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 s E s ssss555SSs IN U.S. Patent Jan. 27, 2004 Sheet 2 of 19 US 6,683,124 B2 HLIÐS013/03SVÆÐNI, 088 0?8008 INT U.S. Patent Jan. 27, 2004 Sheet 3 of 19 US 6,683,124 B2 s AA l u/ O A. DC L 3 E 2 O s5 s 5 5 S S Sc s SE R Sp S S Se O N U.S. Patent Jan. 27, 2004 Sheet 4 of 19 US 6,683,124 B2 s S3S5ss S s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 5 of 19 US 6,683,124 B2 s C No O O No O fy lf C coH NNQ S 5 Ln SS S2. S O us O O us O CY SgC s s s s O (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 6 of 19 US 6,683,124 B2 s O Lif No O O NO O lf A. d NS Sf 5 SS seCen NNN S O Ln r O O us Co Lif cy SgO s s O (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 7 of 19 US 6,683,124 B2 s 553.S5ss s s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 8 of 19 US 6,683,124 B2 s 5 s s s s5s33ss (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 9 of 19 US 6,683,124 B2 33ss s S. 5 s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 10 of 19 US 6,683,124 B2 3Ss 5 55 s s s s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 11 of 19 US 6,683,124 B2 s O No C O NO O L f C Hom N S CD N ?h SS 2. NS S NN Co Ur us O O N O ur Y O S s s s s O (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 12 of 19 US 6,683,124 B2 3.Ss 5 sS s s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 13 of 19 US 6,683,124 B2 35s 3. s55 s s s s (NO))Sd) U.S. Patent Jan. 27, 2004 Sheet 14 Of 19 US 6,683,124 B2 ?IXWNOISSIWE [[TSNOISSIWE // IIISNOLIWII)X} U.S. Patent Jan. 27, 2004 Sheet 15 of 19 US 6,683,124 B2 00.10890990#9079 079 0 009 00098 00078 0008Z 000WZ 0000Z 000Z| 0008 000; (Sd)) U.S. Patent Jan. 27, 2004 Sheet 16 of 19 US 6,683,124 B2 001 089099 (HBS949 079 009 H10NHTHMWM 089 0990#9 –10079009 00098 00078 0008Z 000WZ º0000Z0009|| 000ZI 0008 000; (Sd)) U.S. Patent Jan. 27, 2004 Sheet 17 of 19 US 6,683,124 B2 Z/ºff (BHS%9 H10NHTHMWM 0010890990#9079009089 099 0000ff), 0000Z 000?I 0008 000ff (Sd)) U.S. Patent Jan. 27, 2004 Sheet 18 of 19 US 6,683,124 B2 00/ 089 099 079 009 H10NHEIMVM 089 099 079 079 0000ff) 0000Z 000ZI (Sd)) U.S. Patent Jan. 27, 2004 Sheet 19 of 19 US 6,683,124 B2 001 089 099 079 079 009 H10NHIBMWM 089 099 079 079 009 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.