIGN PATENT DOCUMENTS Sition. WO WO 97/43335 11/1997 72 Claims, 19 Drawing Sheets U.S. Patent Jan. 27, 2004 Sheet 1 of 19 US 6,683,124 B2
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009 0000ff), 0000Z -0009|| +0008 000ff 0 (Sd)) US 6,683,124 B2 1 2 FLUORESCENT PIGMENT COMPOSITIONS plate-out fluorescent pigment comprises a pigment compris ing a polymer Selected from the group consisting of polyesters, melamine-formaldehyde resins and triazine FIELD OF THE INVENTION formaldehyde resins and a fluorescent dye, and a copolymer The present invention relates to fluorescent pigment com of ethylene and carbon monoxide. The copolymer has a positions and processes for the making thereof. The present molecular weight of about 1,000 to about 100,000, the invention also relates to articles formed from the fluorescent copolymer containing carbon monoxide residue in the pigment compositions. amount of about 5 to 30% by weight and the copolymer being in Sufficient amount to disperse the pigment. BACKGROUND OF THE INVENTION U.S. Pat. No. 6,110,566 discloses a colored article having It is generally known that fluorescent pigments are often fluorescent properties comprising a Substantially SolventleSS referred to as daylight fluorescent colors. The term pigment polyvinyl chloride matrix, a thioxanthene fluorescent dye, in this context is inaccurate Since by definition a pigment is and a Secondary or tertiary hindered amine light Stabilizer understood to mean a pure unextended inorganic or organic having a molecular weight less than about 1000 grams/mole. colorant that, unlike a dye, is insoluble in all types of 15 Unlike the fluorescent pigment compositions known Solvents. However, most daylight fluorescent colors are not above, the fluorescent pigment compositions of the present truly pigments but really Solid Solutions of fluorescent dyes invention comprise true pigments. Surprisingly, in the in transparent Synthetic resins that are finely ground to a present invention when either Pigment Violet 19 or Pigment particle size in the range of 2 to 5 microns. These pigments Yellow 192 is used in an effective amount in a polyamide, can alternatively be described as transparent plastic materi with or without the presence of other additives, the result is als colored with fluorescent dyes. Polyamides may be used a bright fluorescent yellow polymeric pigment composition. as carrier materials for these compositions. Unlike conven Pigment Yellow 192 (CAS Registry No. 56279-27-7; tional organic pigments, which are usually precipitated TSCA Inventory Name: 7H,11H-Benz delimidazo[4,5':5,6 Single components, fluorescent pigments are Solid State benzimidazo2, 1-allisoquinoline-7,11-dione, 10, 12 Solutions of common fluorescent dyes in polymeric resins or 25 dihydro-) is a polycyclic pigment having the following matrices. Structure: The daylight fluorescent colors belong to the dye families known as rhodamines, fluoresceins, coumarins, (Ia) naphthalimides, benzoxanthenes and acridines. Typical dyes include Basic Red 1, Basic Violet 10, Basic Violet 11, Basic H Violet 16, Basic Yellow 40, Solvent Yellow 44, Solvent O N N Yellow 131 and Solvent Yellow 135. The fluorescent dyes comprise from about 0.1 to about 15% of the total weight of N n the pigment. HN N U.S. Pat. No. 4,153,618 and U.S. Pat. No. 4,299,959 35 disclose a fluorescent pigment consisting of N-Substituted O iminocoumarins. U.S. Pat. No. 4,911,830 discloses low plate-out fluores Pigment Yellow 192 is not known to fluoresce in polya cent pigment concentrates that are of the daylight fluorescent mides. color type. 40 Pigment Violet 19 (CAS Registry No. 1047-16-1; TSCA U.S. Pat. No. 4,975,220 discloses a fluorescent pigment Inventory Name: Quino 2,3-blacridine-7,14-dione, 5,12 composition comprising a fluorescent dye combined in a dihydro) is a quinacridone pigment having the following polyamide-polyester thermoplastic resin. Structure: U.S. Pat. No. 5,094,777 discloses a fluorescent composi 45 tion including a fluorescent dye and a resin carrier. The (Ib) fluorescent dye is of the daylight fluorescent-type and O H belongs to the dye families known as rhodamines, C N fluoresceins, coumarins, naphthalimides, benzoxanthenes, and acridines. 50 U.S. Pat. No. 5,236,621 discloses a thermoplastic organic N C fluorescent pigment that unlike conventional organic pig H ments is a Solid State Solution of fluorescent dyes. The O fluorescent pigment includes from 85 to 99 weight percent polymer matrix and from 1 to 15 weight percent fluorescent 55 Pigment Violet 19 is known to have a range of shades from dye, the weight percent being based on the combined weight red-violet to bluish red and is not known to fluoresce. of the polymer matrix and dye. Quinacridones are not typically recommended for use in U.S. Pat. No. 5,294,664 discloses an aqueous dispersion polyamides. This is generally because of poor dispersion and of a fluorescent pigment comprising a water insoluble also because of burn out in nylon. The term “burn out” refers polymer, fluorescent dye, emulsifiers, and water. The fluo 60 to the situation in which the thermal stability of the colorant rescent pigment which is Suitable for use as an ink in thin is compromised. For example, there may be coloration film printing has an average particle size of from about 0.01 changes. Polyamide fibers are characterized by high tensile to about 1 microns, and the fluorescent pigment which is Strength, modulus and abrasion resistance; however, polya Suitable for use as either a pigment Suspension or a dry mides require Stabilization against thermo-Oxidative and fluorescent pigment has a particle size up to 10 microns. 65 photodegradation for demanding use applications. U.S. Pat. No. 5,439,971 discloses a low plate-out fluo Therefore, further improvement in the stabilization systems rescent pigment of the daylight fluorescent-type. The low for these materials is presently desired in Such end uses as US 6,683,124 B2 3 4 engineering resins, films, coatings, adhesives, plastics, fibers, monofilaments and nonwovens. Polyamides are also H3C CH3 H3C CH3 Suitable in relatively high temperature processing of injec tion moldings. The polyamide Structure contains labile hydrogens and exerts reductive or basic properties which are 5 H-N No c1 N-H problematic from the Standpoint of colorants. For example, O O in polyamide, an organic dye may undergo a significant loSS HC CH HC CH of Shade upon thermal processing at the typical melt pro cessing temperatures for polyamide. It would be desirable to Other additives may also be present in the Single pigment lessen the tendency of polyamide to exert this influence on concentrate or masterbatch. dyes without Sacrificing the desired physical properties of It is yet another object of the present invention to provide polyamides. One aspect of the present invention is directed a fluorescent article. to additives which are dispersed within the polyamide polymer by melt-processing at high temperatures above the 15 BRIEF DESCRIPTION OF THE DRAWINGS glass transition, as in extrudates or moldings. It was unex FIG. 1 is a graph of wavelength in nanometers (nm) pected to achieve fluorescent yellow pigment compositions Versus relative intensity which illustrates the exposure and non-exposure to ultraViolet light of card wraps of polyamide for use in applications Such as polyamide fibers or molded fiber comprising 0.1% by weight of Pigment Violet 19 and articles that have the advantageous properties of the present NYLOSTABOR S-EEDTM at levels of 0%, 1.5%, 3% or 5%, invention. by weight. Currently, industry relies upon expensive fluorescent pig FIG. 2 is a graph of wavelength in nanometers (nm) ments and optical brighteners that are more on the green or Versus relative intensity which illustrates the exposure and blue side of the visible spectrum. Yellow fluorescent pig non-exposure to ultraViolet light of card wraps of polyamide ments are extremely expensive, require ultraViolet 25 fiber comprising 0.1% by weight of Pigment Violet 19 and protection, and are difficult to disperse. Thus, there is a need NYLOSTABOR S-EEDTM at levels of 0%, 1.5%, 3% or 5%, by weight after 100 hours of exposure in a QUV340 device. for fluorescent pigment compositions Such as in the present FIG. 3 is a graph of wavelength in nanometers (nm) invention that are cost effective and easy to disperse yet are Versus relative intensity, which illustrates the exposure of fluorescent in the yellow region of the electromagnetic card wraps of polyamide fiber comprising Pigment Violet 19 Visible spectrum. and NYLOSTABOR S-EEDTM at levels of 0%, 1.5%, 3%, or 5%, by weight to ultraviolet (UV) light after 100 hours of SUMMARY OF THE INVENTION exposure in a QUV340 device wherein the UV exposed Sides of the card wraps have a lower relative intensity verSuS It is an object of the present invention to provide a 35 than the reverse sides of the card wraps which are exposed fluorescent yellow pigment composition comprising an to heat at 70° C. but unexposed to light and have a higher effective amount of Pigment Violet 19 and a polyamide. The relative intensity. fluorescent composition may be in the form of an article, FIG. 4 is a graph of wavelength in nanometers (nm) Such as a molded, cast, or extruded article. It is another 40 versus whole numbers in counts per Second (cps) for a first object of the present invention to provide a fluorescent control nylon-6 fiber comprising 0.1% by weight of Pigment Violet 19 with no UV absorber present and with no ultra yellow pigment composition comprising an effective violet light exposure (initial). amount of Pigment Yellow 192 and a polyamide. The FIG. 5 is a graph of wavelength in nanometers (nm) fluorescent composition may be in the form of an article, versus whole numbers in counts per Second (cps) for a Such as a molded, cast, or extruded article. It is yet another 45 second control nylon-6 fiber comprising 0.1% by weight of object of the present invention to provide a fluorescent Pigment Violet 19 and with no UV absorber present. yellow pigment composition comprising a compound of the FIG. 6 is a graph of wavelength in nanometers (nm) formula versus whole numbers in counts per Second (cps) for a 50 nylon-6 fiber comprising 0.1% by weight of Pigment Violet H3C CH3 H3C CH3 19 and 0.5% by weight of NYLOSTAB(R) S-EEDTM. FIG. 7 is a graph of wavelength in nanometers (nm) versus whole numbers in counts per Second (cps) for a H-N No 1 N-H nylon-6 fiber comprising 0.1% by weight Pigment Violet 19 | 55 and 0.5% by weight of each NYLOSTAB(R) S-EEDTM and HC CH HC CH SANDUVOR(R) VSU. FIG. 8 is a graph of wavelength in nanometers (nm) versus whole numbers in counts per Second (cps) for a with enhanced fluorescence. nylon-6 fiber comprising 0.1% by weight of Pigment Violet 60 19 and 0.5% by weight SANDUVOR(R) VSU. It is another object of the present invention to provide FIG. 9 is a graph of wavelength in nanometers (nm) processes for making fluorescent yellow pigment composi versus whole numbers in counts per Second (cps) for a tions. In one embodiment of the present invention, the nylon-6 fiber comprising 0.1% by weight of Pigment Violet pigment is added to a carrier material to form a single 19 and 1% by weight of SANDUVOR(R) VSU and pigment concentrate or masterbatch. The Single pigment 65 NYLOSTAB(R) S-EEDTM, wherein the fiber was prepared concentrate or masterbatch can also be enhanced by the from a 25% Pigment Violet 19 masterbatch comprising 3% addition of a compound of the formula by weight of NYLOSTAB(R) S-EEDTM. US 6,683,124 B2 S FIG. 10 is a graph of wavelength in nanometers (nm) versus whole numbers in counts per Second (cps) for a (Ia) nylon-6 fiber comprising 0.1% by weight of Pigment Violet 19 and 1% by weight of SANDUVOR(R) VSU, wherein the H fiber was prepared from a masterbatch without 5 O N N NYLOSTAB(R) S-EEDTM (in contrast to FIG. 9). N N HN N FIG. 11 is a graph of wavelength in nanometers (nm) versus whole numbers in counts per Second (cps) for a nylon-6 fiber comprising 0.1% by weight of Pigment Violet O 19 and 0.5% by weight of SANDUVOR(R) PR25. Pigment Yellow 192 is not known to fluoresce in polya FIG. 12 is a graph of wavelength in nanometers (nm) mides. versus whole numbers in counts per Second (cps) for a Pigment Violet 19 (CAS Registry No. 1047-16-1; TSCA 15 Inventory Name: Quino 2,3-blacridine-7,14-dione, 5,12 nylon-6 fiber comprising 0.1% by weight of Pigment Violet dihydro) is a quinacridone pigment having the following 19 and 0.5% by weight of SANDUVOR(R) 3035. Structure: FIG. 13 is a graph of wavelength in nanometers (nm) versus whole numbers in counts per Second (cps) for a (Ib) nylon-6 fiber comprising 0.1% by weight of Pigment Violet O H 19 and 1% by weight of SANDUVOR(R) 3035. N C FIG. 14 is a diagram of the manner in which samples were mounted to test fluorescence. C N FIG. 15 is a graph of wavelength in nanometers (nm) 25 H versus whole numbers in counts per Second (cps) for a O nylon-6 fiber comprising 0.1% by weight of Pigment Red 122 and NYLOSTABOR S-EEDTM at levels of 0%, 1.5%, 3%, Pigment Violet 19 is known to have a range of shades from and 5%, by weight. red-violet to bluish red and is not known to fluoresce. The pigments employed in the present invention achieve fluo FIG. 16 is a graph of wavelength in nanometers (nm) rescence in the polyamide composition of the present inven versus whole numbers in counts per Second (cps) for a tion when present in an effective amount of less than 1.0% nylon-6 fiber comprising 0.1% by weight of Pigment Red by weight based upon the weight of the polyamide. The 122 and either with NYLOSTAB(R) S-EEDTM at 5% by effective amount of the pigment is preferably from about weight or without NYLOSTAB(R) S-EEDTM. 35 0.005% to 0.25% by weight based on the weight of the polyamide. The amount of pigment employed is most pref FIG. 17 is a graph of wavelength in nanometers (nm) erably from about 0.01% to 0.15% by weight based on the versus whole numbers in counts per Second (cps) of a nylon.6 weight of the polyamide. fiber comprising 0.1% by weight of Pigment Violet 19 and The term “polyamide' as used in the context of the either with NYLOSTAB(R) S-FEDTM at 5% by weight or 40 present invention includes the Syntheticaliphatic polyamide, without NYLOSTABOR S-EEDTM. Semi-aromatic polyamide, aromatic polyamides, polyamide FIG. 18 is a graph of wavelength in nanometers (nm) polyester blends, and polyether blocked amides (i.e. trans versus whole numbers in counts per Second (cps) comparing parent nylons). The polyamides of the present invention can a nylon-6 fiber comprising 0.1% by weight of Pigment be prepared by direct amidation, acid chloride reaction, 45 ring-opening polymerization or other conventional methods. Violet 19 without NYLOSTAB(R) S-EEDTM versus a nylon-6 Polyamides of aromatic diamines and aliphatic diacids can fiber comprising 0.1% by weight of Pigment Red 122 also be prepared by the reaction of the corresponding without NYLOSTABOR S-FEDTM. aromatic diisocyanate and diacids. Examples of polyamides FIG. 19 is a graph of wavelength in nanometers (nm) Suitable for use in the present invention include, but are not versus whole numbers in counts per Second (cps) of a 50 limited to, nylon 6; nylon-6,6; nylon-6,9; nylon-6,10; nylon nylon-6 fiber comprising 0.1% by weight of Pigment Violet 6,11; nylon-6,12; nylon 4,6; nylon 11, nylon 12, nylon 19 and 5% by weight of NYLOSTAB(R) S-EEDTM versus a 12,12; nylon 13; nylon 13,13; and copolymerS Such as nylon-6 fiber comprising 0.1% by weight of Pigment Red nylon-6,6/6; nylon-6,6/6,10; nylon 6/11; nylon 6/12; blends 122 and 5% by weight of NYLOSTAB(R) S-EEDTM. of polyamides Such as nylon-6.6 or nylon 6 with Syndiotactic 55 polystyrene; and copolymers of polyamides Such as nylon 6,T/6.I/6,6; nylon-6,T/6,6; nylon-6,T/D,T; nylon-6,T/6; DESCRIPTION OF THE PREFERRED nylon-6, T/6,I; block copolymerS Such as polyether EMBODIMENTS polyamide block copolymers, poly(m- phenyle net is ophthal amide), poly (p- Pigment Violet 19 and Pigment Yellow 192 are pigments 60 phenyleneterephthalamide); random copolymers; and graft that can be used in effective amounts to produce the fluo copolymers. Manufacturers of Such polyamides include rescent pigment compositions of the present invention. Amoco, BASF, DSM, E.I. dupont, Mitsui, Honeywell, Pigment Yellow 192 (CAS Registry No. 56279-27-7; TSCA Mohawk, Monsanto, Shaw Industries, Akzo, Bayer, Elf Inventory Name: 7H,11H-Benz deimidazo[4',5':5,6 Autochem, Rhodia, Nyltech, Shakespeare, Solutia, and ben Zimidazo2, 1-allisoquinoline-7,11-dione, 10, 12 65 Beaulieu of America, Inc. dihydro-) is a polycyclic pigment having the following The term “polyamide' also includes formulated polya Structure: mides Such as conventional impact toughened polyamide US 6,683,124 B2 7 8 and reinforced polyamide containing glass fiber, mineral or dimethylethyl)-2-ethoxyphenyl-N'-(2-ethylphenyl) (TSCA glass/mineral combinations. The present invention can be Inventory Name) (CAS Registry No. 35001-52-6) which is practiced with polyamides regardless of the polymer mor commercially available as SANDUVOR(R) EPU from Clari phology. Amorphous, Semi-crystalline or highly crystalline ant and TINUVINGR 315 from Ciba Specialty Chemicals. polyamides as well as blends of different crystallinity are Another oxanilide that may be used is ethanediamide, N-(2- benefited. The fibers may also be in a bicomponent or ethoxyphenyl)-N'-(4-isododecylphenyl) (DSL Inventory biconstituent form. Among the Sources for commercially Name) (CAS Registry No. 82493-14-9) which is commer available polyamide resins are BASF, DSM, and E.I. cially available as SANDUVOR(R) 3206 from Clariant. duPont. Formulated polyamides are commercially available A hindered benzoate UV absorber that may be used is from Ferro Corporation, Hanna Engineered Materials, Huls benzoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, hexa America, and A. Schulman. Reinforced polyamides are decyl ester (TSCA Inventory Name) (CAS Registry No. commercially available from Suppliers such as DSM RIM 67845-93-6) commercially available as CYASORB(R) 2908 Nylon. from Cyanamid. Another hindered benzoate UV absorber Preferred polyamides include homopolyamides and/or that may be used is benzoic acid,3,5-bis(1,1-dimethylethyl)- copolyamides made from () -aminocaproic acid, 15 4-hydroxy-, 2,4-bis(1,1-dimethylethyl)phenyl ester (TSCA () -amino et antholic acid, () -aminocaprylic acid, Inventory Name) (CAS Registry No. 4221-80-1) which is () -aminope largo nic acid, () -amino capric acid, commercially available as FERRO(R AM 340 from Ferro ()-aminoundecanoic acid, (D-aminolauric acid, caprolactam, Corp. lactam-7, lactam-8, lactam-9, lactam-10, lactam-11 and/or A benzophenone that may be used is methanone, laurolactam. Preferred polyamides also include polyamides 2-hydroxy-4-(octyloxy)phenylphenyl (TSCA Inventory made from dimethylenediamine, trimethylene diamine, Name) (CAS Registry No. 1843-05-6) which is a broad UV tetramethylene diamine, pentamethylene diamine, absorber that absorbs UV radiation from 290 to 390 nm and hexamethylenediamine, polyetherdiamine and mixtures is commercially available from Clariant as SANDUVOROR thereof as well as Oxalic acid, malonic acid, Succinic acid, 3035. glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic 25 Abenzylidene malonate that may be used is propanedioic acid, Sebacic acid, nonedicarboxylic acid, decanedicarboxy acid, (4-methoxyphenyl)methylene-, dimethyl ester lic acid, undecanedioic acid, dodecanedioic acid, dimerised (TSCA Inventory Name) (CAS Registry No. 7443-25-6). fatty acids and mixtures thereof. This particular UV absorber is commercially available from Conventional additives may optionally be present in the Clariant as SANDUVOR(R) PR 25. Also, another compound polyamide. Such additives include, but are not limited to, that may be use d is tetra ethyl 2,2'-(1,4- delusterants Such as titanium dioxide, antioxidants including phenylenedimethylidyne)-bismalonate (CAS Registry No. primary and Secondary, antistats, antimicrobial agents, flame 6337-43-5). retardants, waxes, dispersing aides, ultraviolet (“UV") sta Examples of benzotriazoles include, but are not limited to, bilizers such as from the hindered amine light stabilizer 2-(2'-hydroxphenyl)benzotriazoles, 2-(2'-hydroxy-5'- (HALS) family, UV absorbers, thermal stabilizers, light 35 methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'- Stabilizers, lubricants, pigments, reinforcing and or non hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'- reinforcing fillers. hydroxyphenyl)benzotriazole, 2-2'-hydroxy-5'-(1,1,3,3- Primary and Secondary antioxidants are Suggested for tetramethylbutyl)phenylbenzotriazole, 2-(3'-5'-di-tert inclusion herein at conventional amounts. Antioxidants butyl-2'-hydroxyhenyl)-5-chlorobenzotriazole, 2-(3'tert include, for example, alkylated monophenols, alkylated 40 butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, hydroquinones, alkylidenebisphenols, hindered alkylbenzyl 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) compounds, acylaminophenols, esters of B-(3,5-di-tert benzo triazole, 2-(2'-hydroxy-4'-Octoxyphenyl) butyl-4-hydroxyphenyl)propionic acid, and the like which benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxy-phenyl) are disclosed in U.S. Pat. No. 5,051.459 incorporated herein benzo triazole, 2-(3',5'-bis(00. dimethylbenzyl)- by reference. A commercially available antioxidant is 45 2"hydroxyphenyl)benzotriazole; mixture of 2-(3'-tert-butyl IRGANOX(R) 1098 from Ciba Specialty Chemicals. 2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5- As stated above, UV absorbers may be included in the chlorobenzo triazole, 2-(3'-tert-butyl-5'-2-(2- compositions of the present invention. These UV absorbers ethylhexyloxy)carbonylethyl-2'-hydroxyphenyl)-5- may be of both the volatile and low volatile types. These UV chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- absorbers include, but are not limited to, the class of 50 methyxycarbonylethyl)phenyl)-5-chlorobenzotriazole, hydroxy-Substituted benzotriazoles, non-hydroxy Substi 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) tuted oxanilides, hydroxy Substituted benzophenones, phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-(2- hydroxy Substituted triazines, p-methoxybenzylidene mal octyloxy-carbonylethyl)phenyl)benzotriazole, 2-(3'-tert onate esters, hindered amines including cell photoreactive butyl-5'-2-(2-ethylhexyloxy) carbonylethyl-2'- hindered amines, hydroxy Substituted hindered benzoates, 55 hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'- and non-hydroxy Substituted benzoxazinones. methylphenyl)-benzotriazole, and 2-(3'-tert-butyl-2'- Non-hydroxy substituted benzoxazinones that may be hydroxy-5'-(2-iso octylo cycarbonyl ethyl) used include, but are not limited to, 2,2'-(1,4-phenylene)bis phenylbenzotriazole, 2,2'-methylenebis4-(1,1,3,3- 4H,3,1-benzoxazin-4-one (ENCS Inventory Name) (CAS tetramethylbutyl)-6-benzotriazol-2-ylphenol; Registry No. 18600-59-4) which is commercially available 60 transesterification product of 2-3'-tert-butyl-5"(2- as CYASORB(R) UV 3638 from Cytec Industries. methoxycarbonylethyl)-2'-hydroxyphenylbenzotriazole Oxanilides that may be used include, but are not limited with polyethylene glycol 300; R-CHCH-COO(CH) to, ethanediamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2- (TSCA Inventory Name) (CAS Registry No. 23949-66-8) ylphenyl; R-CHCH-COO(CH2CH2O) where n=1 which is commercially available as SANDUVOR(R) VSU 65 to 5 and R-3'-tert-butyl-4"hydroxy-5'-2H-benzotriazol-2- from Clariant and TINUVINGR 312 from Ciba Specialty ylphenyl. A benzotriazole that may be used is 2-propenoic Chemicals. Another oxanilide is ethane diamide, N-5-(1,1- acid, 2-methyl-, 2-3-(2H-benzotriazol-2-yl)-4- US 6,683,124 B2 9 hydroxyphenyl]ether ester (TSCA Inventory Name) (CAS Registry No. 96478-09-0) which is commercially available (III) as NORBLOC(R) 7966, and NORBLOC(R) 6000, from Jensen HC CH Pharma., Inc. Other Suitable benzotriazoles Such as 2,2'- metlhylene bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- tetramethylbutyl)phenol (CAS No. 103597-45-1) and R-N NR3 related UV dimers are commercially available as TINU VINGR 360 from Ciba Specialty Chemicals, MIXXIMCE) HC BB100 from Fairmont Chemical Company, LA31 or ADA ÖH, LA31 or Mark LA31 from Adeka Argus or Witco Chemical. 1O Benzotriazoles are disclosed in U.S. Pat. Nos. 4,335,155, 4,405,749, and 4,528,311, that are incorporated herein by (IV) reference. The present invention not only includes benzot HC CH riazole dimerS Such as TINUVINCE 360 but also includes dimers of benzophenones, and dimers of benzophenone:ben 15 Zotriazole. R-N NR3 Examples of triazines include, but are not limited to, 2-(2-hydroxyphenyl)-1,3,5-triazines, 2,4,6-tris(2-hydroxy 4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4- HC ÖH, O octyloxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5- tria Zine, 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4- dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4, 6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2- wherein for either formula (III) or (IV), R is independently hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3, either hydrogen, C-Co alkyl, O, OH, CH, CN, an acetyl 5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- group, C-C is alkoxy, alkoxyalkylenoxyalky, Cs-C2 methylphenyl)-1,3,5-tria Zine, 2,-(2-hydroxy-4- 25 cycloalkoxy, C-C alkenyl, C7-Co phenylalkyl unsubsti dodecycloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5- tuted or mono-, di- or tri-Substituted on the phenyl by C-C, triazine, 2-2-hydroxy-4-(2-hydroxy-3-butyloypropyloxy) alkyl; or aliphatic or aromatic Ci-Coacyl, -COR" (where phenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6- R" is hydrogen, C-C alkyl, phenyl, and -C-C-COO(H diphenyl-1,3,5-triazin-2-yl)-5(hexyl)oxyphenol, and or C-C alkyl)), C-C alkylamino, optionally further 2-hydroxy-4-(2-hydroxy-3-octyloxypropylocy)-phenyl-4, Substituted C-Co alkoxyalkyl, C-Co hydroxyalkyl, 6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Another triazine C-Coalkenyl, Substituted C-Coalkenyl groups, C-Co that may be used is phenol, 2-4,6-bis(2,4-dimethylphenyl)- alkoxy-C-Co-alkyl groups, C-Co-oxy-N-C-C-alkyl 1,3,5-triazin-2-yl)-5-(octyloxy-)- (TSCA Inventory Name) groups, -N-cyclic-C-Cio-alkyl groups, and cyclic-N- (CAS Registry No. 2725-22-6) which is commercially avail 35 C-Cio-alkyl groups-COR" (where R" is hydrogen, C-C, able as CYASORB(E) 1164, from Cytec Industries (formerly alkyl, phenyl, and -C-C-COO(H or C-C alkyl)); R. American Cyanamid). Other commercially available triaz is hydrogen or C-C alkyl. ines include TINUVINGR) 1577, TINUVINGR) 1545, and TINUVINGE 400, commercially available from Ciba Spe Preferred members of the class of compounds according cialty Chemicals. 40 A preferred additive compound for use in an effective to the formula (II) include compounds of the formulae (V), amount in the composition of the present invention is a (VI), (VII) and (VIII), wherein R is a sterically hindered compound of the general formula: amino group adjacent to the carbonyl carbon.
(II) 45 (V)
R-C C-R
(VI) O wherein n=1, 2, 3 or 4, the carbonyl group(S) is (are) in any 50 position on the heterocyclic ring, and R is a Sterically C-R hindered amino group adjacent to the carbonyl carbon. Where n=2, the preferred compound is a compound having the formula: 55
C-R | O (VIII) O O 60 wherein the carbonyl groups are in any position on the R-C C-R heterocyclic ring and at least one R group represents a Sterically hindered amino group adjacent to the carbonyl carbon. Preferably each R group is a sterically hindered R-C C-R amino group. 65 Preferred R groups include, but are not limited to, the O O following: US 6,683,124 B2 11 12 -continued 2-hexylundecyl, and 5,7,7-trimethyl-2-(1,3,3- (VII) trimethylbutyl)hexyl, exemplary cyclic alkyl groups are O cyclohexyl. Examples of alkoxy(alkyl) groups are methoxy, ethoxy, C-R propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, O isopentoxy, heXOXy, 2-ethylhexyloxy, heptoxy, Octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and R-C octadecyloxy, nonadecyloxy. Preferred alkoxy examples are C-R C-C alkoxy, in particular heptoxy and Octoxy. O Examples of the alkoxyalkylenoxyalkyl groups are C1-Co-alkoxy-C-C-alkylenoxy-C-Co-alkyl groups. The C1-Co-alkoxy groups and C1-Co-alkyl groups include A preferred aromatic dicarbonyl compound is a com those mentioned as examples of the alkoxyalkyl groups. pound having the formula (IX): Examples of the C-C-alkylenoxy groups include (IX) -CH-O-, -CHCH-O-, -CH2CHCH-O-, 15 O O HC CH t t 1 YN N-R -CHCH-O-, and -CH2-d'HO-, k Particularly, C-C2-alkoxy-C-C-alkylenoxy-C-C- HC CH alkyl groups are more preferred. Examples of Cs-Cacycloalkyl unsubstituted or mono-, wherein R' and R are independently either hydrogen, di- or tri-Substituted by C-C alkyl are cyclopentyl, C-C alkyl, O, OH, CH, CN, an acetyl group, C-Cls methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, alkoxy, alkoxyalkylenoxyalky, C-C cycloalkoxy, C-C, methylcyclohexyl, dimethylcyclohexyl, alkenyl, C7-C phenylalkyl unsubstituted or mono-, di- or 25 trimethylcyclohexyl, t-butylcyclohexyl, cyclooctyl, cyclo tri-Substituted on the phenyl by C-C alkyl, or aliphatic or decyl and cyclododecyl. Unsubstituted or substituted cyclo aromatic C-Co acyl, -COR" (where R" is hydrogen, hexyl is preferred. C-C alkyl, phenyl, and -C-C COO(H or C-C, Examples of C-C cycloalkoxy are cyclopentoxy, alkyl)), C-C alkylamino, optionally further Substituted cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy C-C alkoxyalkyl, C-Co hydroxyalkyl, C-Coalkenyl, and cyclododecyloxy, including as applied to R. Cyclopen Substituted C-Coalkenyl groups, C1-Co-alkoxy-C-C- toxy and cyclohexoxy are preferred. alkyl groups, C1-Co-oxy-N-C-Co-alkyl groups, Examples of C-Calkenyl are allyl, 2-methylallyl, bute -N-cyclic-C-Cio-alkyl groups, and cyclic-N-C-Cio nyl and hexenyl, 3-butenyl, and 10-undecenyl; examples of alkyl groups-COR" (where R is hydrogen, C-C alkyl, branched alkenyl groups are 1-methyl-2-prope nyl, phenyl, and -C-Cio COO(H or C-C alkyl)); Ris 35 3-methyl-3-butenyl. Allyl is preferred. hydrogen or C-C alkyl. Examples of C7-Co phenylalkyl unsubstituted or mono-, More preferred is the aromatic dicarbonyl compound (X): di- or tri-substituted on the phenyl by C-C alkyl are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and 2-phenylethyl. Benzyl is preferred. Examples of aliphatic and aromatic C-Co acyl are HC CH O O H3C CH3 40 C-C alkanoyl or C-C-alkenoyl, for example, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, benzoyl, R-N N1 NN N-R hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, acryloyl s and crotonyl. Acetyl is preferred. R3' R When more than one hindered amine group is present they HC CH HC CH3 45 can be identical or different, and preferably are identical hindered amine groups. Exemplary aromatic tri-carbonyl compounds are the fol wherein each R" is independently hydrogen, C-C alkyl, lowing (XI) and (XII), O, OH, CH, CN, an acetyl group, C-C alkoxy, (XI) alkoxyalkylenoxyalky, C-C cycloalkoxy, C-C alkenyl, 50 C7-C phenylalkyl unsubstituted or mono-, di- or tri H3C CH3 H3C CH3 substituted on the phenyl by S.C. alkyl, or aliphatic or aromatic C-C acyl, -COR" where R' is defined as C C above, C-C alkylamino, optionally further Substituted R-N o1 No N-R C-C alkoxyalkyl, C-C hydroxyalkyl, C-C alkenyl, Substituted C-Coalkenyl groups, C1-Co-alkoxy-C-Cio 55 alkyl groups, C1-Co-oxy-N-C-Co-alkyl groups, HC CH HC CH -N-cyclic-C-Cio-alkyl groups, and cyclic-N-C-Cio CFO alkyl groups -COR", where R" is hydrogen, C-C alkyl, / phenyl, or -C-C-COO(H or C-C alkyl). Each Ris O independently hydrogen or C-C alkyl. Examples of alkyl groups having not more than twenty 60 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, HC CH octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, HC N CH tridecyl, tetradecyl, hexadecyl and octadecyl; exemplary R branched alkyl groups are isopropyl, isobutyl, t-butyl, 2,2- 65 dimethylpropyl, 2-methylpropyl, cyclohexylmethyl, and cyclohexylethyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, US 6,683,124 B2 14 -continued tetramethyl piperizine, and likewise the N-substituted hin (XII) dered amines, substituted with following N-Substituents may be used: C-C alkyl, O, OH, CHCN, C-C alkoxy, HC CH HC CH alkoxyalkylenoxyalky, C-C cycloalkoxy, C-Calkenyl, C C C7-Cophenylalkyl unsubstituted or mono-, di- or tri R-N N1 a. N N-R Substituted on the phenyl by C-C alkyl, or aliphatic or R3 R3 aromatic C. Coacyl groups. One aspect of the present invention is that some UV HC CH HC CH absorbers if present in the compositions of the present CFO invention inhibit the degree of fluorescence while the pres 3. / RN ence of other UV absorbers does not inhibit the degree of fluorescence. The term “non-inhibiting UV absorber' as used herein refers to a UV absorber that does not inhibit HC CH fluorescence prior to UV exposure. A non-inhibiting UV 15 absorber Suitable for use in the present invention has an HC N CH absorptivity of from about 25 L/(g cm) to about 200 L/(g cm), a wavelength of less than about 370 nm, prefer l ably about 290 to 340 nmi; or a maximum wavelength of about 310 to 315 nm. Non-inhibiting UV absorbers that are wherein R' and R is defined as in (X). preferred in the fluorescent compositions of the present The most preferred compound which is an aromatic invention include, but are not limited to, UV absorbers of the di-amide is 1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6- classes of Oxanilides, Salicylates, benzyl malonates, and tetramethyl-4-piperidinyl (TSCA Inventory Name) (CAS cinnamates. Examples of these non-inhibiting UV absorbers Registry No. 42774-15-2) having the following formula include, but are not limited to, NYLOSTABOR S-EEDTM, 25 SANDUVOR(R) VSU, SANDUVOR(R) PR25, tetraethyl-2, (XIII): 2'-(1,4-phenylenedimethylidyne)-bismalonate (CAS Num ber: 6337-43-5), TINUVING 312, SANDUVOR(R) 3206, (XIII) SANDUVOR(R) PR31, FERRO AM 340, CYASORB(R) H3C CH3 H3C CH3 2908, SANDUVOR(R) EPU, TINUVIN(R) 315 and cyanoacrylates such as SANDUVORCE 3039. Examples of UV absorbers that may be used in the fluorescent compo H-N N-H Sitions of the present invention but that are not preferred because they inhibit the degree of fluorescence include, but O O are not limited to, hydroxy Substituted benzophenones Such HC CH HC CH 35 as SANDUVOR(R) 3035 and hydroxy substituted benzotria Zoles such as NORBLOC(R) 7966, hydroxy substituted tri azines such as CYASORB(R) 1164, and non-hydroxy substi and is commercially available as NYLOSTAB(R) S-EEDTM tuted benoxazinones Such as CYASORBCE) UV 3638. Such from Clariant. inhibiting UV absorbers have wavelengths greater than The aromatic di- or tri-carbonyl ester amide compounds 40 about 340 nm. can be prepared by known means, for example, by the An effective amount of the compound of the formula (II), reaction of an aromatic di- or tri-carboxylic acid di- or especially the compound of the formula (XIII), is from tri-chloride with 2.2,6,6-tetramethyl-4-amino-piperidine. AS 0.01% to 25% by weight based on the weight of the one example 1,3,5-tri-(2,2',6',6'-tetramethylpiperidyl-4)- polyamide. The Surprising effect of enhanced fluorescence is trimesic acid amide is prepared by reaction as follows: 42 45 seen at this level. Preferably, the amount is from 0.05% to grams of trimesic acid are heated for 5 hours at 80 C. with 20% by weight. Most preferably, the amount is 3% to 10% 144.0 ml of thionyl chloride in the presence of catalytic by weight. quantities (3 ml) of dimethylformamide and then the excess It is known that a polyamide or a polyester having thionyl chloride is distilled off. The trimesic acid trichloride incorporated the compound of the formula (XIII) results in thus formed is dissolved in 500 ml of dioxane, then a total 50 an improvement in the heat Stability, light Stability, and of 187.2 g of 2,2,6,6-tetramethyl-4-aminopipyridine is chemical stability of the polymer as well as the stability and added dropwise while stirring, whereby dioxane (2000 ml in the light resistance of the coloring agent in the pigmented all) is constantly added to allow the reaction mixture to polymer. U.S. Pat. No. 5,965,261, U.S. Pat. No. 5,969,014, remain Stirrable. The temperature of the reaction mixture is and WO 97/43335 make Such disclosures, each of which are not allowed to exceed 30° C. The reaction mixture is 55 herein incorporated by reference. However, until now, it was Subsequently boiled for 48 hours with reflux cooling, the not known that the presence of this compound accentuates residue is filtered, washed with acetone, dissolved in approx. the fluorescence of the yellow fluorescent pigment compo 1000 ml of water, precipitated again with soda solution (pH Sitions of the present invention. 10–11), filtered, and the residue washed with water and Various methods can be employed for preparing the vacuum-dried, yielding 89.2 g (72%) of a white powder 60 fluorescent pigment compositions of the present invention. having a melting point of >320 C. Isophthalic acid, or In general, the pigment can be added to the polyamide terephthalic acid likewise can be Substituted in the above, directly by mixing it with the polyamide. It may be mixed and under Suitable conditions the corresponding acid amides while the polyamide is either in the molten state or in dry can be made, e.g. 1,3- or 1,4-di-(2,2', 6,6'- powder form. If in the molten State, the molten polyamide is tetramethylpiperidyl-4)-phthalic acid amide. 65 typically in a Suitable receptacle, Such as an extruder, when In like manner the reaction above can be made Substitut the pigment is introduced into the receptacle. The pigment is ing 2,2,6,6-tetramethyl-4-aminopiperidine with 2,2,6,6- worked into the polyamide to produce a uniform dispersion US 6,683,124 B2 15 16 prior to molding, melt extruding or Spinning. When the AS Stated previously, it is another aspect of the present pigment is added to the polyamide in a powdered form, the invention to include additives in the fluorescent pigment dry mixture is blended and dispersed by Suitable means Such compositions of the present invention. A method that can be as a blender prior to molding, melt extruding or Spinning. used in accordance with the present invention to add addi Another method in accordance with the present invention tives is often referred to in the art as preparing a fully is physically mixing and blending the additive with the formulated System or a custom formulation. In this method, pigment to form a physical mixture and then adding the for example, a 10% loading of an additive may be desired (0.1 g of additive per 100 g of polyamide). Individual mixture to the polyamide. The mixture can then be formed additive masterbatches based upon this loading are then into an article, for example by formula (XIII), is present in prepared and formed into pellets. The individual pellets can the article in an amount of about 0.001% to 0.03% by weight 1O then be added to the polyamide alone or in combination with based upon the weight of the article. More preferably, it is other additive masterbatches. When the additive master from about 0.005% to 0.03% by weight based upon the batch is used to prepare an article, the additive, preferably weight of the article. This method of combining the pigment the compound of the formula (XIII), is present in the article and the additive physically together (without a resin) is in an amount of preferably from about 0.001% to 0.03% by referred to as a mastermix as opposed to a masterbatch. The 15 weight based upon the weight of the article. More preferably, amount of pigment to additive can be mixed in any propor it is from about 0.005% to 0.03% by weight based upon the tion. However, the preferred ratioS of pigment to additive are weight of the article. 50:50, 60:40, 40:60, 70:30 and 30:70. In yet another method, a single pigment concentrate or Another method of combining the pigment with the masterbatch is obtained and let down to get a desired final polyamide to form the fluorescent pigment compositions of percentage of pigment in the polyamide, and a Separate the present invention is by first forming an intermediate additive masterbatch is prepared and Separately let down in concentrate or masterbatch comprising the pigment. This the same way to get the desired final percentage of additive concentrate or masterbatch is referred to as a single pigment in the polyamide. The masterbatch may then be mixed and concentrate or masterbatch when it is comprised of a single added to the polyamide. The resulting composition can be pigment. The concentrate or masterbatch which comprises 25 formed into an article. The additive, preferably the com the pigment is formed of a carrier polymer which is a pound of the formula (XIII), is present in the article in an polyamide or a polymer which is intimately dispersible in or amount of preferably from about 0.01% to 0.4% by weight based upon the weight of the article. More preferably, it is compatible with the polyamide. The terms “concentrate” or from about 0.05% to 0.3% by weight based upon the weight “masterbatch” can be used interchangably. However, the of the article. term “masterbatch' often refers to when there is more than However, the most preferred method in accordance with one pigment present. the present invention is the method in which an additive is However, any method commonly used in the art to added together with the pigment to form the concentrate or incorporate pigments into polymerS may be employed in masterbatch. This method provides enhanced fluorescence accordance with the present invention. Likewise, any of the as the additive and the pigment are in intimate contact. The above mentioned methods or any method commonly used in 35 amount of polyamide may have to be adjusted to maintain the art may be employed to incorporate additives into the desired pigment percentage in the final fluorescent polymers in accordance with the present invention. pigment composition when the weight percentages are based When a specific amount or percentage of pigment, for upon the weight of the polyamide. This masterbatch or example, is needed to achieve a fluorescent polyamide concentrate can then be added to the polyamide to arrive at composition of the present invention, a single pigment 40 a fluorescent pigment composition with enhanced fluores concentrate or masterbatch can be prepared and then can be cence and increased dispersion. “let down” to obtain the desired amount of pigment in the Fluorescence was measured by using Standard Spectros resulting fluorescent polyamide composition. For example, copy methods. The fluorescence of the pigment composi if the fluorescent pigment composition is in the form of a tions of the present invention is seen under black light fiber and the desired pigment level in the final fiber is 1.2% 45 Sources and not under typical visible lighting from incan by weight based on the weight of the polyamide, a 30% descent or fluorescent bulbs. Fluorescence is preferably Seen Single pigment concentrate or masterbatch, for example, can under black light at a wavelength of about 365 nanometers. be let down. The term “let down,” as used herein, refers to The fluorescent yellow pigment compositions of the the ratio of: present invention can be formed into articles Such as molded 50 articles, cast articles, and extruded articles. Examples of molded articles include, but are not limited to, injection molded or blow molded articles. Examples of cast articles wherein include, but are not limited to, films. Examples of extruded X is the amount of the Single pigment concentrate or articles include, but are not limited to, fibers, monofilaments, masterbatch, 55 and masterbatches. The fluorescent yellow pigment compo y is the percentage of pigment in the Single pigment Sitions of the present invention can be used in a variety of concentrate or masterbatch, applications including, but not limited to, Security fibers in X is the batch Size of the fluorescent pigment composition money and Security badges, any form of Security indicators (in the same units as X), and for military and non-military use, carpet in airplanes or y is the percentage of pigment in the final fluorescent 60 hospitals. There is no limit to the number of potential polyamide composition. applications with the fluorescent pigment compositions of Therefore, in the above example, if x' is 100 lb, y' is 1.2% the present invention. and y is 30%, then 4 lb of the 30% single pigment concen EXAMPLES trate or masterbatch is needed to produce a fluorescent polyamide fiber having a pigment concentration of 1.2%. 65 Example 1 Thus, in this example, the let down ratio would be 4:1. It is A 25% by weight Single pigment concentrate of Pigment also sometimes referred to as a 4% let down. Violet 19 was prepared. The pigment used was Pigment US 6,683,124 B2 17 18 Violet 19 commercially available as 13-7013 PV Fast Red Card Samples 1 were mounted in the Sample chamber So ESB (lot 59784) from Clariant. The polyamide used was that the plane of the card was normal to the excitation axis nylon 6. On a 10 lb basis, 2.5 lb of Pigment Violet 19 was 2. The cards were also positioned as precisely as possible So mixed with 7.5 lb of polyamide. The mixture was then that the excitation axis 2 and front-face emission axis 3 formed into a single pigment concentrate. The final compo crossed at the surface of the sample 1 as seen in FIG. 14. sition of the concentrate was 25% by weight of Pigment Since 1 nm slits were used in this experiment for the Violet 19 wherein the percentage by weight was based upon emission slit 4 and the excitation slit 5, Small errors in the the weight of the polyamide. positioning of the Sample could lead to large changes in the measured fluorescence intensities. This problem was elimi Example 2 nated by placing cylindrical lens 6 in the excitation beam 7. A 25% by weight Single pigment concentrate was pre This spread the approximately 1-2 mm wide excitation pared. The pigment used was Pigment Yellow 192 commer beam into a nearly uniform 1 cm beam at the Sample Surface, cially available as SANDOFIL(R) Yellow RL or Polysynthren and essentially eliminated the effects of Sample misalign Yellow RL (lot 7014968) from Clariant. The polyamide used ment. It was found that Samples could be repeatedly was nylon 6. On a 10 lb basis, 2.5 lb of Pigment Yellow 192 15 removed and reinserted with observed intensity variations of was mixed with 7.5 lb of polyamide. The mixture was then only a few percent. formed into a single pigment concentrate. The final compo sition of the concentrate was 25% by weight of Pigment Example 5 Yellow 192 wherein the percentage by weight was based FIG. 1 illustrates the exposure and non-exposure to ultra upon the weight of the polyamide. Violet light of card wraps of polyamide fiber comprising Pigment Violet 19. Fluorescence was measured in accor Example 3 dance with the method of Example 4. In FIG. 1, the nylon This example illustrates the methodology used to prepare 6 fiber of the card wraps comprised, 0.1% by weight of the polyamide fiber Samples of which fluorescence was Pigment Violet 19 based upon the weight of the polyamide. measured. Four Samples were prepared. One Sample was the 25 Each card wrap was spun from a 25% single pigment control. The control was a single pigment concentrate of concentrate of Pigment Violet 19 either with or without the pigment and polyamide. The level of pigment in the Single presence NYLOSTAB(R) S-EEDTM commercially available pigment concentrate was 30% by weight based on the from Clariant. When the NYLOSTABOE) S-EEDTM was weight of the polyamide. The 30%. Single pigment concen added, it was added at levels of 0% by weight, 1.5% by trate comprised 30% Pigment Violet 19 and 70% nylon 6. weight, 3% by weight or 5% by weight to the single pigment The other three samples were prepared with 1.5%, 3% and concentrate. FIG. 1 illustrates that even prior to ultraviolet 5% by weight of NYLOSTAB(R) S-EEDTM, respectively, exposure, the card wraps comprising NYLOSTABOR being added to the pigment and polyamide to form a single S-EEDM had greater fluorescence than the card wraps with masterbatch wherein the weight was based on the weight of only Pigment Violet 19. the polyamide. The additive in powder form was added to 35 the pigment and polyamide to form a powder mixture. Example 6 Powdered nylon 6 was obtained from DSM and dry powder FIG. 2 illustrates the exposure of card wraps of polyamide Pigment Violet 19 was obtained as PV Fast Red ESB from fiber comprising Pigment Violet 19 to ultraviolet light after Clariant. The dry pigment was mixed in the dry powder 100 hours in a QUV340 device used for pigmented plastics nylon and was dispersed in a Henchel blender. Neither 40 and coatings, commercially available from QLV Panel. In pigment dispersing aids nor lubricants were added to the FIG. 2, the fiber of the card wraps comprised 0.1% by weight mixture. The dry powder mixture was extruded. A 30 mm of Pigment Violet 19 based upon the weight of the polya APV twin screw extruder of clam shell design was used. The mide. Each card wrap was spun from the pigmented polya temperature of compounding in the twin Screw extruder was mide fiber either with or without NYLOSTABOE) S-EEDTM 250 C. The melt was extruded and formed into water 45 commercially available from Clariant, present in the fiber. quenched pellets. Additional polyamide was added as When NYLOSTABOR S-EEDTM was added, it was added at needed in order to ensure that the resulting fiber would have levels of 0% by weight, 1.5% by weight, 3% by weight or the desired weight percent of pigment Such that fluorescence 5% by weight to the masterbatch. FIG. 2 illustrates that the was achieved. relative intensity at 550 nm decreased as expected. However, 50 the relative intensity of samples comprising NYLOSTABOR Example 4 S-EEDTM was unexpected. The levels of NYLOSTAB(R) The fluorescence of Pigment Violet 19 in polyamide was S-EEDTM at 5% by weight in the masterbatch equated to 200 measured using spectroScopy. Fluorescence spectra were ppm in the final fiber. obtained on a SPEX Fluorolog-3 controlled by DataMax/32 Example 7 v2.1 software. Excitation spectra were obtained from 300 to 55 560 nm using 589 nm emission, 0.5 s integration, 1 nm slits FIG. 3 which is a graph of wavelength in nm versus (excitation and emission), 2 nm increment, and 950 V relative intensity illustrates the exposure of card wraps of applied to the photomultiplier detector. Emission Spectra polyamide fiber comprising Pigment Violet 19 to ultraviolet were obtained from 500 to 700 nm with 370 nm excitation. light after 100 hours in a QUV340 device versus the reverse All other parameters were the Same as for excitation. Exci 60 side of the card wraps which were exposed to heat at 70° C. tation intensities were divided by the Signal from an internal but unexposed to light. The Side of the card wrap exposed to Standard in order to correct for wavelength variations in ultraViolet light had lower relative intensity as compared to lamp intensity and excitation monochromator throughput. the reverse Side of the card wrap that was not exposed to Emission spectra were not corrected. However, the excita ultraviolet light but only to the heat of the QUV unit which tion reference Signal was measured before and after each 65 was set at 70° C. The data showed that light has a major emission Spectrum in order to monitor lamp Stability. Exci effect on lowering the fluorescence and heat had a minor tation power was found to fluctuate less than 2%. effect. US 6,683,124 B2 19 20 Example 8 AH* represents difference in hue, and This example relates to the effect of polar and nonpolar AE*ab represents total color difference value. Soluble UV absorbers alone and in combination with non TABLE 1. UV absorbing HALS compounds on the fluorescence of 5 Pigment Violet 19 in polyamide. UV absorber masterbatches AL* Aa Ab AC AH* AE*ab were prepared on a 30 mm twin screw extruder at 260 C. 15% NYLOSTABS-EED 2.65 -1.53 2.36 -0.56 2.76 3.87 in a nylon-6 carrier commercially available from DSM. The 3.0% NYLOSTABS-EED 2.25 -0.88 2.25 -0.01 2.41 3.30 UV absorber masterbatches were let down in a 25% by 5.0% NYLOSTABS-EED 3.50 -1.98 4.52 -0.07 4.93 6.05 weight Single pigment concentrate of Pigment Violet 19 in a nylon-6 carrier and fibers were prepared at 260 C. for testing. Card wraps comprising 0.1% by weight of Pigment A trial was conducted, the results of which are shown in Violet 19 and various ultraviolet absorbers and concentra Table 2, comparing the color Space of the polyamide fiber tions thereof were exposed using QLV340 exposure and with 0.25% by weight of Pigment Violet 19 and having fluorescence data was measured. Fluorescence spectroscopy varying amounts of NYLOSTAB(R) S-EEDTM in the final was run in non-relative intensity mode for this experiment. 15 fiber. Whole numbers were compared in counts per Second (cps). These values reflected the true fluorescence for each card TABLE 2 wrap and were to be used for comparison with all other samples in this series as set forth in FIGS. 4 to 13. AL* Aa Ab AC AH* AE*ab 15% NYLOSTABS-EED -1.65 130 O.38 135 0.17 2.14 Example 9 In this example, 25%. Single pigment concentrates of A trial was conducted, the results of which are shown in Pigment Violet 19 in nylon-6 carriers were prepared with Table 3, comparing the color Space of the polyamide fiber and without UV absorbers. The percentage of Pigment 25 with 1% by weight of Pigment Violet 19 and having varying Violet 19 used was such that there would be 0.1% pigment amounts of NYLOSTABOE) S-EEDTM in the final fiber. in the final fiber. The effect of various UV absorbers on the degree of fluorescence was measured and photographed TABLE 3 under black light. A control was prepared which was a 25% single pigment concentrate of Pigment Violet 19. No UV AL* Aa Ab AC AH* AE*ab absorber was added. The control emitted a fluorescence of 15% NYLOSTABS-EED O.31 O.30 -0.04 O.28 -0.11 O.44 15,500 cps. Next, a 25% single pigment concentrate of 3.0% NYLOSTABS-EED O.16 O.65 -0.12 O.6O -0.29 O.68 Pigment Violet 19 was prepared and a second masterbatch of 5.0% NYLOSTABS-EED -0.1O O.78 O.38 O.85 0.15 O.87 1% by weight of SANDUVOR(R) VSU in a nylon-6 carrier was prepared. These masterbatches were added together, and 35 formed into a fiber. The card wraps of resulting fiber emitted Example 11 a fluorescence of 14,500 cps. Yet again, a first masterbatch was prepared from a 25% single pigment concentrate of Hot melt smear tests were conducted with 25% single Pigment Violet 19 with 3% by weight of NYLOSTAB(R) pigment concentrates of Pigment Violet 19 in nylon-6, S-EEDTM and a second masterbatch was prepared compris 40 without and without the presence of NYLOSTAB(R) ing 1% by weight of SANDUVOR(R) VSU. These master S-EEDTM. A hot plate was used to heat the concentrates. The batches were added together and formed into a fiber. The concentrates were Smeared on a glass microscope Slide to card wraps of the resulting fiber emitted a fluorescence of form a melt Smear. The microscope slide was placed under 17,000 cps. It was observed that the optimum method for a transmission microscope at a magnification of 200x. The obtaining maximum fluorescence was to combine the UV 45 results were observed. In the Smear comprising the absorber together with the pigment in the Same masterbatch NYLOSTAB(R) S-EEDTM, the pigment was completely dis Such that they were in intimate contact. It was also observed persed in the nylon 6 as evidenced by the uniform red color that adding the UV absorber to a masterbatch other than the of the pigment. In contrast, in the Smear without pigment resulted in fluorescence but the degree of fluores NYLOSTAB(R) S-EEDTM, the pigment was not uniformly cence Was not as great. distributed in the nylon 6 as evidenced by the dark, non 50 uniform spots in the red color of the pigment. Example 10 Example 12 A trial was conducted, the results of which are shown in Table 1, comparing the color Space of the polyamide fiber Single pigment concentrates of Pigment Yellow 192 in with 0.1% by weight of Pigment Violet 19 and having 55 nylon-6 carriers were prepared. A control was prepared varying amounts of NYLOSTAB(R) S-EEDTM in the final without the presence of NYLOSTAB(R) S-EEDTM. A single fiber. A 25% by weight Single pigment concentrate of pigment concentrate was prepared with a 50:50 blend of Pigment Violet 19 was used to color the fiber. In the tables Pigment Yellow 192 and NYLOSTAB(R) S-EEDTM and below, achieved 0.1% by weight of Pigment Yellow 192 and 0.1% AL represents difference in lightneSS/darkness value; "+" is 60 by weight of NYLOSTAB(R) S-EEDTM in the final polyamide lighter and "-" is darker, fiber. Another masterbatch was prepared with a 60:40 blend Aa represents difference on red/green axis; "+" is redder of Pigment Yellow 192 and NYLOSTAB(R) S-EEDTM and and - IS greener, achieved 0.1% by weight of Pigment Yellow 192 and Ab represents difference on yellow/blue axis; "+" is yel 0.067% NYLOSTAB(R) S-EEDTM in the final polyamide lower and "-' is bluer, 65 fiber. The fluorescence of the fibers that were prepared from AC represents difference in chroma; "+" is brighter and “-” each of Said masterbatches was observed visually and pho is duller, tographed under black light. US 6,683,124 B2 21 Comparative Example 1 25% single pigment concentrates of Pigment Violet 19 in TABLE 4 a nylon-6 carrier were prepared with and without the pres ence of UV absorbers. The weight percentage of Pigment AL* Aa Ab AC AH* AE*ab Violet 19 used Was Such that there Would be 0.1% pigment 5 1so NyLOSTAB SEED -1.67 1.48 -0.02 141 0.46 2.23 in the final fiber based upon the weight of the polyamide. 3.0% NYLOSTABS-EED -1.73 1.62 -0.14 158 0.39 2.37 The effect of various UV absorbers on the degree of fluo 5.0% NYLOSTABS-EED 1.10 -0.12 -0.01 -0.11 -0.05 1.10 rescence was measured and photographed under black light. A control was prepared which was a 25% single pigment concentrate of Pigment Violet 19. No UV absorber was A trial was conducted, the results of which are shown in added. Fluorescence was observed. A 25% single pigment Table 5, comparing the color Space of polyamide fiber with concentrate of Pigment Violet 19 was prepared and another 0.25% Pigment Red 122 and with varying amount of masterbatch of 10% SANDUVOR(R) 3035 in a nylon-6 NYLOSTABOE) S-EEDTM in final fiber. carrier was prepared such that the final fiber would have 0.5% SANDUVOR(R) 3035. Another 25% single pigment TABLE 5 concentrate of Pigment Violet 19 was prepared and a Second 15 masterbatch of 10% SANDUVOR(R) 3035 in a nylon-6 AL* Aa Ab AC AH* A*ab carrier was prepared such that the final fiber would have 1% 3% NYLOSTABS-EED -1.38 1.66 -0.45 1.72 O.O9 2.21 SANDUVORCE 3035. The fiber with 0.5% of SANDU VOR(R) 3035 in the final fiber had a visibly quenched A trial was conducted, the results of which are shown in fluorescence. The fiber with 1% of SANDUVORCE 3035 in Table 6, comparing the color Space of polyamide fiber with the final fiber had a visibly quenched fluorescence. 1% by weight of Pigment Red 122 having varying amounts Comparative Example 2 of NYLOSTABOE) S-EEDTM in the final fiber. A Study was conducted between fiber having a concen tration of 0.1% by weight of Pigment Violet 19 and fiber TABLE 6 having a concentration of 0.1% by weight of Pigment Red 25 122 to compare their fluorescence. Pigment Red 122 (CAS AL* Aa Ab AC AH* AE*ab Registry No. 980-26-7); TSCA Inventory Name: Quino.2, 15% NYLOSTABS-EED -2.18 O.35 2.62 O.O1 2.65 3.43 3-blacridine-7,14-dione, 5,12-dihydro-2,9-dimethyl-) is a 3.0% NYLOSTABS-EED -2.96 O.77 3.03 O.39 3.11 4.30 quinacridone pigment having the following structure: 5.0% NYLOSTABS-EED -193 0.76 2.15 O.47 2.24
A color Space comparison of the results with Pigment Violet 19 versus the results with Pigment Red 122 demon strated that although the color strength of Pigment Red 122 was greater than Pigment Violet 19, the Pigment Red 122 did not exhibit fluorescence as did the Pigment Violet 19. 35 It will therefore be readily understood by those persons skilled in the art that the present invention is Susceptible of broad utility and application. Many embodiments and adap tations of the present invention other than those herein described, as well as many variations, modifications and A Single pigment concentrate of Pigment Red 122 was 40 equivalent arrangements, will be apparent from or reason prepared without any NYLOSTAB(R) S-EEDTM as a control. ably Suggested by the present invention and the foregoing Single pigment concentrates of Pigment Red 122 were description thereof, without departing from the Substance or prepared with 1.5% by weight, 3% by weight and 5% by Scope of the present invention. Accordingly, while the weight of NYLOSTAB(R) S-EEDTM, respectively. A single present invention has been described herein in detail in pigment concentrate of Pigment Violet 19 was prepared relation to its preferred embodiment, it is to be understood without any NYLOSTAB(R) S-EEDTM as a control. A single 45 that this disclosure is only illustrative and exemplary of the pigment concentrate of Pigment Violet 19 was also prepared present invention and is made merely for purposes of with 5% by weight of NYLOSTAB(R) S-EEDTM. The results providing a full and enabling disclosure of the invention. of this comparison are shown in FIGS. 15-19. The fiber The foregoing disclosure is not intended or to be construed comprising Pigment Violet 19 exhibited fluorescence while to limit the present invention or otherwise to exclude any the fiber comprising the Pigment Red 122 did not. 50 Such other embodiments, adaptations, variations, modifica tions and equivalent arrangements, the present invention Comparative Example 3 being limited only by the claims appended hereto and the A trial was conducted, the results of which are shown in equivalents thereof. Table 4, comparing the color Space of polyamide fiber with I claim: 0.1% by weight of Pigment Red 122 having varying 55 1. A fluorescent pigment composition comprising: amounts of NYLOSTABOE) S-EEDTM in the final fiber. A a) a polyamide, and 25% by weight of Single pigment concentrate of Pigment b) a pigment of formula (Ib) Red 122 was used to color the fiber. In the tables below, AL represents difference in lightneSS/darkness value; "+" is (Ib) lighter and "-" is darker, O 60 H Aa represents difference on red/green axis; "+" is redder C N and "-" is greener, Ab represents difference on yellow/blue axis; "+" is yel lower and "-' is bluer, N C AC represents difference in chroma; "+" is brighter and “-” H is duller, 65 AH* represents difference in hue, and AE*ab represents total color difference value. US 6,683,124 B2 23 24 in an amount of less than one percent by weight, wherein the percent by weight is based upon the weight of the (V) polyamide, wherein the polyamide and the pigment of O O formula (Ib) are in the form of a dry mixture. R-C C-R 2. The fluorescent pigment composition as claimed in (VI) claim 1, wherein the amount of the pigment of the formula O (Ib) is 0.005 to 0.25 percent by weight. 3. The fluorescent pigment composition as claimed in C-R claim 1, wherein the amount of the pigment of the formula 1O (Ib) is 0.01 to 0.15 percent by weight. 4. The fluorescent pigment composition as claimed in claim 1, further comprising a compound of formula (II) C-R 15 (II) O (VII) f / \ O |R Cin L C-R O and wherein R-C C-R R is a Sterically hindered amino group adjacent to the O carbonyl carbon, and (VIII) n is 1, 2, 3, or 4. 25 O O 5. The fluorescent pigment composition as claimed in R-C C-R claim 4, wherein in the compound of the formula (II), n=2 and R is R-C C-R (III) H3C CH3 O O
R-N NR3- or wherein R is a Sterically hindered amino group adjacent to 35 the carbonyl carbon. 7. The fluorescent pigment composition as claimed in HC CH claim 4, wherein the compound of the formula (II) is present (IV) in an amount of 0.05 to 20 percent by weight, wherein the HC CH percent by weight is based upon the weight of the polya 40 mide. 8. The fluorescent pigment composition as claimed in R-N NR3 claim 4, wherein in the compound of the formula (II), R is
HC H3C CH3 3 ÖH, O 45
N N-R wherein for either the formula (III) or the formula (IV): R' R3 is independently either hydrogen, C-C alkyl, O, OH, HC CH CH, CN, an acetyl group, C-C is alkoxy, 50 alkoxyalkylenoxyalky, C-C cycloalkoxy, C-C alkenyl, C7-C phenylalkyl unsubstituted or mono-, di- or tri wherein R' is hydrogen, C-C alkyl, O, OH, CH, CN, an Substituted on the phenyl by C-C alkyl, or aliphatic or acetyl group, C-C alkoxy, alkoxyalkylenoxyalky, C-C2 aromatic C, Co acyl, -COR" (where R" is hydrogen, cycloalkoxy, C-C alkenyl, C7-Co phenylalkyl unsubsti C-C alkyl, phenyl, and -C-C COO(H or C-C, 55 tuted or mono-, di- or tri-Substituted on the phenyl by C-C, alkyl)), C-Co alkylamino, optionally further Substituted alkyl; or aliphatic or aromatic Ci-Coacyl, -COR" (where C-C alkoxyalkyl, C-C hydroxyalkyl, C-C alkenyl, R" is hydrogen, C-C alkyl, phenyl, and -C-C-COO(H Substituted C-Coalkenyl groups, C1-Co-alkoxy-C-Cio or C-C alkyl)), C-Co alkylamino, optionally further alkyl groups, C1-Co-oxy-N-C-Co-alkyl groups, Substituted C-Co alkoxyalkyl, C-Co hydroxyalkyl, 60 C-C alkenyl, Substituted C-Coalkenyl groups, C1-Co -N-cyclic-C-Cio-alkyl groups, and cyclic-N-C-Cio alkoxy-C-Cio-alkyl groups, C1-Co-oxy-N-C-C-alkyl alkyl groups-COR" (where R" is hydrogen, C-C alkyl, groups, -N-cyclic-C-Cio-alkyl groups, and cyclic-N- phenyl, and -C-C-COO(H or C-C alkyl)); and R is C-Cio-alkyl groups-COR" (where R" is hydrogen, C-C, hydrogen or C-C alkyl. alkyl, phenyl, and -C-Co. COO(H or C-C alkyl)); and 6. The fluorescent pigment composition as claimed in 65 wherein R is hydrogen or C-Cs alkyl. claim 4, wherein the compound of the formula (II) is 9. The fluorescent pigment composition as claimed in Selected from the group consisting of: claim 1, further comprising a non-inhibiting UV absorber. US 6,683,124 B2 25 26 10. The fluorescent pigment composition as claimed in claim 9, wherein the non-inhibiting UV absorber has a (II) wavelength of less than about 370 nm. / \ 11. The fluorescent pigment composition as claimed in |R-C- claim 9, wherein the non-inhibiting UV absorber has an absorptivity from about 25 L/(g'cm) to about 200 L/(g cm). 12. The fluorescent pigment composition as claimed in wherein claim 9, wherein the non-inhibiting UV absorber is selected R is a Sterically hindered amino group adjacent to the from the group consisting of Oxanilides, benzyl malonates, carbonyl carbon, and Salicylates, cinnamates, and triazines. n is 1, 2, 3, or 4. 17. The article as claimed in claim 16, wherein the 13. A fluorescent pigment composition comprising: compound of the formula (II) is present in an amount of 0.05 a) a polyamide, to 20 percent by weight, wherein the percent by weight is b) a pigment of formula (Ib) based upon the weight of the polyamide. 15 18. The article as claimed in claim 16, wherein in the (Ib) compound of the formula (II), R is O H HC CH C N
N N-R C R3 | O HC CH 25 in an amount of less than one percent by weight, and wherein R' is hydrogen, C-C alkyl, O, OH, CH, CN, an acetyl group, C-C alkoxy, alkoxyalkylenoxyalky, C-C2 c) a compound of the formula (XIII) cycloalkoxy, C-C alkenyl, C7-Co phenylalkyl unsubsti tuted or mono-, di- or tri-Substituted on the phenyl by C-C, (XIII) alkyl; or aliphatic or aromatic Ci-Coacyl, -COR" (where R" is hydrogen, C-C alkyl, phenyl, and -C-C-COO(H HC CH HC CH or C-C alkyl)), C-Co alkylamino, optionally further Substituted C-C alkoxyalkyl, C-C hydroxyalkyl, H-N N 1 N-H C-Coalkenyl, Substituted C-Coalkenyl groups, C-Co 35 alkoxy-C-C-alkyl groups, C1-Co-oxy-N-C-C-alkyl O O groups, -N-cyclic-C-Cio-alkyl groups, and cyclic-N- HC CH HC CH C-Co-alkyl groups-COR" (where R' is hydrogen, C-C, alkyl, phenyl, and -C-Co. COO(H or C-C alkyl)); and R is hydrogen or C-C alkyl. wherein the polyamide, the pigment of formula (Ib) and the 19. The article as claimed in claim 15, further comprising compound of the formula (XIII) are in the form of a dry 40 a non-inhibiting UV absorber. mixture. 20. The article as claimed in claim 19, wherein the 14. The fluorescent pigment composition as claimed in non-inhibiting UV absorber has a wavelength of less than claim 13, wherein the compound of the formula (XIII) is about 370 nm. present in an amount of 0.05 to 20 percent by weight, 21. The article as claimed in claim 19, wherein the wherein the percent by weight is based upon the weight of 45 non-inhibiting UV absorber has an absorptivity from about the polyamide. 25 L/(g cm) to about 200 L/(g cm). 15. An article comprising: 22. The article as claimed in claim 19, wherein the non-inhibiting UV absorber is selected from the group a) a polyamide, and consisting of Oxanilides, benzyl malonates, Salicylates, b) a pigment of formula (Ib) 50 cinnamates, and triazines. 23. An article comprising: (Ib) a) a polyamide, O H b) a pigment of formula (Ib) C N 55 (Ib) O H N C C N H
60 N C in an amount of less than one percent by weight, wherein H the percent by weight is based upon the weight of the O polyamide, wherein the polyamide and the pigment of formula (Ib) are melt processed. 65 in an amount of less than one percent by weight, wherein the 16. The article as claimed in claim 15, further comprising percent by weight is based upon the weight of the a compound of the formula (II) polyamide, and US 6,683,124 B2 27 c) a compound of the formula (XIII) (III) (XIII) HC CH HC CH HC CH R-N NR3- or H-N N 1 N-H HC O O CH HC CH HC CH (IV) H3C CH3 wherein the polyamide, the pigment of formula (Ib) and the compound of the formula (XIII) are melt processed. R-N NR3 24. The article as claimed in claim 23, wherein the 15 compound of the formula (XIII) is present in an amount of HC 0.05 to 20 percent by weight, wherein the percent by weight dH, O is based upon the weight of the polyamide. 25. A fluorescent pigment composition comprising: a) a polyamide, and wherein for either the formula (III) or the formula (IV): R' b) a pigment of formula (Ia) is independently either hydrogen, C-C alkyl, O, OH, CH, CN, an acetyl group, C-C is alkoxy, (Ia) alkoxyalkylenoxyalky, C-C cycloalkoxy, C-C alkenyl, C7-C phenylalkyl unsubstituted or mono-, di- or tri H Substituted on the phenyl by C-C alkyl, or aliphatic or O N N aromatic C-Co acyl, -COR" (where R" is hydrogen, N n C-C alkyl, phenyl, and -C-C COO(H or C-C, HN N alkyl)), C-Co alkylamino, optionally further Substituted C-C alkoxyalkyl, C-Co hydroxyalkyl, C-Coalkenyl, Substituted C-C alkenyl groups, C1-Co-alkoxy-C-C- alkyl groups, C1-Co-oxy-N-C-Co-alkyl groups, -N-cyclic-C-Cio-alkyl groups, and cyclic-N-C-Cio in an amount of less than one percent by weight, wherein the 35 percent by weight is based upon the weight of the alkyl groups-COR" (where R" is hydrogen, C-C alkyl, polyamide, wherein the polyamide and the pigment of phenyl, and -C-C-COO(H or C-C alkyl)); and R is formula (Ia) are in the form of a dry mixture. hydrogen or C-C alkyl. 26. The fluorescent pigment composition as claimed in claim 25, wherein the amount of the pigment of the formula 40 31. The fluorescent pigment composition as claimed in (Ia) is 0.005 to 0.25 percent by weight. claim 28, wherein the compound of the formula (II) is 27. The fluorescent pigment composition as claimed in Selected from the group consisting of: claim 26, wherein the amount of the pigment of the formula (Ia) is 0.01 to 0.15 percent by weight. 45 (V) 28. The fluorescent pigment composition as claimed in claim 25, further comprising: R-C C-R a compound of the formula (II) (VI) O (II) 50 | C-R
. . . ) and 55 wherein C-R R is a Sterically hindered amino group adjacent to the O carbonyl carbon, and (VIII) O n is 1, 2, 3, or 4. 60 29. The fluorescent pigment composition as claimed in C-R claim 28, wherein the compound of the formula (II) is O present in an amount of 0.05 to 20 percent by weight based R-C upon the weight of the polyamide. C-R 30. The fluorescent pigment composition as claimed in 65 claim 28, wherein in the compound of the formula (II), n=2 O and R is US 6,683,124 B2 29 30 -continued c) a compound of the formula (XIII) (VII) O O | | (XIII) R-C C-R 5 H3C CH3 H3C CH3
R-C C-R H-N ? N-H | | O O O O 1O HC CH HC CH wherein R is a Sterically hindered amino group adjacent to the carbonyl carbon. wherein the polyamide, the pigment of formula (Ia) and the 32. The fluorescent pigment composition as claimed in compound of the formula (XIII) are in the form of a dry claim 28, wherein in the compound of the formula (II), R is mixture. 15 38. The fluorescent pigment composition as claimed in HC CH claim 37, wherein the compound of the formula (XIII) is present in an amount of 0.05 to 20 percent by weight, wherein the percent by weight is based on the weight of the N N-R polyamide. R3 2O 39. An article comprising a) a polyamide, and HC CH b) a pigment of formula (Ia) wherein R' is hydrogen, C-C alkyl, O, OH, CH, CN, an (Ia) acetyl group, C-C alkoxy, alkoxyalkylenoxyalky, C-C2 25 cycloalkoxy, C-C alkenyl, C7-Co phenylalkyl unsubsti H tuted or mono-, di- or tri-Substituted on the phenyl by C-C, O N N alkyl; or aliphatic or aromatic Ci-Coacyl, -COR" (where N N R" is hydrogen, C-C alkyl, phenyl, and -C-C-COO(H HN N or C-C alkyl)), C-C alkylamino, optionally further Substituted C-Co alkoxyalkyl, C-Co hydroxyalkyl, O C-C alkenyl, Substituted C-Coalkenyl groups, C1-Co alkoxy-C-Co-alkyl groups, C1-Co-oxy-N-C-Co-alkyl in an amount of less than one percent by weight, wherein the groups, -N-cyclic-C-Cio-alkyl groups, and cyclic-N- percent by weight is based upon the weight of the 35 polyamide, wherein the polyamide, and the pigment of C-Co-alkyl groups-COR" (where R' is hydrogen, C-C, formula Ia) are melt processed. alkyl, phenyl, and -C-Co. COO(H or C-C alkyl)); and 40. The article as claimed in claim 39, further comprising wherein R is hydrogen or C-C alkyl. a compound of the formula (II) 33. The fluorescent pigment composition as claimed in claim 25, further comprising a non-inhibiting UV absorber. (II) 34. The fluorescent pigment composition as claimed in 40 claim 33, wherein the non-inhibiting UV absorber has a wavelength of less than about 370 nm. 35. The fluorescent pigment composition as claimed in . . . ) claim 33, wherein the non-inhibiting UV absorber has an 45 wherein absorptivity from about 25 L/(g'cm) to about 200 L/(g cm). R is a Sterically hindered amino group adjacent to the 36. The fluorescent pigment composition as claimed in carbonyl carbon, and claim 33, wherein the non-inhibiting UV absorber is selected n is 1, 2, 3, or 4. from the group consisting of Oxanilides, benzyl malonates, 41. The article as claimed in claim 40, wherein the Salicylates, cinnamates, and triazines. compound of the formula (II) is present in an amount of 0.05 37. A fluorescent pigment composition comprising: 50 to 20 percent by weight, wherein the percent by weight is a) a polyamide, based on the weight of the polyamide. 42. The article as claimed in claim 40, wherein in the b) a pigment of formula (Ia) compound of the formula (II), R is (Ia) 55
H ON N N n HN N 60
O wherein R' is hydrogen, C-C alkyl, O, OH, CH, CN, an acetyl group, C-C is alkoxy, alkoxyalkylenoxyalky, Cs-C2 cycloalkoxy, C-C alkenyl, C7-C phenylalkyl unsubsti in an amount of less than one percent by weight, wherein the 65 tuted or mono-, di- or tri-Substituted on the phenyl by C-C, percent by weight is based upon the weight of the alkyl; or aliphatic or aromatic C-Coacyl, -COR" (where polyamide, and R" is hydrogen, C-C alkyl, phenyl, and -C-C-COO(H US 6,683,124 B2 31 32 or C-C alkyl)), C-Co alkylamino, optionally further in a carrier polymer to form a masterbatch, and Substituted C-C alkoxyalkyl, C-C hydroxyalkyl, C-Coalkenyl, Substituted C-Coalkenyl groups, C-Co b) melt processing the masterbatch with a polyamide to alkoxy-C-Cio-alkyl groups, C1-Co-oxy-N-C-C-alkyl form the fluorescent pigment composition. groups, -N-cyclic-C-C-alkyl groups, and cyclic-N- C-Cio-alkyl groups-COR" (where R" is hydrogen, C-C, 46. The process as claimed in claim 45, further compris alkyl, phenyl, and -C-C-COO(H or C-C alkyl)); and ing adding an additive to the masterbatch. R is hydrogen or C-Cs alkyl. 47. The process as claimed in claim 45, further compris 43. An article comprising: ing forming the fluorescent pigment composition into an a) a polyamide, article. b) a pigment of formula (Ia) 48. The process as claimed in claim 47, wherein the article is molded, cast, or extruded. (Ia) 49. The process as claimed in claim 47, wherein the additive is present in the article in an amount of about H 15 0.001% to 0.03% by weight based upon the weight of the O N N article. N n 50. The process as claimed in claim 49, wherein the HN N additive is present in the article in an amount of about 0.005% to 0.03% by weight based upon the weight of the O article. 51. The process as claimed in claim 46, wherein the in an amount of less than one percent by weight, wherein the additive is a non-inhibiting UV absorber having a wave percent by weight is based upon the weight of the length of less than about 370 nm. polyamide, and 52. The process as claimed in claim 46, wherein the c) a compound of the formula (XIII) 25 additive is a compound of the formula (XIII)
HC CH HC CH H3C CH3 H3C CH3
H-N N 1 N-H H-N N c1 N-H O O | HC CH HC CH HC CH HC CH wherein the polyamide, the pigment of formula (Ia) are melt 35 processed and the compound of formula (XIII) are melt 53. The process as claimed in claim 45, further compris processed. ing preparing a Second masterbatch comprised of an additive 44. The article as claimed in claim 43, wherein the in a carrier polymer and adding the Second masterbatch to compound of the formula (XIII) is present in an amount of the polyamide. 0.05 to 20 percent by weight, wherein the percent by weight 40 54. A process of preparing a fluorescent pigment is based upon the weight of the polyamide. composition, the process comprising: 45. A process of preparing a fluorescent pigment composition, the proceSS comprising: a) physically mixing an additive with a compound of the a) incorporating a compound of formula (Ia) formula (Ia) 45 (Ia) (Ia)
H H O N N ON N N n N n HN N HN N
55 or a compound of formula (Ib) or a compound of the formula (Ib) (Ib) (Ib) O O H 60 H C N C N
N C N C H H 65 US 6,683,124 B2 33 34 to form a dry physical mixture, or a compound of formula (Ib) b) adding the dry physical mixture to a polyamide to form (Ib) the fluorescent pigment composition. O 55. The process as claimed in claim 54, wherein the H compound of the formula (Ia) or the compound of the C N formula (Ib) is mixed with the additive in a ratio of com pound to additive of 50:50. N C 56. The process as claimed in claim 54, wherein the H compound of the formula (Ia) or the compound of the formula (Ib) is mixed with the additive in a ratio of com pound to additive of 60:40. 57. The process as claimed in claim 54, wherein the b) obtaining a masterbatch comprising an additive, compound of the formula (Ia) or the compound of the c) letting down the masterbatches independently, and formula (Ib) is mixed with the additive in a ratio of com 15 d) adding the masterbatches to a polyamide to form a pound to additive of 40:60. fluorescent pigment composition. 58. The process as claimed in claim 54, wherein the 67. The process as claimed in claim 66, further compris compound of the formula (Ia) or the compound of the ing forming the fluorescent pigment composition into an formula (Ib) is mixed with the additive in a ratio of com article. pound to additive of 70:30. 68. The process as claimed in claim 67, wherein the article 59. The process as claimed in claim 54, wherein the is molded, cast, or extruded. compound of the formula (Ia) or the compound of the 69. The process as claimed in claim 66, wherein the formula (Ib) is mixed with the additive in a ratio of com additive is a compound of formula (XIII): pound to additive of 30:70. 60. The process as claimed in claim 54, wherein the 25 H3C CH3 H3C CH3 additive is a non-inhibiting UV absorber having a wave length of less than about 370 nm. 61. The process as claimed in claim 54, wherein the H-N No 1 N-H additive is a compound of formula (XIII) | HC CH HC CH H3C CH3 H3C CH3 70. The process as claimed in claim 67, wherein the H-N N c1 N-H additive is present in the article in an amount of about 0.01% 35 to 0.4% by weight based upon the weight of the article. | 71. The process as claimed in claim 70, wherein the HC CH HC CH additive is present in the article in an amount of about 0.05% to 0.3% by weight based upon the weight of the article. 62. The process as claimed in claim 54, further compris 72. A proceSS for making a fluorescent pigment compo ing forming the fluorescent pigment composition into an 40 Sition comprising the Step of adding a compound of formula article. (Ia) 63. The process as claimed in claim 62, wherein the article is molded, cast, or extruded. (Ia) 64. The process as claimed in claim 62, wherein the 45 additive is present in the article in an amount of about H 0.001% to 0.03% by weight based upon the weight of the O N N article. N n 65. The process as claimed in claim 64, wherein the HN N additive is present in the article in an amount of about 0.005% to 0.03% by weight based upon the weight of the 50 article. 66. A process of preparing a fluorescent pigment composition, the proceSS comprising: or a compound of formula (Ib) a) obtaining a masterbatch comprising a compound of 55 formula (Ia) (Ib) O H (Ia) C N
N C H HN N
65 into molten polyamide.
k k k k k