WO2006023687A2 - Ultraviolet light (uv) absorbing compounds and compositions containing uv absorbing compounds - Google Patents
Ultraviolet light (uv) absorbing compounds and compositions containing uv absorbing compounds Download PDFInfo
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- WO2006023687A2 WO2006023687A2 PCT/US2005/029482 US2005029482W WO2006023687A2 WO 2006023687 A2 WO2006023687 A2 WO 2006023687A2 US 2005029482 W US2005029482 W US 2005029482W WO 2006023687 A2 WO2006023687 A2 WO 2006023687A2
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- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Cosmetics (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800340089A CN101035848B (en) | 2004-08-20 | 2005-08-18 | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
JP2007528031A JP4926062B2 (en) | 2004-08-20 | 2005-08-18 | Ultraviolet (UV) absorbing compound and composition containing UV absorbing compound |
BRPI0514471-0A BRPI0514471B1 (en) | 2004-08-20 | 2005-08-18 | ULTRAVIOLET (UV) LIGHT ABSORBENT COMPOUNDS AND COMPOSITIONS CONTAINING UV ABSORBENT COMPOUNDS |
EP05791413.7A EP1814939B1 (en) | 2004-08-20 | 2005-08-18 | Ultraviolet light (uv) absorbing compounds and compositions containing uv absorbing compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/922,734 | 2004-08-20 | ||
US10/922,734 US7381762B2 (en) | 2004-08-20 | 2004-08-20 | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2006023687A2 true WO2006023687A2 (en) | 2006-03-02 |
WO2006023687A3 WO2006023687A3 (en) | 2006-12-21 |
Family
ID=35910489
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/029482 WO2006023687A2 (en) | 2004-08-20 | 2005-08-18 | Ultraviolet light (uv) absorbing compounds and compositions containing uv absorbing compounds |
Country Status (6)
Country | Link |
---|---|
US (1) | US7381762B2 (en) |
EP (1) | EP1814939B1 (en) |
JP (1) | JP4926062B2 (en) |
CN (1) | CN101035848B (en) |
BR (1) | BRPI0514471B1 (en) |
WO (1) | WO2006023687A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009528439A (en) * | 2006-03-03 | 2009-08-06 | ディーエスエム アイピー アセッツ ビー.ブイ. | Heterocyclic substituted novel condensation polymers |
CN107033730A (en) * | 2011-02-07 | 2017-08-11 | 威士伯采购公司 | Container and other product coating compositions and coating method |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7691918B2 (en) * | 2006-10-13 | 2010-04-06 | Alcon, Inc. | Intraocular lenses with unique blue-violet cutoff and blue light transmission characteristics |
TWI435915B (en) * | 2007-08-09 | 2014-05-01 | Alcon Inc | Ophthalmic lens materials containing chromophores that absorb both uv and short wavelength visible light |
TW200916531A (en) * | 2007-08-09 | 2009-04-16 | Alcon Inc | Ophthalmic lens materials containing chromophores that absorb both UV and short wavelength visible light |
MX2010013530A (en) * | 2008-06-20 | 2010-12-21 | Basf Se | Agrochemical formulations comprising a pesticide, an organic uv-photoprotective filter and coated metal-oxide nanoparticles. |
TWI453199B (en) | 2008-11-04 | 2014-09-21 | Alcon Inc | Uv/visible light absorbers for ophthalmic lens materials |
JP5597647B2 (en) | 2008-12-30 | 2014-10-01 | ノバルティス アーゲー | Trifunctional UV absorbing compound and use thereof |
JP2012520259A (en) * | 2009-03-13 | 2012-09-06 | ビーエーエスエフ ソシエタス・ヨーロピア | Composition comprising a pesticide and a benzotriazole UV absorber |
WO2011053995A1 (en) * | 2009-11-02 | 2011-05-05 | Inolex Investment Corporation | Uv absorbing complex polyester polymers, compositions containing uv absorbing complex polyester polymers, and related methods |
US9125411B2 (en) | 2010-04-15 | 2015-09-08 | Basf Se | UV absorbers for reducing the E/Z isomerization of pesticides |
MY158272A (en) | 2010-12-13 | 2016-09-30 | Novartis Ag | Ophthalmic lenses modified with functional groups and methods of making thereof |
JP5731452B2 (en) * | 2012-08-10 | 2015-06-10 | シプロ化成株式会社 | Novel benzotriazole derivative compound and water-soluble ultraviolet absorber containing the same |
JP2015042698A (en) * | 2013-08-26 | 2015-03-05 | 三菱樹脂株式会社 | Biaxially oriented polyester film |
US10717714B2 (en) | 2017-07-07 | 2020-07-21 | Chitec Technology Co., Ltd. | Reactive ultraviolet absorber and application thereof |
TWI680975B (en) * | 2018-06-26 | 2020-01-01 | 奇鈦科技股份有限公司 | Uv absorbing compound and applications thereof |
CN112752793B (en) * | 2018-07-30 | 2024-01-30 | 奥升德功能材料运营有限公司 | Nylon terpolymer |
CN111058146B (en) * | 2018-10-17 | 2022-06-10 | 东丽纤维研究所(中国)有限公司 | Woven fabric with heterochromatic effect and application thereof |
JPWO2020162592A1 (en) * | 2019-02-08 | 2021-11-04 | 三井化学株式会社 | Polymerizable compositions for optical materials, optical materials and their uses |
JP7362049B2 (en) * | 2019-11-14 | 2023-10-17 | 国立大学法人福井大学 | Benzotriazole copolymer and ultraviolet absorber using the same |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4853471A (en) | 1981-01-23 | 1989-08-01 | Ciba-Geigy Corporation | 2-(2-Hydroxyphenyl)-benztriazoles, their use as UV-absorbers and their preparation |
DE3264154D1 (en) | 1981-01-23 | 1985-07-25 | Ciba Geigy Ag | 2-(2-hydroxyphenyl)-benzotriazoles, their use as ultraviolet stabilizers and their preparation |
DE3475617D1 (en) * | 1983-07-26 | 1989-01-19 | Ciba Geigy Ag | Compounds which can be copolymerised |
JPH064601B2 (en) | 1987-11-04 | 1994-01-19 | 三井石油化学工業株式会社 | Method for purifying N-cyano-N'-methyl-N "-[2-{(5-methyl-1H-imidazol-4-yl) methylthio} ethylguanidine |
US5459222A (en) | 1993-06-04 | 1995-10-17 | Ciba-Geigy Corporation | UV-absorbing polyurethanes and polyesters |
US5585228A (en) | 1994-11-30 | 1996-12-17 | Eastman Kodak Company | Benzotriazole based UV absorbing compounds and photographic elements containing them |
IT1275534B (en) * | 1995-07-14 | 1997-08-07 | Pirelli | VULCANIZABLE RUBBER MIXTURE FOR TIRES OF VEHICLE TIRES |
US5994431A (en) | 1996-05-03 | 1999-11-30 | 3M Innovative Properties Company | Amide functional ultraviolet light absorbers for polyolefins |
US6291586B2 (en) | 1996-05-03 | 2001-09-18 | 3M Innovative Properties Company | Amide functional ultraviolet light absorbers for polyurethanes and polyureas |
US5962683A (en) * | 1996-06-28 | 1999-10-05 | Ciba Specialty Chemicals Corp. | Oxazoline compounds as stabilizers |
CZ14299A3 (en) | 1996-07-18 | 1999-04-14 | Ciba Specialty Chemicals Holding Inc. | Triazine, benzotriazine and benzophenone derivatives being substituted and bridged by polyoxyalkylene intended for use as uv absorbers |
JP3714574B2 (en) | 1997-03-26 | 2005-11-09 | ダイセル化学工業株式会社 | Ultraviolet absorber, method for producing the same and synthetic resin composition |
US6268415B1 (en) * | 1999-05-03 | 2001-07-31 | Ciba Specialty Chemicals Corporation | Stabilized adhesive compositions containing highly soluble, photostable benzotriazole UV absorbers and laminated articles derived therefrom |
JP3425588B2 (en) | 2000-04-06 | 2003-07-14 | 大塚化学ホールディングス株式会社 | Recording medium with excellent weather resistance, water resistance and visibility |
US6566507B2 (en) * | 2000-08-03 | 2003-05-20 | Ciba Specialty Chemicals Corporation | Processes for the preparation of benzotriazole UV absorbers |
US6307055B1 (en) | 2000-12-27 | 2001-10-23 | Council Of Scientific And Industrial Research | Diol-functionalized UV absorber |
-
2004
- 2004-08-20 US US10/922,734 patent/US7381762B2/en active Active
-
2005
- 2005-08-18 EP EP05791413.7A patent/EP1814939B1/en active Active
- 2005-08-18 JP JP2007528031A patent/JP4926062B2/en active Active
- 2005-08-18 CN CN2005800340089A patent/CN101035848B/en active Active
- 2005-08-18 BR BRPI0514471-0A patent/BRPI0514471B1/en active IP Right Grant
- 2005-08-18 WO PCT/US2005/029482 patent/WO2006023687A2/en active Application Filing
Non-Patent Citations (2)
Title |
---|
None |
See also references of EP1814939A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009528439A (en) * | 2006-03-03 | 2009-08-06 | ディーエスエム アイピー アセッツ ビー.ブイ. | Heterocyclic substituted novel condensation polymers |
US8951509B2 (en) | 2006-03-03 | 2015-02-10 | Dsm Ip Assets B.V. | Heterocyclic substituted condensation polymers |
CN107033730A (en) * | 2011-02-07 | 2017-08-11 | 威士伯采购公司 | Container and other product coating compositions and coating method |
Also Published As
Publication number | Publication date |
---|---|
EP1814939A4 (en) | 2009-07-29 |
JP4926062B2 (en) | 2012-05-09 |
US7381762B2 (en) | 2008-06-03 |
US20060041038A1 (en) | 2006-02-23 |
EP1814939A2 (en) | 2007-08-08 |
JP2008510718A (en) | 2008-04-10 |
BRPI0514471A (en) | 2008-06-10 |
EP1814939B1 (en) | 2017-10-04 |
CN101035848B (en) | 2010-12-29 |
BRPI0514471B1 (en) | 2021-10-13 |
WO2006023687A3 (en) | 2006-12-21 |
CN101035848A (en) | 2007-09-12 |
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