Fluorone and pyronin y derivatives

• US 5,451,343 A
• Filed: 11/19/1993
• Issued: 09/19/1995
• Est. Priority Date: 05/20/1991
• Status: Expired due to Fees

• Current Assignee: Spectra Group Limited, Inc. (Formlabs Incorporated)
• Original Assignee: Spectra Group Limited, Inc. (Formlabs Incorporated)
• Inventors: Shi, Jianmin, Neckers, Douglas C.
• Primary Examiner(s): WU, SHEAN CHIU
• Application Number:
  US08/154,880
• Time in Patent Office: 669 Days
• Field of Search: 252/582, 252/589, 430/270, 430/281, 430/345, 430/914, 430/921, 430/923, 430/925
• US Class Current: 252/582
• CPC Class Codes: C07D 311/78 Ring systems having three or more relevant rings
• CPC Class Codes: C07D 311/82 Xanthenes
• CPC Class Codes: C07D 311/84 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08G 59/68 characterised by the catalysts used
• CPC Class Codes: C09B 11/24 Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• CPC Class Codes: C09B 11/28 Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
• CPC Class Codes: G03F 7/028 with photosensitivity-increasing substances, e.g. photoinitiators
• CPC Class Codes: G03F 7/029 Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• CPC Class Codes: G03F 7/031 Organic compounds not covered by group G03F7/029
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0755 Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: Y10S 430/115 Cationic or anionic
• CPC Class Codes: Y10S 430/122 Sulfur compound containing
• CPC Class Codes: Y10S 430/124 Carbonyl compound containing
• CPC Class Codes: Y10S 430/126 Halogen compound containing

Abstract

The present invention relates to a novel class of compounds which absorb light at wavelengths greater than 350 nm and are useful as fluorescers or as photoinitiators. The present invention provides compounds of the formulas (I) and (II) and their equivalents (the nomenclature of the compounds used herein is based on the numbering of positions as shown in formula (I)): ##STR1## where: when W is ═O, W¹ is hydrogen or --OR⁹ and when W is ═NR⁺₂, W is hydrogen or NR₂⁺², A is hydrogen, alkenyl, alkyl or an election withdrawing group, and the remaining groups are as defined in the disclosure.

Claims

1. A photohardenable composition comprising a polymerizable compound and a compound of the formula I or II ##STR13## where R¹, R², R⁵ and R⁶ are the same or different and represent a hydrogen atom or a halogen atom and R¹ and R² can combine to form a ring;

R³ and R⁴ are the same or different and represent a hydrogen atom, a halogen atom, a benzoyl group, a group of the formula --L(CH₂)_n R⁸ where n is 1 to 8, R⁸ is hydrogen, hydroxy, amino, dialkylamino, --COR¹⁶ or --COOR¹⁴ where R¹⁶ is hydrogen, chlorine, COCl, C1-C8 alkyl, NR₂ or aryl and R¹⁴ is hydrogen, C1-C8 alkyl, aryl, COR, 2,4-dinitrophenyl, N-imido or NR₂ and L is a direct bond or >

C═

O, provided that at least two of R¹ -R⁶ are iodo or bromo;

W is ═

O or ═

NR₂ +Z-- where R is hydrogen or lower alkyl, Z is a counter ion, when W is ═

O, W¹ is hydrogen or --OR⁹ where R⁹ is hydrogen, C1-C8 alkyl, acyl or a group of the formula --(CH₂)_n R¹⁰ where n is 1 to 8 and R¹⁰ is amino, dialkylamino, hydroxy, acryloyl or methacryloyl and when W is ═

NR₂ +Z--, W¹ is hydrogen or --NR₂ ;

Y is oxygen, sulfur, selenium, tellurium, >

C═

O, or N--R¹³ where R¹³ is 4-methylphenyl, A is hydrogen, alkenyl, alkyl, or an electron withdrawing group (EWG) selected from the group consisting of COOR¹¹, COR¹², C(O)OCOR¹¹, CONR₂, CN, NO₂, NCS, NCO, SO₂ R¹², SO₃ R¹¹, SO₂ NR₂, CX₃² ;

R¹¹ is hydrogen, alkyl, aryl, or aralkyl R¹² is hydrogen, alkyl, aryl, or aralkyl, X² can be the same or different and is a halogen atom.

2. The composition of claim 1 wherein said compound is represented by the Formula (I).

3. The composition of claim 2 wherein said compound is represented by the Formula (III) or (IV) ##STR14## where Y¹ is oxygen, sulfur or >

NR¹³.

4. The composition of claim 3 wherein X¹ is 0.

5. The composition of claim 4 wherein said compound is represented by the Formula (III).

6. The composition of claim 5 wherein A is hydrogen.

7. The composition of claim 5 wherein A is CN.

8. The composition of claim 5 wherein said composition includes a coinitiator capable of accepting an electron from or donating an electron to said compound.

9. The composition of claim 8 wherein said conitiator is N-phenylglycine or an N,N-dialkylaniline.

10. The composition of claim 9 wherein said compound is selected from the group consisting of

5,7-diiodo-3-methoxy-6-fluorone (DIMF),

5,7-diiodo-3-ethoxy-6-fluorone (DIEF),

5,7-diiodo-3-butoxy-6-fluorone (DIBF),

5,7-diiodo-3-octoxy-6-fluorone (DIOF),

4,5-diiodo-3-hydroxy-6-fluorone,

9-cyano-5,7-diiodo-3-methoxy-6-fluorone (CDIMF),

9-cyano-5,7-diiodo-3-ethoxy-6-fluorone (CDIEF),

9-cyano-5,7-diiodo-3-butoxy-6-fluoorone (CDIBF),

9-cyano-5,7-diiodo-3-octoxy-6-fluorone (CDIOF),

3-hydroxy-2,4,5,7-tetraiodo-6-fluorone (TIHF),

3-hydroxy-2,4,5,7-tetrabromo-6-fluorone (TBHF),

3-hydroxy-2,4,5,7-tetrachloro-6-fluorone (TCHF),

3-hydroxy-2,4,5,7-tetrafluoro-6-fluorone (TFHF),

9-cyano-3-hydroxy-2,4,5,7-tetraiodo-6-fluorone (TIHCF),

9-cyano-3-hydroxy-2,4,5,7-tetrabromo-6-fluorone (TBHCF),

9-cyano-3-hydroxy-2,4,5,7-tetrachloro-6-fluorone (TCHCF),

9-cyano-3-hydroxy-2,4,5,7-tetrafluoro-6-fluorone (TFHCF),

3-hydroxy-4,5,7-triiodo-2octanoyl-6-fluorone,

9-cyano-3-hydroxy-4,5,7-triiodo-2-octanoyl-6-fluorone,

3-hydroxy-4,5,7-triiodo-2-octanoyl-6-fluorone,

9-cyano-3-hydroxy-4,5,7-triiodo-2-octyl-6-fluorone,

3-hydroxy-2,4,5,7-tetraiodo-6-thiafluorone,

3-hydroxy-4,5,7-triiodo-2-pentanoyl-6-fluorone,

9-cyano-3-hydroxy-4,5,7-triiodo-2-pentanoyl-6-fluorone,

3-hydroxy-4,5,7-triiodo-2-pentyl-6-fluorone,

9-cyano-3-hydroxy-4,5,7-triiodo-2-pentyl-6-fluorone,

2,7-di-t-butyl-4,5-diiodo-3-hydroxy-6-fluorone,

9-cyano-2,7-di-t-butyl-4,5-diiodo-3-hydroxy-6-fluorone,

7-benzoyl-2,4,5-triiodo-3-hydroxy-6-fluorone,

9-cyano-3-hydroxy-7-butyroyl chloride-6-fluorone.

11. The composition of claim 10 wherein said composition additionally includes an onium salt.

12. The composition of claim 11 wherein said composition includes a diphenyliodonium salt.

13. The composition of claim 5 wherein R¹⁰ is acryloyl or methacryloyl.